2007

2008

2009

An Overview of the Library Resources for the Students of Chemistry

Chris Jocius, Reference Library, MS&T

 

Microalgase-Based Bioremediation and Biofuels

Paul K. Nam, Dept. of Chem., MS&T

Abstract: Aquatic microalgae are photosynthetic microorganisms that have great potential to be the solution to growing energy and environmental challenges, as more practical and environmentally benign methods for renewable biofuel production, carbon dioxide sequestration and wastewater remediation. Multidisciplinary collaborative research is conducted to develop economical and environmentally-sustainable technologies for microalgae that utilize carbon dioxide and wastewater as nutrient sources and yield algal biomass that can be converted to biofuels. Unicellular microalgae are fast growing and efficient converters of solar energy and carbon dioxide, thereby producing many times the biomass per unit area of land when compared to terrestrial plants. We have established a collection of microalgae species, specifically native species that adapt well to local environmental conditions and can resist the invasion by undesirable species. Cultivation conditions for the maximum production of algal biomass and target biochemicals have been investigated. Efficient techniques for harvesting and dewatering algal biomass are developed in the lab and tested for the field application. A pilot open-pond cultivation system that can utilize carbon dioxide in the flue gas generated from a coal-fired power plant is constructed for the demonstration of large-scale (10,000 gallons) algae cultivation and harvesting processes. Supercritical catalyst-free transesterification reaction is evaluated for the efficient production of biodiesel from oil-bearing crops including microalgae. Improved methods for pretreatment and hydrolysis of microalgae as cellulosic ethanol feedstock are also being investigated. Ultimately, these innovations will contribute in the development of an integrated self-supported system/process that incorporates the microalgae cultivation process with bio-refinery that is dedicated to algae-based biofuels and products. 

 

Assemblies of Nanoparticles as 3D Scaffols for New Materials: from Mechanically Strong Polymer Crosslinked Aerogels to Porous Iron and Silicon Carbide

Nicholas Leventis, Dept. of Chem., MS&T

Abstract: Monolithic, low-density 3-D assemblies of nanoparticles, known as aerogels, are pursued for unique properties above and beyond those of their individual building blocks. Specifically, since those materials are characterized by large internal void space (>80% v/v) they demonstrate low thermal conductivity, low dielectric constants and high acoustic impedance. The most common type of aerogels are based on silica and they are environmentally sensitive (hydrophilic, fragile) limiting their practical applications in certain nuclear reactors as Cherenkov radiation detectors, as devices for capture of hypervelocity particles in space (NASA’s Stardust Program), and as thermal insulation of electronic boxes aboard planetary vehicles such as the Sojourner Rover on Mars (1997), and the two Mars Exploration Rovers Spirit and Opportunity (2004).

The fragility problem of silica aerogels is traced to well-defined weak points in their skeletal framework, the interparticle necks.  Using the surface functionality of the inorganic nanoparticles as a focal point, we have directed attachment of a conformal polymer coating over the entire skeletal framework, bridging the nanoparticles and rendering all necks wider [1,2]. Thus, although the bulk density may increase by a factor of 3 (still an ultra-lightweight material), the mesoporosity (pores in the range 2-50 nm) remains almost unchanged, while the strength of the material can increase by up to a factor of 300 above the strength of the underlying inorganic framework. In that regard, polymer crosslinked aerogels may combine a multiple of the specific compressive strength of carbon fiber reinforced composites with the thermal conductivity of styrofoam. The crosslinked aerogel technology has been demonstrated with several different polymers such as polyurethanes/polyureas, epoxies and polyolefins, while ~35 different metal and semimetal sol-gel oxides from the periodic table have been crosslinked successfully yielding a combination of structural, magnetic and optical properties.  Currently polymer crosslinked aerogels are evaluated as starting materials for the carbothermal synthesis of carbide and pure metal aerogels [3,4], while applications being explored include thermal and acoustic insulation, ballistic protection (armor), membranes for use in separation technology, dielectrics and supports for catalysts.

Energy Conservation Awareness Activities in Schrenk Hall

Sasidhar Siddabattuni, Dept. of Chem., MS&T

 

Transparent Conductors: From Basic Principles to Controllable Properties

Dr. Julia Medvedeva, Dept. of Physics, MS&T

Abstract: Many optoelectronic technologies, including photovoltaic cells, flat panel displays, organic light-emitting diodes and energy-efficient windows, require materials which possess a unique combination of two seemingly contradictory properties - optical transparency and electrical conductivity. Such a combination is attained in a few oxides - doped In2O3, ZnO, CdO and SnO2.

Here, we summarize the key electronic features essential for achieving good carrier transport while maintaining sufficient optical transmission in a typical transparent conducting oxide (TCO). The role of the following factors governing the electrical and optical properties is discussed: (i) the local and long-range crystal symmetry; (ii) the electronic configuration of the cations; and (iii) the carrier generation mechanism employed. The results not only provide microscopic insight into the underlying phenomena in conventional TCOs but also serve as a solid foundation for further search for efficient transparent conductors beyond those traditionally employed.

 

 

Investigation of Pharmaceuticals and Personal Care Products in Missouri Natural and Drinking Water Using LC-MS/MS

Chuan Wang, Dept. of Chem., MS&T

Abstract: The trace amount of pharmaceuticals and personal care products (PPCPs) in natural waters has dramatic effects on the aquatic environment. Furthermore, the PPCPs in surface water may also have possible health impacts on humans because surface water is used as drinking water after treatment by water treatment facilities.  Therefore, the analysis of pharmaceuticals and personal care products in natural and treated waters become very important to provide information about the removal of PPCPs in drinking water and waste water treatment processes.

In this presentation, a comprehensive method has been developed and validated in two different water matrix for the analysis of sixteen important PPCPs by a single solid phase extraction (SPE) of 0.25 L water sample followed by analysis using liquid chromatography coupled with tandem mass spectrometry. Sixteen compounds which representing antibiotics, hormones, analgesics, stimulants, antiepileptic and X-ray contrast media were analyzed in both untreated and treated drinking waters. Water samples were collected from 34 different water treatment facilities across Missouri in both winter and summer seasons. The method detection limit for these compounds ranged from 1 to 20 ng/L. The details about method development, method validation, occurrence data, quality assurance and the trend of the PPCPs in different types of water and seasons will be discussed.  In addition, the treatability of PPCPs by free chlorine will also be presented.

 

Synthesis and Fluoride Anion Binding Studies of Fluorinated Boron-Based Anion Receptors

Nanditha G. Nair, Dept. of Chem., MS&T

Abstract: A series of fluorinated boron based anion receptors were synthesized and their fluoride ion binding was studied using spectroscopic techniques. Structures of the fluorinated boroxines, tris(2,6-difluorophenyl)-boroxin (DF), tris(2,4,6-trifluorophenyl)boroxin (TF), and tris(pentafluorophenyl)boroxin (PF), and boroxin-fluoride complexes have been confirmed by comparing their 19F and 11B NMR chemical shifts with those obtained by DFT-GIAO method and also by mass spectroscopic studies.

The stoichiometry of the fluoride anion binding to these boroxines has been shown to be 1:1 using 19F NMR, UV-vis spectroscopy. Further confirmation was obtained by mass spectroscopic studies for DF. UV-vis spectroscopic studies show the co-existence of more than one complex, in addition to 1:1 complex, for perfluorinated boroxin, PF. DFT calculations (B3LYP/6-311G**) show that the fluoride ion complex of DF prefers unsymmetrical, covalently bound structure over the symmetrically bridged species  by 12.5 kcal/mol.

Analysis and Occurrence of Disinfection By-Products in Fresh and Salt Water

Honglan Shi, Dept. of Chem., MS&T

Abstract: Haloacetic acids (HAAs), trihalomethanes (THMs), and bromate are toxic water disinfection by-products (DBPs) that US Environmental Protection Agency regulated in drinking water.  Iodoacetic acids, halonitromethanes (HNMs) are the emerging DBPs that have been recently found in the disinfected drinking waters with much higher toxicity than the regulated DBPs at the same concentrations.  This seminar will present our new rapid and sensitive methods [1] for the analysis of these DBPs, the occurrence screening study of the DPBs in 34 Missouri drinking water treatment systems, occurrence and formation studies of these DBPs in seawater/saltwater based aquaria in the SeaWorld Parks.  Several types of State-of-the-Arts analytical instrumentations were used to perform the experiments, including ion chromatography-inductively couple plasma/mass spectrometry (IC-ICP/MS), liquid-liquid extraction followed by gas chromatography-mass spectrometry (LLE-GC-MS), and solid phase microextraction (SPME)-GC-MS.  The highly cytotoxic and genotoxic emerging HNMs were detected in most of the Missouri drinking waters with the concentrations in the range from non-detectable to 6.71 µg/L, within the range of the national wide screening studies (up to 10 µg/L).  All of these DBPs were formed in the aquaria of SeaWorld Parks at much higher concentrations than those in the drinking water.  These DBPs are not only harmful to the SeaWorld Park workers and marine animals; they may also be the major causes of the eye irritation problems in the SeaWorld Park aquaria [2].

Determination and Quantification of 2-Hydroxy(Methylthio)4-Butanoic Acid and Pantothenic Acid in Bovine Serum and Sea Water Using RPLC, ESI-MS, LC-MS, and the Tandem MSDetoxification of Jatropha Curcas Oil and Meal: Characterization and Quantification of Phorbol Esters a Toxic Component of Jatropha Curcas

Balaji Viswanathan, Dept. of Chem., MS&T

 

Mesoscopic Physics of Photons: Particle Versus Wave Trasport Through Random Media

Dr. Alexey Yamilov, Dept. of Physics, MS&T

Abstract: The term mesoscopic physics refers to a wide range of quantum (or, more precisely, interference) phenomena which occur in solids between the macroscopic and microscopic size. Quantum or not, the interferencephenomena are common to waves of any nature, including the electromagnetic waves. I will explore the similarities and differences between mesoscopic electronic transport and  the light propagation in disordered media. In particular, I will discuss an exciting possibility of coherent amplification of photons which adds a new dimension to the fundamental study of mesoscopic transport and leads to a new physical phenomenon - random lasing.

 

 

Traditional and Non-traditional Chemistry Careers

Lisa Balbes, ACS Career Personnel

Abstract: A chemistry background prepares you for much more than just a laboratory career. The broad science education, analytical thinking, research methods, and other skills learned are of value to a wide variety of types of employers, and essential for a plethora of types of positions. By understanding your own personal values and interests, you can make informed decisions about what career paths to explore, and identify positions that match your needs. This talk will discuss a  variety of traditional and nontraditional careers for chemists, including positions in industry, academia and government,  chemical information, patent work, technical writing, education, human resources, sales and marketing, and much more. We will discuss typical tasks, education or training requirements, and personal characteristics that make for a successful career in each field, illustrated with specific examples. Valuable tips and advice about planning career transitions will also be provided.

 

Dynamics of Polymers at Interfaces using TMDSC and Deuterium NMR

Boonta Hetayothin, Dept. of Chem., MS&T

Abstract: The effect of molecular mass on the adsorption of poly(methyl methacrylate) (PMMA) on silica was determined by using temperature-modulated differential scanning calorimetry (TMDSC). A two-component model, based on loosely-bound polymer with a glass transition temperature (Tg) similar to that of bulk polymer and more tightly-bound polymer with a Tg higher than that of the loosely bound polymer, was used to interpret the thermograms. PMMA (with a high and medium molecular masses of 450 kDa and 85 kDa, respectively) had similar amounts of tightly bound polymer (approximately 0.78 mg/m2) adsorbed on the surface of silica with a corresponding thickness of about 0.65 nm.The low molecular mass, 32 kDa PMMA, had a smaller amount of tightly bound polymer (about 0.48 mg/ m2) adsorbed on the silica surfaces, corresponding to a thickness of 0.40 nm. The ratios of heat capacity increments of the loosely bound and tightly bound components (ΔCpA/ΔCpB) in the glass transition regions, indicating the relative mobility of the two components, were also estimated.  

A study of the effect of functional groups on adsorbed polymers, such as poly(methyl methacrylate) (PMMA), poly(vinyl acetate) (PVAc) and poly(methyl acrylate) (PMA) on silica surfaces, was also determined using TMDSC. In this study, polymers of high molecular mass (200-450 kDa) were used. The results showed little difference in the amount of the tightly bound component for adsorbed PMMA and PVAc on silica (0.78 mg/m2), while the amount of the tightly bound in adsorbed PMA on silica showed less, but not significantly different (0.72 mg/m2) amounts.  These tightly bound amounts of polymers adsorbed on the silica surfaces corresponded to the thicknesses of about 0.65 nm for PMMA and PVAc and 0.60 nm for PMA.  

The dynamic behavior of a plasticizer that affects bulk and adsorbed PVAc on silica was also studied using deuterium NMR (2H NMR). This study probed the effect of plasticizer on small adsorbed amounts of polymer (PVAc) on silica (approximately 0.8 mg polymer/m2silica). The deuterated plasticizer, dipropylene glycol dibenzoate (DPGDB-d10), was synthesized and used as a plasticizer for PVAc. Bulk PVAc and adsorbed PVAc on silica were prepared with approximately 10% and 25% plasticizer and used for this study. The changes of the lineshape of 2H NMR spectra suggested that, as the temperature increased the motion of the polymer segments also increased, and was even more pronounced in the presence of plasticizer. Additionally, the relaxation times of both pure deuterated plasticizer (DPGDB-d10) and plasticized bulk PVAc were observed.

 

2010

Plagiarism: Using Sources Responsibly

Daniel Reardon, Assistant Director, Writing Center, MS&T

Abstract: Integrating sources logically and responsibly is the first order of professional research for all scientists and technologists.  First, in order to do research, we must thoroughly understand work in our own fields; that work will inform, guide, and direct our own.  Researching the ideas of others has become more and more difficult in our present age, however.  In our information fluid age, when vast amounts of data are easily accessible and quickly changed, we have now, more than ever, a moral and ethical responsibility to honestly and properly acknowledge the ideas of others that have influenced our own.  It is all too easy, however, to copy, whether deliberately or unintentionally, ideas or portions of text without properly citing the sources of this information.  This type of copying—plagiarism—demonstrates incompetence. If we fail to record our sources and then later forget that we used those sources, we are still liable and open to the charge of theft of intellectual property.  By learning to properly and at all times, regardless of medium, record where we obtain ideas—whether we use them or not—we will maintain professional integrity with everything we write.  This presentation will offer several key principles and strategies for responsible research documentation and plagiarism avoidance.

 

Repair of the Flawed Introduction of Chemical Potential into Thermodynamics

Gary L. Bertrand, Dept. of Chem., MS&T

 

Investigating Antioxidant Chelation for the Treatment of Lead Poisioning

Weiqing Chen, Dept. of Biological Sciences, East China Normal University, Shanghai, China

Abstract: The toxic effects of lead have been manifested as inducements of imbalance between pro-oxidant and antioxidant homeostasis and high affinities for thiol groups in the functional proteins.  Prior in vivo studies on the treatment of lead poisoning using EDTA, N-acetylcysteine (NAC) and N-acetylcysteine amide (NACA) as chelators showed differences in their ability to decrease both Pb(II) levels and oxidative stress.  This present study, performed in vitro, was undertaken to further delineate their chelating abilities.  Pb-antioxidant complexations were performed at 0-10° C, dissolving antioxidant and Pb acetate in deionized, distilled water.  UV-vis spectroscopy was used to investigate the binding interactions of Pb with these antioxidants in solution while X-ray photoelectron spectroscopy (XPS) was used to quantify the amount of Pb bound to the antioxidant.  Job’s Method plots obtained from UV data revealed 1:1, 1:2.5 and 1:1.5 stoichiometric ratios for EDTA:Pb, NAC:Pb and NACA:Pb coordination, respectively.  Deconvolution of the XPS Pb 4f orbitals indicated a greater amount of covalently bound Pb(II) accompanying Pb-NACA complexation as compared to the formation of Pb-NAC and Pb-EDTA.  In comparing Pb coordination to NAC and NACA, the increase in the amount of Pb bound to the antioxidant in the XPS data correlated with differences in their point of zero charge (PZC) values.  Insights into the binding of Pb to this series of antioxidants will be discussed.

 

NMR Investigations of Hydrothermal Liquefaction of Biomass

Wenjia Zhang, Dept. of Chem., MS&T

Abstract: Hydrothermal liquefaction of cellulosic biomass to synthetic fuel has gained considerable attention for it is conducted in aqueous solution at temperatures and pressures significantly lower compared with biomass pyrolysis or gasification. To elucidate the mechanisms of hydrothermal carbonization, the hydrothermal reaction of D-glucose as a moel substrate was examined using quantitative analysis of 1H, 13C and two-dimensional NMR. For the investigation, we have developed and optimized a new presaturation sequence (EXCEPT = EXponentially Converging Eradication Pulse Train) to suppress the water 1HNMR signal.The studies confirm that D-glucose is first dehydrated in aqueous solutions to 5-hydroxymethylfurfural (5-HMF) and subsequently re-hydrated to 4-oxopentanoic acid (levulinic acid). The invesigation also reveals the formation of other compounds, some of which are yet unidentified. 

 

An Approach to Binary Radiation Therapy Mediated by Neutron Capture

M. Frederick Hawthorne, University of Missouri

 

 

An Overview of Environmental Regulations for the Chemist

Dennis L. Whitney, Environmental Engineer, American Airlines, Retired

Abstract: Since the National Environmental Policy Act was passed and signed by President Richard Nixon in 1969, a large number of environmental laws have been enacted. The major laws that affect the chemical community are the Resource Conservation and Recovery Act, RCRA, the Clean Water Act, the Comprehensive Environmental Response Comprehensive Liability Act, CERCLA, also know as the Superfund Act, and the Superfund Amendments and Reauthorization Act know as SARA Title III, and the Clean Air Act. There have also been other laws that regulate petroleum spills, asbestos management, toxic chemicals regulated by the Toxic Substances Control Act, the management of nuclear (radioactive) waste, the transportation of hazardous wastes, and the cleanup of hazardous waste spills. There are also regulations concerning the safety of chemical workers published by the Occupational Safety and Health Administration.

Chemical students and professionals at all levels should be aware of the nature of these laws because, in many cases, they may be held personally, and sometimes criminally, liable for damages that may occur due to non-compliance.

 

 

Oxidative Stress in HIV-Associated Dementia

Dr. Atrayee Banerjee, Dept. of Chem., MS&T

Abstract: An increased risk of HIV-1 associated dementia (HAD) has been observed in patients abusing methamphetamine (METH). Since both HIV viral proteins (gp120, Tat) and METH induce oxidative stress, drug abusing patients are at a greater risk of oxidative stress-induced damage. The objective of this study was to determine if N-acetylcysteine amide (NACA) protects the blood brain barrier (BBB) from oxidative stress-induced damage in animals exposed to gp120, Tat and METH. To study this, CD-1 mice pre-treated with NACA/saline, received injections of gp120, Tat, gp120 + Tat or saline for 5 days, followed by three injections of METH/saline on the fifth day, and sacrificed 24 h after the final injection. Various oxidative stress parameters were measured, and animals treated with gp120+Tat+Meth were found to be the most challenged group, as indicated by their GSH and MDA levels. Treatment with NACA significantly rescued the animals from oxidative stress. Further, NACA-treated animals had significantly higher expression of tight junction (TJ) proteins and BBB permeability as compared to the group treated with gp120+Tat+METH alone, indicating that NACA can protect the BBB from oxidative stress-induced damage in gp120, Tat and METH exposed animals, and thus could be a viable therapeutic option for patients with HAD.         

HAART Drugs Induce Cytotoxicity Via Oxidative Stress and Mitochondrial Dysfunction in Blood-Brain Barrier Cells

Kalyan Manda, Dept. of Chem., MS&T

Abstract: The blood–brain barrier (BBB) is a diffusion barrier which selectively regulates the flow of molecules from blood to the brain.  Dysfunction of the BBB that was observed in the course of HIV infection has been confirmed by variety of pathological studies. Alterations in the barrier function of the brains endothelium have also been implicated in HIV-1-associated neurocognitive disorders (HAND) as well as other neurological disorders like multiple sclerosis and Alzheimer’s disease.

The era of highly active antiretroviral therapy (HAART) has led to a considerable decline in new cases of a severe form of HAND, called HIV-1-associated dementia (HAD). However there has been a significant increase in the number of existing cases with a milder form of HAND.  In view of these developments, we hypothesized that HAART drugs may induce oxidative stress in the BBB thereby exacerbating the condition. Exposure of human blood brain endothelial cells (hCMEC/D3) to a combination of two HAART drugs, Zidovudine (3’-azido-2’,3’-deoxythymidine; AZT) and indinavir (IDV) significantly reduced viability after a 72 hr treatment, in a dose-dependent manner. Oxidative stress parameters like glutathione (GSH) and malondialdehyde (MDA) were found to be significantly altered after exposure. Loss of mitochondrial membrane potential (Ψm) assessed using fluorescent microscopy and decreased ATP levels revealed that cytoxicity was mediated through mitochondrial dysfunction. Permeability of dextran and measurement of trans-endothelial electrical resistance (TEER) across a monolayer of cells indicated that the integrity of BBB was compromised after the treatment. The results from our studies suggest that treatment with AZT + IDV may oxidatively challenge the BBB during antiretroviral therapy via mitochondrial dysfunction, thereby altering the functionality of this layer.

Control and Design of Structural Variations in Nickel Trimer Complexes

Carla Schmiesing, Dept. of Chem., MS&T

 

Electrodeposition of Superlattices in the Magnetite/Zinc Ferrite System which Exhibit Resistance Switching

Rakesh V. Gudavarthy, Dept. of Chem., MS&T

Abstract: In this work, both defect-chemistry and compositional superlattices in the Fe3O4/ZnFe2O4 system are electrodeposited. There is interest in depositing thin films and superlattices based on Fe3O4 because the conducting cubic phase transforms to the insulating monoclinic phase below the Verwey transition at 120 K, making it a good candidate for resistance random access memory (RRAM) devices. For such RRAM devices, it is often necessary to have nanophase material. Electrodeposition can produce such nanophase material with precise control of composition and morphology by simply controlling the temperature, pH and overpotential. In ZnFe2O4, the Zn(II) substitutes for Fe(II) producing a material that is antiferromagnetic below the Néel temperature.

 Films of Fe3O4 are electrodeposited with stoichiometries that depend on the applied potential. We prepare the films by electrochemical reduction of a Fe(III)-TEA (triethanolamine) complex at 80 oC in strongly alkaline solution. Because of the electrochemical-chemical nature of the deposition mechanism, it is possible to control the composition of film through the applied overpotential. At low overpotentials at which j = 0, the surface concentration of Fe(TEA)3+ should be equal to the bulk concentration, whereas at high overpotential at which j = jL the surface concentration of Fe(TEA)3+ should approach zero. Hence the material should have an excess of Fe3+ at low overpotential and an excess of Fe2+at high overpotential. X-ray diffraction, Mössbauer and magnetic studies have confirmed that stoichiometric magnetite can be produced at -1.065 V vs. Ag/AgCl. Superlattices of the material are electrodeposited by pulsing the applied potential between -1.01 and -1.065 V vs. Ag/AgCl. Compositional superlattices can be produced by adding Zn(II) to the deposition bath.

 We have shown that epitaxial magnetite films and superlattices on single crystal Au(111) substrate exhibit resistance switching.1 A stoichiometric Fe3O4 on Au(111) produced at -1.065 V has only one resistance switch. On the other hand, the superlattices on Au(111) have multistate resistance switching and a unique negative differential resistance feature.

 

Toward Higher Energy Density Dielectrics Through Nanocomposites

Sasidhar V. Siddabattuni, Dept. of Chem., MS&T

Abstract: Dielectric materials that are capable of storing large amounts of electric energy are desirable for many electronic and electric systems.  Since the electric energy density in a linear dielectric material is equal to kEb2/2, where k is the dielectric constant (e’) of the material and Eb is the dielectric breakdown strength, both large e’ and high Eb are required for large electric energy storage.  While ceramic materials like barium titanate usually have large e’, they are limited by their relatively small Eb, poor processability and mechanical properties.  On the other hand, polymers usually have higher Eb and excellent mechanical properties and processability but suffer from a smaller e’.  A higher Eb is more beneficial to enhance energy density than a proportional increase in e’.  Thus, numerous efforts have been ongoing to combine polymers of high Ebwith nanoparticles of high e’ with the desire to enhance the dielectric film energy storage density through nanocomposites.  In this work, we strengthen the nanocomposite filler-polymer interface through the use of bifunctional reagent, 2-aminoethyl dihydrogen phosphate (AEP), to modify the surface of titania and barium titanate.  The AEP filler surface can then covalently react with polymer matrix during cure to achieve a strong, covalent interface when used with thermosetting composites, such as an epoxy polymer matrix.  Results show that interfacial covalent bonding is an effective approach to increase the electrical resistance of a polymer-particle composite to charge flow and dielectric breakdown.  Interface-modified composites retain the glass transition temperature of pure polymer, reduce Maxwell-Wagner relaxation of the polymer-particle composite, and have a reduced sensitivity to dielectric breakdown compared to composites with adsorbed interfaces. 

 

The Sexuality of the Chemistry of Explosives and Explosives at S&T or Why Things Go Boom... How Chemistry Plays In Explosives

Prof. Paul Worsey, Dept. of Mining and Nuclear Engineering, MS&T

Abstract: A humorous take on explosives chemistry and the perhaps the reason why it should be left in the hands of Chemists. This will be followed by a brief condensed history of the chemistry of explosives to present, a briefing on where 99% of explosives are used, and what the explosives program is up to at Missouri S&T.

Job Search Techniques & Interviewing

Edna M. Grover-Bisker, Associate Director, Career Opportunities Center, MS&T

 

Novel Imaging Platform for Deciphering Motions in Living Cells

Prof. Ning Fang, Dept. of Chem., Iowa State University

Abstract: Characteristic translational and rotational motions of bimolecular and nanoparticles are fundamental to most chemical and biological phenomena. Translational motion can be readily revealed by a variety of single-particle/molecule tracking methods. However, rotational motion is much more difficult to resolve due to technical limitations. The prominent examples of lacking knowledge on rotational motion are endocytosis and intracellular transport in live cells. The current understanding of rotational motion was acquired mostly in vitro using methods based either on fluorescence polarization or on super-localization of translational probes. Resolving dynamic rotational motion in living cells or other complex environments is still challenging. We developed novel optical imaging tools, based on plasmonic nanoparticle probes and differential interference contrast (DIC) microscopy, to visualize and decipher?single-nanoparticle/molecule translational and rotational motion in complex environments and address outstanding questions in chemical and biological systems that were previously unattainable. Our current efforts are focused on deciphering rotational motions involved in receptor-mediated endocytosis, intracellular transport, and rotational diffusion on the cell membrane.

 

Oxidation of Zirconium Diboride Based Ultra-High Temperature Ceramics

William G. Fahrenholtz and Gregory E. Hilmas, Dept. of Material Science and Engineering, MS&T

Abstract: Oxidation behavior of zirconium diboride based ultra-high temperature ceramics will be discussed. When exposed to oxidizing environments, ZrB2 undergoes stoichiometric oxidation forming ZrO2 and B2O3. At elevated temperatures, B2O3 volatilizes, leaving a layer of porous ZrO2, which is not protective and allows rapid oxidation of the underlying ceramic. The most common strategy for improving oxidation resistance is to add silicon containing compounds such as SiC or MoSi2, which results in formation of a SiO2 layer that provides improved oxidation protection at intermediate temperatures. This presentation will focus on key aspects of the response of ZrB2-based ceramics to oxidizing environments. Cross sections of oxidized specimens will be characterized to determine the composition and thickness of reaction layers. Thermodynamic tools will be used to interpret the evolution of structure during oxidation. In addition, the addition of tungsten will be discussed as an alternative to silica formers for improving oxidation protection.

Smelting in the Age of Nano Metal Aerogels

Naveen K. Chandrasekaran, Dept. of Chem., MS&T

The History of the Chemistry Set

Dennis L. Whitney, Environmental Engineer, American Airlines, Retired

Abstract: Toy chemistry sets have been a favorite and useful tool in chemical education since they were first introduced by Mr. Gilbert and Mr. Porter in the 1920s. Unfortunately, they are now no longer widely available.  A short discussion will be presented as to both how the chemistry set evolved from mining tools and the magic sets that were popular in the last century and the cause of their recent decline as a popular toy for children. Some vintage chemistry sets will be displayed.

Surface Plasmon Resonance Imaging

Dr. Yi Chen, Institute of Chemistry, Chinese Academy of Sciences, Beijing, China

Abstract: Surface plasmon resonance imaging (SPRi) was developed based on a phenomenon of surface plasmon wave which was first observed in 1902 [1] but elucidated in theory half a century later, in 1959 [2]. SPRi appeared for the first time in 1987 [3]. However, it has also been delayed to develop into an analytical method, though, it is inherently a high throughput technique suitable for study of intact biological macromolecues [4]. We have worked on SPRi since 1997, starting from the design and fabrication of SPRi systems due to the unavailability of a commercial instrument at that time. With laboratory-fabricated systems controlled also with laboratory-edited image workstations, color or grey images of chemical microdots spotted on gold sensing surfaces were easily imaged at a density of up to about 5000 dots/cm2. Methods were then explored for high throughput analysis of various samples and chemical or biochemical processes. Some examples will be discussed like protein denaturing, enzymatic digesting or decomposing, and molecular recognizing events. These works suggest that SPRi could become a novel high throughput platform for characterization and determination of intact biological molecules including not only proteins but also DNA, saccharides and many glycol-conjugates. Further studies are however needed and waiting for conduction.

Compliance with Environmental Regulations

Dr. Alice Beechner Reeves, President & Principal, Paragon Business Solutions, Inc. 

 

Bogan with Poems on Science

Prof. James J. Bogan, Curators' Teaching Professor of Art History and Film, MS&T

Abstract: Professor Bogan will present some of his poems that have been inspired by science and engineering. In addition he will screen his most recent short film, MAN vs. TREE, to illustrate how the experimental method can be used in documentary film production.

 

Chemistry in Shakespeare

Prof. Nicholas W. Knight, Dept. of English, MS&T

Abstract: By using references found in Shakespeare’s 30 plays, written between 1588 and 1610, we can discern his awareness of the current developments in the sciences of chemistry, biochemistry, medicine, astronomy, physics, geography, geology, and psychology. He explicitly refers to both the much earlier work of Galen (~130–~200), and his near-contemporary Paracelsus (1490–1541), in All’s Well that Ends Well, moving from alchemy and astrology to medicine. In Romeo and Juliet, he deals with drugs and poisons. Not only are these plays evidence of Shakespeare’s knowledge of the scientific developments of his time, but a close analysis of Documented Polypharmacology in Treating Diseases a treatise by his son-in-law, John Hall, reveals, for his period of time, an advanced knowledge of the methodology and practice of medicine, both in Shakespeare’s own family and in the nobility in Shakespeare’s England. 

Electrodeposition of Metal Oxides

Niharika Burla, Dept. of Chem., MS&T

 

Aerogels and Films through Free-Radical Chemistry

Mr. Anand Sadekar, Dept. of Chem., MS&T

 

The Role of Materials in the Development of Mankind

Dr. Wayne Huebner, Dept. of Materials Science and Engineering, MS&T

Abstract: Advances in the development of man can be traced to his mastery of the world of materials around him.   This presentation will initially focus on the ages of man from the Stone Age through today's Nano/Bio Age, with particular emphasis on the evolution of our understanding of structure-processing-property relation-ships. Then I will present many examples of leading-edge materials research at S&T.

 

The Heat Capacity of Sodium Atoms as an Ideal Gas and a Real Gas

Dr. Louis Biolsi, Dept. of Chem., MS&T

 Abstract: The ideal gas heat capacity of sodium atoms is calculated to high temperatures. At higher temperatures, the increasing size of the atoms as a con-sequence of the population of highly excited electronic energy levels must be considered or the heat capacity becomes very large.

The sodium atoms are also considered to be a real gas that obeys the virial equation of state. The first non-ideal term in the virial expansion is evaluated. This involves the second virial coefficient which depends on the interaction between two sodium atoms. Contributions to the heat capacity of sodium atoms from the virial coefficients associated with the lowest ten states of the sodium dimer are considered.

 

 

2011

The Characterization of Ultrafine Particulate Matter from Combustion Processes

Dr. Philip D. Whitefield, Dept. of Chem., MS&T

 

 

 

Treatability of Envrionmental Contaminants and Removal of Disinfection By-Products in Drinking Water Using LC-MS/MS

Yinfa Ma, Dept. of Chem., MS&T

Abstract:  Environmental contaminants in natural and drinking waters, such as pesticides, herbicides and pharmaceuticals and personal care products (PPCPs), may exert possible health impacts on humans In addition, many disinfection byproducts (DBPs), such as  N-nitrosamines, halonitromethanes (HNMs), could also exist in drinking water after water treatment processes at water treatment facilities. Therefore, efficient treatment and removal of these emerging contaminants and DBPs in natural and treated waters become an important issue for environmental researchers so to provide safe drinking waters for human and animals.

In our recent study, chemical and physical methods for removal of selected PPCPs and DBPs in natural and drinking waters have been investigated by using liquid chromatography coupled with tandem mass spectrometry (LC-MS/MS) and other analytical techniques. The details on method development, quality control/assurance, removal efficiency, and potential solutions for a clean drinking water will be discussed.  

 

 

 

Organfluorine Chemistry in the Design of Cell Cycle Inhibitors

Dr. V. Prakash Reddy, Dept. of Chem., MS&T

Abstract:  In view of the unique applications of organofluorine compounds in bioorganic and medicinal chemistry, a series of novel purine-based fluoroaryl triazoles have been synthesized using the Cu(I) catalyzed 1,3-dipolar cycloadditions, and assayed for their potency in cell cycle inhibition using Ab cultures.  Some of these triazole derivatives are found to have comparable effect as that of Roscovitine, and Flavopiridol, the widely used cyclin-dependent kinase (CDK) inhibitors currently under clinical trials, in cell cycle suppression. The beneficial effects of these triazole based purine derivatives on the Amyloid-beta (Ab) induced neurotoxicity is significant, and thus they would have potential therapeutic applications. General synthetic methodologies for organofluorine compounds will also be discussed.

Optimization of the Response Times in Photorefractive Polymeric Composites through the Inclusion of Semiconductor Nanocrystals

Jeffrey G. Winiarz, Dept. of Chem., MS&T

Abstract:  The phenomenon of photo refractivity, which involves the creation of a reversible hologram generated by the crossing of two coherent beams in an appropriate medium, can be realized in polymeric composite materials which simultaneously exhibit photoconductive and electro-optic properties. The nanocomposite approach offers opportunities to produce high performance and relatively low cost optoelectronic media, suitable for many applications. Especially promising are nanocomposites of polymers and inorganic semiconductor nanocrystals commonly known as quantum dots. Initially, experiments focused on the optical absorption properties of quantum dots and their dependence on composition and size. The broad tunability of the spectral response and increased photo-charge generation efficiency were particularly interesting with respect to photorefractive composites. More recently, however, time-of-flight experiments have revealed that the mere inclusion of semiconductor nanocrystals significantly enhances the mobility of charge carriers in polymeric composites. This enhanced mobility translates into an improved response time; an issue which has plagued this class of materials since their inception and has precluded their use in many practical applications. This seminar will present experimental evidence confirming that through judicious selection of an appropriate semiconductor material, the loading content of the photosensitizing nanocrystals can be increased while avoiding detrimental effects such as substantial optical absorption losses. Through increased loading, the enhanced charge-carrier mobility associated with the nanocrystals can be more fully exploited leading to improved response times. In addition, data will be presented which demonstrates the ability to achieve unprecedented response-times through enhanced charge-carrier mobility via the inclusion of semiconductor nanocrystals in more traditionally organically photosensitized photorefractive composites.

A General Scheme for Representing Potential Energy Suraces for Multi-channel Reactions

Dr. Richard Dawes, Dept. of Chem., MS&T

Abstract: The potential energy surface (PES) is central to how chemists think about the structure and dynamics of molecular systems, in terms of minima or asymptotes connected by paths across landscapes and over energetic barriers.  The concept of an adiabatic energy hypersurface is a result of the Born-Oppenheimer approximation and is usually sufficiently accurate even for high-resolution spectroscopic applications. When necessary, most treatments of non-adiabatic dynamics begin with a set of (coupled) adiabatic electronic states, making the potential energy surface ubiquitous to theoretical chemistry.

      I will describe some methods used to compute accurate molecular electronic energies and fit them into analytic functional forms (PESs). A strategy for multichannel reactions and representative results from studies of spectroscopy and dynamics will be shown. 

Topics in Nuclear Magnetic Resonance Spectroscopy and Imaging

Dr. Rex E. Gerald II, Argonne National Laboratory, Dept. of Chem., MS&T

 

History, Politics, Hope for the Future- Energy?

Dr. Jack Magruder, Prof. of Chemical Education, President of A.T. Still University of Health Sciences

 

Further Materials Research at MS&T

Dr. Wayne Huebner, Dept. of Material Sciences and Engineering, MS&T

Abstract: Advances in the development of man can be traced to his mastery of the world of materials around him.  This presentation will initially focus on the ages of man from the Stone Age through today's Nano/Bio Age, with particular emphasis on the evolution of our understanding of structure-processing-property relation-ships. Then I will present many examples of leading-edge materials research at S&T.

 

In vivo Inhibition of L-Buthionine-(S,R)-Sulfoximine(BSO)-Induced Cataracts by a Novel Antioxidant,

N-acetylcysteine Amide

Joshua W. Carey, Dept. of Chem., MS&T

Abstract: Cataracts are the most common cause of treatable blindness worldwide. It has been shown that cataracts likely develop due to the effects of oxidative stress. Oxidative stress is caused by an imbalance between the production of reactive oxygen and a biological system's ability to readily detoxify the reactive intermediates or easily repair the resulting damage. A normal lens has several antioxidant enzymes and a high concentration of ascorbate and GSH that protect it from the damages of oxidative stress. The ability of the lens to resist oxidative damage decreases dramatically with the age related decrease in the production of GSH by the cell. GSH is an important thiol for protecting against GSH and maintaining the transparency of the lens. The effects of GSH on normal lens function can be studied by depleting the intercellular levels of GSH using L-Buthionine-(S,R)-sulfoximine (BSO). BSO is an inhibitor of γ-glutamyl-cysteine synthetase, which is known to deplete the levels of GSH both in vivo and in vitro. The role of GSH can be studied by inducing BSO generated cataracts in an animal model. When GSH levels are depleted the formation of a cataract occurs; however it has been suggested that by increasing the levels of antioxidants in the cell it is possible to prevent the formation of cataracts. Recent research using N-acetylcysteine amide, (NACA) a novel antioxidant, have led to the theory that it may be possible to reverse the effects of oxidative damage in low grade cataracts.

 

Inorganic Chemistry for the Mineral Collector

Dennis L. Whitney, Environmental Engineer, American Airlines, Retired

Abstract: The collection and classification of minerals may be either a hobby or a profession that involves the study of geology, mineralogy, and inorganic chemistry. The history of mineral collecting and the Old Dana, Strunz, and New Dana classification systems used to classify a systematic mineral collection will be discussed.

The assay of a mineral typically does not provide information about its systematic mineralogy, but rather provides only its bulk chemical composition in terms of its corresponding elemental oxides. The reasons for this unusual approach to reporting the composition of a mineral will be discussed. Exotic and unusual mineral specimens will be displayed and the processes involved in assembling a mineralogical study collection will be discussed.

Biomarkers for Noninvasive Early Cancer Detection

Sanjeewa Gamagedara, Dept. of Chem., MS&T

Abstract: Cancer is the second leading cause of death, accounting 13% of all deaths worldwide. Deaths from cancer are projected to continue rising, with an estimated 12 million deaths in 2030. Cancer develops rapidly and early diagnosis and treatment greatly improve the patient’s chances of survival. Biomarkers are good potential candidates for this early cancer diagnosis.

    Part I:Recently pteridines become a focal point of cancer screening research because certain pteidines levels have been shown to reflect the presence of cancers. This study analyzed eight pteridines; 6,7-dimethylpterin, 6-biopterin, D-(+)-neopterin, 6-hydroxymethylpterin, pterin, isoxanthopterin, xanthopterin and pterin-6-carboxylic acid using a house-built high-performance capillary electrophoresis with laser-induced fluorescence detection (HPCE-LIF). The levels of pteridines were reported as a ratio of pteridine to creatinine. Statistical hypothesis testing was conducted and P-values were calculated to analyze the data.

    Part II: Sarcosine and related matebolomic profiles recently drew a lot of attention because a debate regarding their possible role as potential clinical markers for prostate cancer. In this study, levels of sarcosine and related metabolites in 126 patients with genitourinary malignancies (63 prostate cancers & 63 bladder cancers) were analyzed using a validated LC/MS/MS method. Statistical hypothesis testing, Multivariate analysis of variance, correlation study, and principal component analysis were conducted to analyze the data. For prostate cancer these biomarker levels were compared in T1,T2 stages and Gleason scores <7, ≥7.  The detailed experimental conditions and results will be presented at the seminar.

 

Corrosion Coatings Based on Rare-Earth Oxide Inhibitors

Dr. Matt O'Keefe, Dept. of Material Sciences and Engineering, MS&T

 

The Art and Science of Microscopy

Clarissa Wisner, Electron Microscope Specialist, MS&T

 Abstract: 

In 1661, Henry Powers, wrote a poem “In Commendation of ye Microscope,”

 

"Of all the Inventions none there is Surpassed

the Noble Florentine's Dioptrick Glasses

For what a better, fitter guift could bee

in this World's Aged Luciosity.

To help our Blindnesse so as to devise

a paire of new & Artificial eyes,

by whose augmenting power wee

now see more than all the world Has euer donn Before."

 

This poem is still so true today, with all the innovations to the world of microscopy.  But not all work in microscopy is scientific in nature.  There is a growing industry that uses the microscope to enhance walls, textiles, pottery and other ordinary everyday things.  The merging of these two dissimilar words is not only exciting, but interesting as one follows the history of the science of microscopy to the pop culture art world.

We will take a journey from the beginning of the microscope in the 16th century to the present that will not only give historical facts but beautiful images to entice everyone to take up microscopy as a hobby!

 

Nanoscale Acrylate Unimolecule Micelles

Cynthia Riddles, Dept. of Chem., MS&T

 

General Laboratory Safety Training

Phyllis Lewis, Environmental Specialist, Environmental Health and Safety

Abstract: 

  • Hazardous Waste Management
    • Federal Regulation & University Policy
    • Types of waste handled by Environmental Health and Safety
      • Chemical, Bio-hazardous, Universal
    • Proper storage of wastes
    • Proper labeling of wastes
    • Filling out the waste pick-up request form
    • Fire Safety (10 minute video)
    • Spill Response 
  • Laboratory Safety
    • General laboratory housekeeping
    • Safety policies
    • Common hazards in the laboratory
      • Chemicals, Bio-hazards, Radiation, Compressed Gas Cylinders
    • Labeling & Storage
    • Chemical inventory:  Chemtrack
    • Personal Protective Equipment
    • Emergency Response

 

 

An Overview of the Library Resources for the Students of Chemistry

Christopher Jocius, Head of the Reference Department C.L. Wilson Library, MS&T

Abstract: An overview of the resources available for chemistry graduate students at the Missouri University of Science and Technology library will be presented. This will include how to access and use the ACS based Scifinder to search the chemical scientific literature. 

Organic/Inorganic Aerogels through Ring Opening Metathesis Polymerization

Dhairyashil Mohite, MS&T

Abstract: Aerogels are open-pore, low-density nanostructured solids with high surface areas, low thermal conductivities, low dielectric constants and high acoustic attenuation. The most common type, silica aerogels, are made by base-catalyzed gelation of tetramethylorthosilicate (TMOS) and consist of a self-assembled, 3D skeletal framework of silica nanoparticles. Despite their attractive bulk properties, these materials are extremely fragile, which limits their applications. Strength of aerogels can be increased by providing interparticle polymeric tethers which covalently connect the skeletal nanoparticles. These new, mechanically strong porous materials are referred to as polymer crosslinked aerogels. Organic aerogels on the other hand are derived solely from organic polymers, mainly based on resorcinol-formaldehyde (RF), melamine-formaldehyde (MF), and phenol-furfural (PF) resins. Other polymer-based aerogels reported include polyurethane/polyurea, polystyrene, polydicyclopentadiene, and lately polyimides.

     Part A: Strong Silica Aerogels Crosslinked with Polynorbornene via Ring Opening Metathesis Polymerization (ROMP) Crosslinking of silica aerogels is demonstrated by ring opening metathesis polymerization (ROMP) by providing the surface of silica particles with the norbornene functionality using a new nadimide derivative of 3-aminopropyltriethoxysilane (APTES). Norbornene monomer is introduced in the mesopores and a ROMP process is started using 2ndgeneration Grubbs’ catalyst at ambient temperature. The growing polymer engages norbornene moieties bound on the surface of 

silica forming a conformal coating of polynorbornene on the mesoporous surfaces throughout the entire skeletal framework. The amount of polymer incorporated in the mesoporous structure is controlled by the concentration of the monomer in the mesopores. Despite the increase in bulk density (up to 0.6-0.7 g cm-3), decrease in porosity (down to ~50% v/v), and decrease in surface area (down to ~150 m2 g-1), the materials remain mesoporous. The mechanical properties in terms of strength, modulus and the energy absorption capability relative to the native (non-crosslinked) counterparts are increased dramatically.

     Part B: Organic (Polyimide and Polydicyclopentadiene) Aerogels by ROMP Polyimide aerogels are synthesized by crosslinking through ROMP of a bisnadimide bifunctional monomer, bis-NAD, using a second generation Grubbs’ catalyst. Aerogels with different bulk densities (ranging from 0.13 to 0.66 g cm-3) were obtained by varying the monomer concentration in the sol (from 2.5% to 20% w/w). With increasing density, the interconnected nanoparticle structure changed from macro- to mesoporous and the percent ratio of the micropore area relative to the BET surface area decreased from 28% to 9%. bis-NAD aerogels demonstrate excellent mechanical strength and high specific energy absorptions.

     Synthesis of mechanically strong polydicyclopentadiene (pDCPD)-based organic aerogels is carried out through ROMP by reinforcing through post-gelation grafting with polymethylmethacrylate (PMMA) using free radical chemistry initiated with AIBN. Solid 13C CPMAS NMRs confirm the grafting of PMMA on pDCPD structure. Homogeneous aerogels with bulk density ~0.43 g cm-3 were obtained consisting of interconnected nanoparticles with narrow pore size distribution. Such pDCPD-X-MMA aerogels demonstrate excellent mechanical strength.

Organofluorine Compounds: From Superacids to Medicinal Chemistry

V. Prakash Reddy, Dept. of Chem., MS&T

Abstract: Due to the unique properties of C-F bond, organofluorine compounds have unusual physicochemical properties.  They are components of superacids, widely used polymeric materials, anesthetics, agrochemicals, as well as numerous pharmaceuticals.  Understanding the effects of C-F bond on the stabilization of reactive intermediates is essential in designing new synthetic methods, and for the designing of the biologically and medicinally active compounds.  In general, fluoroalkyl groups such as trifluoromethyl and gem-difluoromethylene groups are expected to destabilize the carbocationic intermediates. However, experimental evidence is of limited scope for the fluorinated carbocation intermediates due to the difficulty of their formation.  Insights gained from the effect of substituents on the relative stabilization or destabilization of the carbocations and other reactive intermediates, in conjunction with factors such as hydrophobic and lipophilic nature of fluorinated compounds are of fundamental interest in the design of the biologically and medicinally relevant novel organofluorine compounds.  In this context, our studies on some of the fluorinated carbocations in superacid media and overview of our recent synthetic strategies for organofluorine compounds will be discussed.

The Characterization of Ultrafine Particulate Matter from Combustion Processes

Philip D. Whitefield, Dept. of Chem., MS&T

Abstract: This presentation will discuss the need for ultrafine particulate matter (PM) characterization for both environmental, economic and defense related purposes.  It will provide a basic introduction to the fast, real time experimental methods employed to determine PM, size distribution, number and mass concentration, composition and hydration properties using extractive sampling methods.  The application of these methods will be described using examples from the work of the Aerospace Emissions Program at MS&T.   In particular gas turbine engine emission characteristics using conventional and alternative aviation fuels will be described as will the changes observed in the PM properties as the engine exhaust expands and disperses in the engine exhaust plume.

Correlation for Yield of Competitive Reactions in Reactors with Turbulent Mixing

Gary K. Patterson, Dept. of Chemical and Biological Engineering, MS&T

Abstract: A correlation for yield of a product of competitive reactions with turbulent mixing resulted in a plot of [yield/perfect yield] versus a mixing Damkoehler number, the ratio of mixing time to reaction time, written as follows:  DaM = τMR, where τM ≈ 2(L2/ε)1/3 and τR = 1/(k1k2CAfCBres)1/2.  Such competitive reactions are represented by A + B  R; R + B  S and A + B → R; C + B   S.  The scale of mixing L is approximated in a stirred vessel by Df = (4Qf/πUbt)1/2  and the rate of turbulence energy dissipation rate in a stirred vessel ε is given by NiNPD2N3/[(T/D)3(π/4)].  [Symbols are defined as follows:  k1 and k2 are rate constants for reactions 1 and 2, CAf and CBres are molar concentrations of the feed A and the resident B, Df is the diameter of the feed jet as stretched or compressed by the flow, Qf is the volumetric feed rate, Ubt is the blade tip speed of an impeller, Ni is the ratio εfeed pointaverage , NP is the impeller power number, N is the impeller rotation rate, T is the vessel diameter, and D is the impeller diameter.]

     A recent more detailed dimensional analysis has shown the need to include the effect of the ratio of reaction rate constants, k2/k1, in the correlation, even though the ratio of yield to perfect yield removes most of the divergence.  The new correlation effectively separates experimental data for different k2/k1-ratios.  The seminar will include the details of the dimensional analysis, consequences for other types of mixed reactors, for instance static mixers, and sources of data used.

 

 

Learning in the Undergraduate Chemistry Laboratory: Perspective from a South African Research University

Karen Wallace, University of Western Cape, South Africa

Abstract: First-year chemistry students at most South African universities typically had limited or no exposure to laboratory work while at school. This applies especially to students from lower socio-economic beginnings who attended township or rural schools. The University of the Western Cape (UWC), a historically black university (HBU), draws at least half of its students from this demographic.

My presentation will focus on two aspects of laboratory learning that is addressed by my research in the above context, namely:

  • The role of the postgraduate students as facilitators in the first-year laboratory experience; and
  • The use of online video clips to support student preparation for laboratories. 

Addressing the first of these, I will report on a qualitative study performed in my department to characterise postgraduate participation in the undergraduate laboratories. Teaching assistants (or demonstrators as they are called at South African universities) have become indispensable to the delivery of teaching particularly to first-year students, due mainly to the growing need in tertiary institutions to balance increasing student numbers and needs with pressure on academic staff time and institutional resources. At most universities the role of teaching assistants falls to postgraduate students who are being trained in disciplinary research. In addition to funding their own studies, their participation in teaching activities is increasingly being recognised as preparation for possible careers in tertiary teaching.

A theoretical framework that views learning as participation in a community of practice was used to characterise demonstrators’ engagement with their task of facilitating student learning. Learning as participation is more than engagement in the activities and practices of a social or professional group of people; it encompasses both active participation and the construction of an identity in relation to the group and its practices. I will attempt to present a qualitative interpretation of what learning in a demonstrator/postgraduate community might mean: from emerging conceptions about student learning and the learning of chemistry, to a deeper understanding of the meanings of professional behaviour and academic enterprise. I will also report on the outcomes of an intercessionary process consisting of various measures aimed at improving demonstrating practice in the first-year laboratories at my institution.

The second aspect of laboratory learning that will be addressed is student preparation for laboratory work. Students attending the first-year chemistry laboratory course at UWC are required to prepare a flow diagram, showing the procedure they intend to follow during the execution of the practical, prior to each laboratory session. The rationale behind this requirement is to increase the students’ level of preparation for laboratories, with at least some of the transformative tasks occupying the working memory during the execution of the practical taken care of beforehand. In order to assist students in the transformation of procedural texts into flow diagrams, short video clips were uploaded to UWCs e-learning platform. The results of a pilot experiment in which the flow diagrams of students who had watched the clips were compared with those of students who had not watched the clips will be presented.

Chemistry of the Solar System

Dennis L. Whitney, Environmental Engineer, American Airlines, Retired

Abstract: The nature of the creation of the environment we inhabit has intrigued philosophers since the dawn of our conciseness.

The application of the principles of nuclear, inorganic, and geological chemistry to the study of geological specimens and meteorites has led to new insight into the nature of the process that have lead to our current environment. The fact that the earth supports life seems to have an important effect on the nature of this environment.

Probing Actinide Electronic Structure Using High-resolution Photoelectron Spectroscopy

Dr. Michael C. Heaven, Dept. of Chem., Emory University

Abstract: High-level theoretical models of the electronic structures and properties of actinide compounds are being developed by several research groups.  This is a challenging problem due to the need for explicit treatment of relativistic effects, and the circumstance that many of these molecules exist in states where the f and/or dorbitals are partially filled.  Current theoretical models are being evaluated through comparisons with experimental results.  Gas phase data are most suitable for this purpose, but there have been very few gas phase studies of actinide compounds.  We are addressing this issue by carrying out spectroscopic studies of simple uranium and thorium compounds.  Multiple resonance spectroscopy and jet cooling techniques are being used to unravel the complex electronic spectra of these compounds. 

          Our recent studies have focused on the electronic structures of the oxides, sulfides fluorides and nitrides of Th and Hf.  Comparisons between isoelectronic species indicate that relativistic affects play a relatively minor role in the ionic bonding of ThO, ThO+, ThF and ThF+.  ThO and the ions HfF+ and ThF+ have been identified as excellent candidates for measurements that probe the electric dipole moment of the electron (a manifestation of CP symmetry violation).  The characteristics that render these molecules favorable for studies of fundamental constants will be reviewed, and the first gas phase spectra for the Th fluoride and nitride species will be presented.

NMR Experiments Performed in Weak and Inhomogeneous Magnetic Fields

Dr. Rex E. Geral, Dept. of Chem., MS&T

 

Photorefractive Polyvinyl Carbazol Composites Using PbS Nanocrystals as a Photosensitizer

Jong-Sik Moon, Dept. of Chem., MS&T

Abstract: Inspired by the promise of enhanced spectral response, photorefractive polymeric composites photosensitized with semiconductor nanocrystals have emerged as an important class of materials. In addition to providing efficient photosensitization, however, extensive study of these hybrid composites has indicated that the inclusion of nanocrystals also provides an enhancement in the charge-carrier mobility, and subsequent reduction in the photorefractive response time. Unfortunately, the included nanocrystals have also been shown in most cases to increase the deep trap concentration, resulting in a significant decrease in the photorefractive performance, specifically diminished diffraction efficiencies as well as reduced two beam coupling gain coefficients. Nonetheless, evidence suggests that this problem can be largely avoided through the inclusion of semiconductor nanocrystals possessing a relatively narrow band-gap. Here, we fully exploit this quality by doping PbS nanocrystals into a newly formulated photorefractive composite based on molecular triphenyldiamine photosensitized with C60. Through this approach, unprecedented response times of 400 ms are observed, opening the door for video and other high-speed applications. It is further demonstrated that this improvement in response time occurs with little sacrifice in photorefractive efficiency, with internal diffraction efficiencies of 72% and two-beam-coupling gain coefficients of 500 cm-1 being measured. A thorough analysis of the experimental data is presented, supporting the hypothesized mechanism of enhanced charge mobility without the accompaniment of superfluous traps. It is anticipated that this approach can play a significant role in the eventual commercialization of this class of materials.

 

 

 

The Chemistry and Remarkable Applications of Cyanoximes and their Metal Complexes

Nikolay Gerasimchuk, Dept. of Chem., Missouri State University

Abstract: During the last two decades my research interests were dedicated to the new class of weak organic acids – cyanoximes. These low molecular weight organic molecules represent series of new ligands for coordination chemistry.[1] Both unbound to metal free ligands, their Na+ and K+ salts and other metal complexes show a large spectrum of biological activity from growth regulation in plants to in vitro cytotoxicity. Currently 37 cyanoximes are known, and were more than two hundreds cyanoxime complexes synthesized and studied using a variety of different spectroscopic methods and x-ray analysis. Stereochemistry of cyanoxime ligands,[2] structures and properties of the most interesting coordinations compounds are reviewed in this presentation.[3,4] A broad spectrum of applications of both cyanoximes and their metal complexes is outlined in this lecture as well.[5-11]  

How to Use Gaussian09 at MS&T? What Can You Learn from Gaussian09?

Richard Dawes, Dept. of Chem., MS&T

 

2012

General Laboratory Safety Training

Phyllis Lewis, Environmental Specialist, Environmental Health & Safety

Abstract: 

  • Hazardous Waste Management
    • Federal Regulation & University Policy
    • Types of waste handled by Environmental Health and Safety
      • Chemical, Bio-hazardous, Universal
    • Proper storage of wastes
    • Proper labeling of wastes
    • Filling out the waste pick-up request form
    • Fire Safety (10 minute video)
    • Spill Response
  • Laboratory Safety
    • General laboratory housekeeping
    • Safety policies
    • Common hazards in the laboratory
      • Chemicals, Bio-hazards, Radiation, Compressed Gas Cylinders
    • Labeling & Storage
    • Chemical inventory:  Chemtrack
    • Personal Protective Equipment
    • Emergency Response

The Characterization of Ultrafine Particulate Matter from Combustion Processes (Continued)

Philip D. Whitefield, Dept. of Chem., MS&T

 Abstract: This presentation will discuss the need for ultrafine particulate matter (PM) characterization for both environmental, economic and defense related purposes.  It will provide a basic introduction to the fast, real time experimental methods employed to determine PM, size distribution, number and mass concentration, composition and hydration properties using extractive sampling methods.  The application of these methods will be described using examples from the work of the Aerospace Emissions Program at MS&T.   In particular gas turbine engine emission characteristics using conventional and alternative aviation fuels will be described as will the changes observed in the PM properties as the engine exhaust expands and disperses in the engine exhaust plume.

The Use of SciFinder in Chemical Research

Dr. Steve Dueball, Applications Specialist, Chemical Abstract Service, American Chemical Society

Chelating Compounds as Potential Flash Rust Inhibitors in Waterborne Coating Systems

Jigar Mistry, MS&T

Abstract: 

Part 1: Chelating Compounds as Potential Flash Rust Inhibitors in Waterborne Coating Systems

 Waterborne coatings on ferrous substrates usually show flash rusting which decreases the adhesion of the coating and the corrosion products can form a stain. This study investigates chelating compounds as potential flash rust inhibitors.  Compounds being evaluated include amine alcohols, diamines and sulfur containing amines.  A new corrosion inhibitor 2,5-(S-acetic acid)-dimercapto-1,3,4-thiadiazole (H2ADTZ) was synthesized. The performance characteristics of this new-generation additive as a flash rust inhibitor were evaluated. 

Part 2: 1,3,2-Thiadiazolidine-2,5-dithione: Synthesis and Structure of Alkylated Derivatives

The observed structure of 1,3,2-thiadiazolidine-2,5-dithion (also known as 2,5-dimercapto-1,3,4-thiadiazole (DMTD)) has been previous reported in three different forms including  -Dithiol and -Dithion tautomeric isomers. This paper clarifies which structure is the correct one and also reports synthesis and characterization of the structure of mono- and dialkylated DMTD. The methods of x-ray crystallography, NMR spectroscopy and ab-initio electronic sturcture calculations were combined to aid in understanding the reactivity and structure of each compound. 

Part 3: Melamine & Aziridine Cure of Acrylic Colloidal Unimolecular Polymers. 

Colloidal unimolecular polymers (CUPs) were prepared and tested for application as a coating resin.  These CUP particles were true nano particles and were found to be crosslinkable with melamine and aziridine.  Formulations were prepared with melamine for bake cure and with aziridine for both bake and ambient cure coatings.  These formulations were evaluated for MEK abrasion resistance, adhesion, hardness, gloss, flexibility, abrasion and impact resistance properties. The formulated new clear coat resin system has a low VOC and good gloss and transparency.

 

Electrodeposition/Eletrochemical Reduction of Epitaxial Metal Oxide Films and Superlattices

Zhen He, Dept. of Chem., MS&T

Abstract: 

Part 1: Electrodeposition of CoxFe3-xO4 Epitaxial Films and Superlattices. Spinel ferrites are of interest because of their potential applications in spintronics (spin-based electronics), nonvolatile memories, and magnetoreception devices. Cobalt ferrite (CoFe2O4) is an inverse spinel ferrite. The utility of CoFe2O4 is mainly based on its high coercivity, and magnetocrystalline and shape anisotropy. The magnetic and electric properties of CoFe2O4 depend on its Co:Fe ratio. Here, we present a one-step electrodeposition of CoxFe3-xO4 (0<x<1) thin films from an alkaline Fe3+-Co2+-triethanolamine solution. The atomic Co:Fe ratio in the deposited CoxFe3-xO4 thin films can be tuned by controlling the deposition potential. The effects of the chemical composition on the structure and electric properties of the CoxFe3-xO4 films are investigated. Superlattices in CoxFe3-xO4 system are also electrodeposited from the same solution by simply pulsing between two potentials. Compared to CoxFe3-xOindividual films, superlattices exhibit resistance switching and a more pronounced negative differential resistance (NDR) feature at lower current during perpendicular transport measurements.

Part 2: Room-Temperature Electorchemical Reduction of Epitaxial Magnetite Films to Epitaxial Iron Films.

The electorchemical reduction of oxides to metals has been studied for decades. Eralier work produced polycrystalline bulk metals. Here, we report that pre-electrodeposited epitaxial face-centered cubic magnetite thin films can be electrochemically reduced to epitaxial body centered cubic iron thin films in an aqueous solution on single crystalline gold substrates at roome temperature. This technique opens new possibilites to produce special epitaxial metal/metal oxide heterojunctions and a wide range of epitaxial metallic alloy films from the corresponding mixed metal oxides. 

Developing Novel Synthesis Protocols for the Fabrication of Functional Nanomaterials for Advanced Devices

Sukhada Patil, Dept. of Chem., MS&T

Abstract: 

Patterned Growth of CdTe Nanowire Arrays for High Efficiency Solar Cells.

In modern nanodevices while nanostructuring is expected to increase the efficiency of the device manifold, the device geometry also plays an important role in determining the practicability of the device. In that regards, the real challenge lies in assembling the semiconducting nanowires in pre-determined regions to increase the signal to noise ratio to a practically useable value. We have successfully developed a simple, reproducible and scalable technique for growing nanowires as dense arrays on patterned substrates through electrodeposition on patterned nanoelectrodes. The success of protocol was tested on CdTe as model system, as CdTe is potential economical substitute for Si. It is easily synthesizable, and has a forgiving composition where the photovoltaic efficiency is retained over a considerable stoichiometry range. The vertically aligned CdTe nanowires grown over large area by our technique were exceptionally homogeneous in terms of the nanowires diameter and length. The ensemble of the CdTe nanowire arrays covering an area of 65 X 65 μm2, exhibited a photocurrent density in the mA range, which was higher than that of CdTe film grown under similar conditions. Results for patterned nanowires growth encompassing CdTe and other nanowires growth would be discussed in detail.

Synthesis of Superconducting Nanocables of Iron Selenide Encapsulated in Carbon Nanotubes.

Another technically important material for nanodevices is superconductors. Recent discovery of superconductivity in iron selenide have attracted considerable attention due to the simplicity of the structure. We have synthesized superconducting FeSe nanowires encapsulated inside carbon nanotubes by a simple vapor transport reaction at 800°C. The superconductivity of these nanocables was determined through magnetic measurement and Tc of 10K was obtained for the ensemble of nanowires. The FeSe filling length inside the carbon nanotubes could be varied through controlling reaction conditions and the diameter of nanowires could be controlled through reaction parameters. Carbon nanotubes protect the FeSe nanowires from O2/moisture and also under e-beam damage while preserving superconducting characteristics.

 

Designing Novel Synthesis for Production of Functional Nanowires and Nanoarrays of Superconducting and Thermoelectric Materials

Prachi Sood, Dept. of Chem., MS&T

Abstract: 

Part A: Quest for obtaining superconducting nanowires from Fe pnictide based superconductors.

Recently iron pnictide based compounds have been under immense scrutiny owing to discovery of superconductivity in the doped LnFeAsO (1111) and the AFeAs (A = alkali metal) series.  The iron pnictide layer is believed to be responsible for superconductivity in these compounds.  Nanostructures of these superconductors are perfect low dimensional models for understanding the fundamental properties of these novel superconductors.  The sacrificial template method can be possibly used to synthesize nanostructured morphologies of these superconductors, where, one of the reactants, the binary iron pnictide will be used as a morphology directing agent. We have developed a one-pot soft chemical method to synthesize monodisperse iron arsenide core- shell nanoparticles. These FeAs nanoparticles are phase pure and superparamagnetic as revealed by powder x-ray diffraction and magnetic characterization. The highest TB achieved is 247 K.  Further, attempts are being made to introduce alkali metal ions in the solution to form nanostructures of the ternary [111] superconducting phase.  Results encompassing synthesis of FeAs nanoparticles and LiFeAs nanowires and [111] nanostructures will be presented.

 Part B: Producing nanowires arrays of high ZT thermoelectric materials.

Chalcogenides have been proven to have excellent thermoelectric properties. According to recent reports it has been proven that the nanostructures especially the nanowires increase ZT of thermoelectric materials by increasing the phonon boundary scattering. Recently, Na doped PbS- PbTe alloy thermoelectric systems have attracted attention due to their high power factor. Modification of density of states (DOS) by substitution of Te by Se effectively tunes the location of the valence bands of PbTe, which at high doping can maximize promotion of carriers into the heavy hole band to enhance power factor. It can be argued that nano columns of such a system containing basal p - type PbTe layer with cubic PbS with 2% Na doping can further increase the magnitude of ZT.  Such functional arrays can be used as practical devices integrated within the device geometry. Preliminary results in this project will be shared.

 

 

 

Oxidative Stress and Cardiovascular Diseases

Arunendra Saha Ray, Dept. of Chem., MS&T

 

Molecular and Electronic Structure of Transition Metal and Actinide Complexes with Monoanionic Schiff Base Ligands

Dr. Justin Walensky, Dept. of Chem., University of Missouri-Columbia

 

Biorenewable Composites from Vegetable Oil

Rongpeng Wang, Dept. of Chem., MS&T

 

Characterization of Polymer Patterns Used in the Metal Castings Process

Hongfang Zhao, Dept. of Chem., MS&T

Abstract: Investment casting, known as a lost-wax casting, has been widely employed to manufacture of quality metal components in automobile, aerospace and biomedical industries because of its ability to produce accurate and complex castings. In a investment casting process, a wax pattern is dipped in ceramic slurry to form the ceramic shell and then is removed by melted or burned out in an autoclave to create cavities; molten metal is introduced in the mold and solidified to form the casting. Finally the ceramic shell is destroyed to release the metal castings. While there are some limitations of wax pattern, such as distortion when storing and handling issues due to weight and brittleness. In addition, as the demand of industry, wax pattern could be replaced by polymer pattern because of its advantages of less expansion on heating, facilitated pattern removal, in some cases less expensive and handling easily. Applicability of different low density rigid polymer pattern materials for investment casting process was experimentally investigated. Densities, elastic moduli and thermal expansion of polymer patterns were measured. Pattern removal process from the shell was examined by thermal gravimetrical analysis (TGA). Comparison was done among physico-chemical properties of different low density rigid polymer pattern materials important for the investment casting process. The simulation of another metal casting process, lost foam casting, was performed by suing Magmasoft to help to predict and improve the casting qualities.

 

General Laboratory Safety Training

Phyllis Lewis, Environmental Specialist, Environmental Health and Safety

Abstract: 

  • Hazardous Waste Management
    • Federal Regulation & University Policy
    • Types of waste handled by Environmental Health and Safety
      • Chemical, Bio-hazardous, Universal
    • Proper storage of wastes
    • Proper labeling of wastes
    • Filling out the waste pick-up request form
    • Fire Safety (10 minute video)
    • Spill Response
  • Laboratory Safety
    • General laboratory housekeeping
    • Safety policies
    • Common hazards in the laboratory
      • Chemicals, Bio-hazards, Radiation, Compressed Gas Cylinders
    • Labeling & Storage
    • Chemical inventory:  Chemtrack
    • Personal Protective Equipment
    • Emergency Response

Occurrence, Degradation, and Control/Limitation of Emerging Dirnking Water Contaminants in Missouri Drinking Water Systems

Dr. Honglan Shi, Dept. of Chem., MS&T

Abstract: Emerging contaminants in drinking water is a very active research area in recent years due to their common concurrent and uncertain risks to human health. Many drinking water emerging contaminants, including pharmaceuticals and personal care products (PPCP), N-nitrosamines (including NDMA), perchlorate, chlorination disinfection byproducts (including halonitromethanes, and iodo-DBPs), cyano(algal)toxins, and pesticide degradation products in Missouri drinking water and source water systems, have been studied. These studies include occurrence screening, formation and degradation, and removal. Due to the very low concentrations of these contaminants in drinking water, several ultra-sensitive and rapid analytical methods have been developed by using state-of-the-art instrumentation such as ultra-fast liquid chromatography tandem mass spectrometry and gas chromatography-mass spectrometry. Major different source waters (river water, lake water, and underground well water) have been included in these studies.  Different methods for control and removal of these water contaminants have been developed/evaluated with both adsorption and oxidation technologies. Different oxidative treatments and conditions, activated carbon and nano-materials for removal efficiency of the contaminants and their precursors will also be overviewed.

Rapid Screening Methods for On-Site Pharmaceutical Surveillance

Connie M. Gryniewicz-Ruzicka, CDER, Division of Pharmaceutical Analysis, U.S. Food and Drug Administration, Saint Louis, MO

Abstract: Consumer exposure to poor quality, counterfeit and adulterated pharmaceutical products has prompted the FDA to develop rapid and reliable screening methods to assess the quality and safety of pharmaceutical products.  Spectroscopic methods are attractive for this application because portable formats are available and samples can Consumer exposure to poor quality, counterfeit and adulterated pharmaceutical products has prompted the FDA to develop rapid and reliable screening methods to assess the quality and safety of pharmaceutical products.  Spectroscopic methods are attractive for this application because portable formats are available and samples can be analyzed on-site with analysis times on the order of minutes.  This presentation will briefly describe the current spectroscopic methods, including Raman, near infrared (NIR), x-ray fluorescence (XRF) and ion mobility (IMS) spectrometries, being utilized by the FDA for field surveillance of pharmaceutical products. Method development, chemometric data analysis and field deployment will be discussed. 

 

 

Opportunities in Nanoscience with Gold Nanoparticles

Dr. George C. Schatz, Dept. of Chem., Northwestern University

 

 

 

Creating Functional Nanostructures for Smart Devices

Dr. Manashi Nath, Dept. of Chem., MS&T

 

 

 

In Vivo Microdialysis Studies of Seizure Induced Oxidative Stress

Dr. Craig E. Lunte, Dept. of Chem., University of Kansas

Abstract: It has been postulated that oxidative stress is a result of several neurobiological conditions, including epilepsy.  Epilepsy is a disease that affects 1% of the worlds population1. Of that 1%, it is estimated that 20% are resistant to current medications2.  An important secondary effect of seizures is oxidative stress.  Oxidative stress is a result of a deviation from the body’s natural balance between reactive oxygen species (ROS) and endogenous antioxidants, which act to deplete ROS in the body.  Oxidative stress due to epileptic seizures can cause localized neurotoxicity, which can in turn affect a multitude of biochemical pathways.  Specifically, localized brain damage from seizures leads to imbalances in ion and neurotransmitter levels, changing membrane potentials, which results in neuronal hyperexcitability.  The increase of glutamate and catecholamines and subsequent Ca2+ influx specifically lead to ROS formation.  It has been reported that ROS levels increase during and after seizure events3,4.  In addition to epilepsy, oxidative stress in the brain plays an important role in cellular damage due to methamphetamine use5, chronic diseases (i.e. bipolar disorder6) and in degenerative diseases (i.e. scrapie7 and Alzheimer’s disease8,9).

      The goal of this study was to use both a status epilepticus steady-state chemical model and a focal seizure model in rats using the convulsant, 3-mercaptopropionic acid (3-MPA), and to compare the changes in striatal neurotransmission to several biomarkers of oxidative stress.  In vivo microdialysis was combined with electrophysiological methods in order to provide a complete evaluation of the dynamics of the results obtained. The biomarkers monitored included, malondialdehyle (MDA) as a marker of lipid peroxidation, nitrite as a marker of reactive nitrogen species formation, and several prostaglandins.  The neurotransmitters monitored were GABA, glutamate, and the catecholamines.

            In the status epilepticus (systemic dosing) model, glutamate increased and GABA decreased monotonically while changes in dopamine (DA) concentration were bimodal.  Electrical activity in the brain rapidly returned to normal after administration of 3-MPA ceased, while glutamate remained elevated and GABA depressed for several hours after administration ceased. Administration of cyclothiazide (CTZ) diminished neurotransmitter activity but not the changes in GABA and glutamate, possibly indicating Glu receptor desensitization with the seizure model.

      Interestingly, in the focal ischemia model, both glutamate and GABA were observed to increase.  The increase in glutamate was several times greater than that of GABA, indicating that excitatory processes still dominated.  The ECoG data for the focal seizure (local dosing) model were inconsistent and weak when observed.  This was a result of the very local nature of the excitatory event and difficulty in co-locating the microdialysis probe and recording electrode.

      In this model, MDA was observed to increase upon administration of 3-MPA, indicating that lipid peroxidation was occurring.  No changes in nitrite were observed indicating that this was not a result of reactive nitrogen species being formed.  A small increase in several prostaglandins has been observed, but the changes are small.  We are working to improve our analytical method for determination of prostaglandins and hope to have more significant results in the near future.

 

 

 

Nanopore in Personalized Medicine: Single-Molecule Epigenetic Study

Dr. Li-Qun Gu, Dalton Cardiovascular Research Center, Dept. of Biological Engineering, University of Missouri-Columbia

Abstract: Nanopores are nanometer-wide tiny pores fabricated using modern protein engineering and fashion nanotechnology. Due to the molecular-scale pore size, the binding of a single analyte molecule to the pore lumen can characteristically alter the ion current through the pore. The current change is specific to the type of target molecules and their configuration in the pore, therefore generating a signature that serves as an electronic fingerprint for target molecule recognition. Used as a biosensor, the nanopore can simultaneously identify and quantify multiple target species for a variety of biomedical detections, with targets ranging from metal ions and cellular second messengers to protein and pathogen oligonucleotides. The nanopore is being developed as a rapid, label-free and low-cost technology for DNA sequencing and various genetic and epigenetic detections. Toward this goal, single-molecule nucleic acids and their interaction with nanopore has been extensively characterized, which includes many topics such as how the nanopore conductance is sensitively changed with the sequence of a single-stranded DNA or RNA in pore and how a double-stranded DNA is unfolded. We developed a new generation of programmable nanopore biosensors, called aptamer-integrated nanopore. Such a single molecule detector is integrated with aptamers, in vitro created short nucleic acids molecules that mimic antibodies to bind target proteins with high selectivity and high sensitivity. The nanopore sensor is being combined with smart polymers and microfludics to create robust chip device for future medical diagnosis, treatment, and high-throughput screening at the molecular level. Recently, we proposed a robust nanopore method of differentiating and quantifying cancer-associated microRNAs (miRNAs) in human blood samples, an approach with the potential in non-invasive and cost-effective cancer detection. MiRNAs are small regulating RNA molecules that are recognized as potential biomarkers of cancers.

Investigation of Native Microalgae as Sustainable Sources of Fuel, Feed, and Food

Dayananda Chandrappa, Dept. of Chem., MS&T

Microchip-based Analysis Systems for Monitoring Biological Events

Dr. R. Scott Martin, Dept. of Chem., Saint Louis University

Abstract: The use of microchip-based devices for performing analytical assays such as separations has become an established research area.  While one of the often stated advantages of these systems is integration of multiple processes, there are very few studies that involve the use of microchips to integrate cell-based in vitro mimics with an analysis system.  This talk will discuss work from our labs on developing such a system.  This approach uses a microfluidic device that integrates multiple processes such as cell culture, fluidic pumping, valving, electrophoresis and electrochemical detection.  Issues encountered with integrating these otherwise separate techniques will be discussed as will the use of the device to continuously monitor the on-chip stimulated release of neurotransmitters from PC 12 cells.  In addition, recent work towards developing polystyrene-based microchip devices to improve the success of on-chip cell culture as well as the performance of electrochemical detection will be presented.

Chemical Doping of Topological Insulators

Yew San Hor, Dept. of Physics, MS&T

Abstract: A novel kind of three-dimensional insulators called topological insulators, which have a bulk insulating gap but non-trivial topological surface states has been discovered. The surface states of these topological insulators show Dirac-like behavior with the spin polarization locked perpendicular to the electron momentum by the effect of strong spin-orbit interaction. As the locking protects the surface electrons from back scattering, they are predicted to have high mobilities. The spin-resolved nature of the surface states has been confirmed in angle-resolved photoemission spectroscopy experiments. However, it has been a challenge to resolve the lack of transport information due to the dominant bulk conductance in the material. By chemical doping, the chemical potential of the material can be tuned to fall inside the band gap and therefore suppress the bulk conductivity. On the other hand, a topological insulator can also be tuned to a bulk superconductor. This means that Cooper pairing is possible in a topological insulator with implications for study of Majorana fermion physics and potential quantum computing devices. Moreover, detection of the surface currents is a crucial first step in the investigation of novel phenomena, such as axion electrodynamics, in magnetic doped topological insulators.

Advanced Microcontrollers in the Chemistry Laboratory: Stirred and Temperature-Regulated Reaction

Dr. Rex E. Gerald, Dept. of Chem., MS&T

Role of NACA in Radiation Induced Oxidative Stress in Cancer Therapy

Rakesh Kacham, Dept. of Chem., MS&T

Comparative Evaluation between N-Acetyl Cysteine and N-Acetyl Cysteine Amide in Acetaminophen-Induced Oxidative Stress

Ahdab N. Khayyat, Dept. of Chem., MS&T

Abstract: Acetaminophen (APAP) is the most widely used pharmaceutical analgesic-antipyretic agent in the world, but its toxicity is a common cause of drug-induced hepatotoxicity. With APAP toxicity, cellular glutathione (GSH) is depleted. This results in the availability of N-acetyl-p-benzoquinone imine (NAPQI) that binds to cellular macromolecules, which leads to cell necrosis. N-acetyl cysteine (NAC), a GSH precursor, is the only approved antidote for an acetaminophen overdose. It is a negatively charged molecule that diminishes its penetration into the cells, thereby requiring fairly high doses that increase the side effects. In addition, oral and I.V. administration of NAC in a hospital setting is laborious and costly. Recently, a neutral compound that is structurally very similar to NAC (an amide form of NAC, called NACA) has been developed to improve NAC’s bio-availability.Therefore, in this study, we conducted an investigation to determine the mechanism of APAP- induced hepatotoxicity. We also evaluated the hepatoprotective effectiveness of NACA and compared it with NAC in the hepatic cell line, HepaRG. This comparison was based on several oxidative stress parameters, including the levels of intracellular reactive oxygen species, GSH, various antioxidant enzyme activities, mitochondrial membrane potential, and lactate dehydrogenase levels. Our preliminary data shows a dose-dependent decrease in cell viability in HepaRG cells upon exposure to APAP for 24 hours. The cell viability decreased to approximately 50% of the control when treated with 20mM APAP which increased to 70% upon NACA pretreatment. Oxidative stress parameters, upon NACA and NAC pretreatment are compared and discussed.

 

2013

General Laboratory Safety Training

Phyllis Lewis, Environmental Specialist, Environmental Health and Safety

Abstract:

Hazardous Waste Management

  • Federal Regulation & University Policy
  • Types of waste handled by Environmental Health and Safety
    • Chemical, Bio-hazardous, Universal
  • Proper storage of wastes
  • Proper labeling of wastes
  • Filling out the waste pick-up request form
  • Fire Safety (10 minute video)
  • Spill Response 

Laboratory Safety

  • General laboratory housekeeping
  • Safety policies
  • Common hazards in the laboratory
    • Chemicals, Bio-hazards, Radiation, Compressed Gas Cylinders
  • Labeling & Storage
  • Chemical inventory:  Chemtrack
  • Personal Protective Equipment
  • Emergency Response

Using Agricultural By-products as Sorbents to Treat Metal Pollution

Dan Yongbo, Dept. of Chem., MS&T

 

Dynamics of Cycloaddition Reactions

Dr. Lai Xu, Dept. of Chem., MS&T

 

Mechanically Strong Nanoporous 3D Assemblies of Metal, Polymer, and Carbon Aerogels

Shruti Suryakant Mahadik, Dept. of Chem, MS&T

 

Nanostructure-initiator Mass Spectrometry with Acoustic Depostition: Multiplexed, High-throughput Pipeline for Metabolic and Enzymatic Activity Screening

Xiaoliang Cheng, Life Science Division, Lawrence Berkeley National Laboratory

Abstract: A major challenge in Synthetic Genomics is the disconnect between the rate of gene discovery and functional analysis. Determining the function of a gene now requires a disproportionate amount of effort relative to that required for gene identification. Similarly, construction of multigene pathways for biofuel production is relatively straightforward and results in enormous clone libraries, however, only a small fraction of clones can be tested due to analysis constraints inherent with traditional LC/GC-MS analysis. We are addressing this analytical bottleneck using acoustic printing to transfer nanoliter volumes onto nanostructure-initiator mass spectrometry surfaces, enabling us to perform 10,000’s of assays/day, an increase in throughput of 1000-fold. This effort will serve as the foundation in the development of this new technology that will have several applications, including enzyme "cocktail" engineering for enhanced performance in industrially relevant biorefining operating environments for the production of sugars from biomass.

 

Isocyanate Derived Organic Aerogels

Chakkaravarthy Chidambareswarapattar, Dept. of Chem., MS&T

Abstract: Aerogels are bulk monolithic materials, consisting of 3D assemblies of nanoparticles with high open porosity, high surface areas and are pursued for thermal insulation.  After the synthesis of resorcinol-formaldehyde (RF) aerogels in 1989, for a number of years “organic aerogels” and “RF-aerogels” were almost synonymous terms.  This is slowly changing as other classes of organic aerogels show up in the literature, including polyurethane, polyurea and more recently polystyrene, polybenzoxazine, polydicylcopentadiene and polyimide (PI) aerogels. The latter are pursued for the good chemical resistance, excellent mechanical properties and high thermal stability of their polyimide skeletal framework.  Typically, polyimides are synthesized from a di-anhydride and a diamine with the classic DuPont two-step process via polyamic acids, which are converted to polyimides chemically with the use of dehydrating agents (e.g., acetic anhydride) along with base catalysts (e.g., pyridine).  The first PI aerogels were described in 2006, and they were synthesized by that route.  Here, we report polyimide aerogels via an alternative one-step room-temperature route that involves reaction of the same dianhydrides with the corresponding diisocyanates. The final aerogels are chemically indistinguishable (by IR and 13C CPMAS NMR) from those synthesized via the polyamic acid route. However, in terms of properties, the two materials are vastly different. Aerogels synthesized via the isocyanate route are nanofibrous as opposed to nanoparticulate morphology obtained from the amine route.

Following our successful synthesis of PI aerogels via the one-step isocyanate route [1], we have correlated bulk mechanical properties with the structure of the monomers.  Thus, realizing the importance of multifunctional monomers in terms of imparting mechanical strength, we resort into a trifunctional isocyanate [tris(4-isocyanatophenylmethane): Desmodur RE; courtesy of Bayer, Corp. USA] with two different di-anhydrides, pyromellitic dianhydride (PMDA) and benzophenone tetracarboxylic dianhydride (BTDA).  The resulting polyimide aerogels, PI-PMDA and PI-BTDA, are stable up to 400 oC (by TGA), as expected from polyimides. Despite relatively high bulk densities by aerogel standards (up to 0.6-0.7 g cm-3) and a decrease in porosity (down to ~50% v/v) PI-PMDA remain mesoporous and have high surface area (up to 435 m2 g-1). On the other hand, with the same primary particle sizes, PI-BTDA shrink less, have lower bulk densities and higher porosities (up to 80%). Clearly, decreasing the molecular rigidity of the dianhydride (from PMDA to BTDA) has an immediate impact on the material properties of the resulting aerogels. Both kinds of PI aerogels are extremely robust materials with high energy absorption capabilities (e.g., PI-PMDA: 82±4 J g-1 at 0.68 g cm-3; PI-BTDA: 47±1 J g-1 at 0.37 g cm-3).  Upon pyrolysis at 800 oC under Ar, PI aerogels are converted to carbon aerogels in high yields (52-59 % w/w).   Along the way, design of other isocyanate derived organic aerogels is briefly discussed.

 

 

Grabbing Scorpions: Fast, Functional Resin-Supported Chelates

Prof. Patrick Desrochers, Dept. of Chem., University of Central Arkansas

Abstract: The rapid one-pot synthesis of a functional scorpionate using microwave assisted methods will be described.  Despite the 50+ year history and vitality of the scorpionate field (typically hydrotris(pyrazolyl)borate chelates used with every metal on the periodic table), the development of heterogeneous supported scorpionates is still in its infancy, with our own work (Inorg. Chem. 2011) representing one of only a handful of examples.  The promise is great: couple the benefits of mature ligand development with the proven utility of heterogeneous systems.  Immobilized metal affinity chromatography and high-throughput combinatorial methods are two such areas that could benefit from the use of versatile metal scorpionate chelates. The challenge is also great: supported scorpionates are generally difficult or expensive to make.  Therefore, we demonstrate that such chelates can be reproducibly prepared inexpensively in a single step by MW irradiation of a mixture of pyrazole, NaH, and resin-supported phenylboronic acid.  Results will demonstrate this supported-chelate is fully functional.  Active coordination complexes of Cr(III), Cu(II), Co(II), and Rh(I) will be described.  This area of research has great potential to significantly benefit the inorganic discipline and by association, the biochemical, material, and industrial applications it serves

Chasing Trilobites: The Ordovician Period of the Anti-Atlas Mountains

Dennis L. Whitney, Environmental Engineer, American Airlines, Retired

Abstract: During the Ordovician period, which was approximately 490 to 445 million years ago, the Ozark Plateau, which contains Rolla, Jefferson City, and Springfield, was near the equator and on the eastern coast of the North American massif, whereas the Anti-Atlas Mountains of the Northwestern Sahara Desert were also near the equator and on the western shores of Gondwanaland. As a consequence, there is a very good chance that the paleoclimates of these two regions may have been very similar. However, the fossil record indicates that the paleoecology was perhaps dissimilar. Recently, fossil discoveries in the Atlas Mountains have revealed a new and diverse paleoecology. The discovery of this new fossil record has led to new insight into the nature of life in the Ordovician period.

On a recent trip to Morocco, the speaker investigated the quarries, where many of these fossils have been discovered. The new discoveries will be discussed along with their significance to the paelogeography and paleoecology of the Ordovician formations to both the Anti-Atlas Mountains and the Ozark Plateau. The significance of the different paelofaunas of the two regions will be discussed and fossil specimens will be displayed in order to support the discussion.

The comparison of these two paleoecologies indicates that the eastern shore of the North American massif possibly had a different paleoecology than the western shores of Gondwanaland. The fossil record in the Ozarks consists of mostly mollusks, whereas the fossils discovered in the Anti-Atlas Mountains reveal a rich diversity of living creatures, many of which are new to science. These ongoing discoveries are intriguing to scientists and have opened several new avenues of research into the evolution of life. 

 

Colloidal Unimolecular Particles

Sager Gade, Dept. of Chem., MS&T

Abstract: 

Part I. Molecular Weight and Functionality Effects on Colloidal Unimolecular Polymer Formation and Stability

The formation of anionic stabilized colloidal unimolecular polymer, CUP, particles from single polymer strands was investigated as a function of molecular weight.  The CUP particle size was correlated with the absolute molecular weight and its distribution.  The characteristics of the particles were evaluated with respect to viscosity, acid number, size distribution and stability.  The particle size varied from less than three nanometers to above eight nanometers representing polymers with molecular weight in the range of 4,000 to 153,000. Lower molecular weight polymers were found to be unstable due to insufficient ionic stabilization.

Part II. Synthesis of Amino Functional Colloidal Unimolecular Polymer Particles and their Use as Epoxy Curing Agents

The synthesis and utilization of cationic stabilized CUP particles utilizing a low Tg acrylic polymer for the curing of epoxy resins. Copolymer of ethyl acrylate / acrylic acid were synthesized and reacted with aziridine to produce amino modified polymer and hence cationic stabilized CUP particles. This copolymer exhibits cold flow and produce a continuous film. Use of these CUP particles as epoxy curing agents was investigated. 

 

Colloidal Semiconductor Quantum Belts, Platelets, and Magic-size Nanoclusters

William E. Buhro, George E. Pake Professor of Arts & Sciences Chair, Dept. of Chem., Washington University, Saint Louis, MO

Abstract: Pseudo-1D nanocrystals such as quantum wires (QWs) and quantum belts (QBs, nanoribbons) are in principle capable of transporting energy (excitons) and charge over long distances, and thus may have applications in solar-energy conversion and other technologies.  However, excitons and charge carriers in QWs and QBs sample extremely large surface areas and thus have a high probability of encountering surface trap sites, precluding efficient transport.

          I will describe semiconductor QBs in which excitons are efficiently delocalized over the entire length of the nanostructures, and the photoluminescence efficiencies are as high as 40%, rivaling those of quantum rods.  Crystalline, colloidal CdSe quantum platelets (QPs) are prepared at room temperature.  The QBs and QPs are obtained from (CdSe)13 nanoclusters entrained within lamellar-template structures.  Their excellent optical properties result from the smooth facets and effective passivation afforded by the template synthesis, which minimize surface trap-site populations.  The isolation and characterization of [(CdSe)13(n-alkylamine)13] derivatives will also be described.

 

Carbon Dioxide Capture and Hydrocarbon Separations in Metal-Organic Frameworks

Jeffrey R. Long, Materials Sciences Divison, Lawrence Berkely National Laboratory and Dept. of Chem., University of California-Berkeley

Abstract: Owing to their high surface areas, tunable pore dimensions, and adjustable surface functionality, metal-organic frameworks (MOFs) can offer advantages for a variety of gas storage and gas separation applications.  In an effort to help curb greenhouse gas emissions from power plants, we are developing new MOFs for use as solid adsorbents in post- and pre-combustion CO2 capture, and for the separation of O2 from air, as required for oxy-fuel combustion.  In particular, MOFs with open metal cation sites or alkylamine-functionalized surfaces are demonstrated to provide high selectivities and working capacities for the adsorption of CO2 over N2 under dry flue gas conditions.  Breakthrough measurements further show compounds of the latter type to be effective in the presence of water, while calorimetry data reveal a low regeneration energy compared to aqueous amine solutions.  MOFs with open metal cation sites, such as Mg2(dobdc) (dobdc4– = 2,5-dioxido-1,4-benzenedicarboxylate), are highly effective in the removal of CO2 under conditions relevant to H2 production, including in the presence of CH4 impurities.  Redox-active Fe2+ sites in the isostructural compound Fe2(dobdc) allow the selective adsorption of O2 over N2 via an electron transfer mechanism.  The same material is demonstrated to be effective at 45 °C for the fractionation of mixtures of C1 and C2 hydrocarbons, and for the high-purity separation of ethylene/ethane and propylene/propane mixtures.  Finally, it will be shown that certain structural features possible within MOFs, but not in zeolites, can enable the fractionation of hexane isomers according to the degree of branching or octane number.

 

Investigation and Identification of Existing Contaminants in the Environment

Ruipu Mu, Dept. of Chem., MS&T

 

Formal Music Instruction in Grades 5 through 12 Improves Performance in Undergraduate Science and Engineering

Robert Cesario, Dept. of Arts, Languages, and Philosophy, Director of Bands and Orchestras, MS&T

Abstract: 

Introduction. Universities have made efforts to increase capacity to alleviate the shortage of professional nurses, scientists, and engineers. While admission numbers have increased, attrition in undergraduate programs remains high. Stringent admission criteria exist, but educators strive to identify additional criteria that are better individual predictors of success. Filling a limited number of slots with students who are unlikely to succeed expends increasingly sparse resources of time, money, clinical, and laboratory space. Evidence suggests that participation in organized music groups is associated with greater ability in math, reading, cognition, critical thinking, verbal skills, motivation, concentration, confidence, and teamwork. The purpose of this study was to determine if formal music instruction in grades 5 through 12 were associated with improved performance in undergraduate nursing programs and, by extension, presumably science and engineering programs.          

Methods. The anonymous, online, survey examined the following hypotheses. Undergraduate students who participated in organized music instruction in grades 5 through 12 are more likely to (1) graduate from their chosen programs than students who have not had this experience, (2) have higher grade point averages upon finishing their degrees, and (3) do well on subsequent professional exams. In addition, it was hypothesized that there would be a positive relationship between duration of music instruction between grades 5 and 12 and the exit GPA of undergraduate students. For the survey all 78 accredited associate degree, diploma, and baccalaureate level nursing programs in Texas were invited to participate, yielding 306 completed surveys. 

Results. The three hypotheses were supported (p < 0.001). Of those who had graduated from a nursing program, a greater proportion, 64.8 %, had been in some type of organized music program. Graduates who had participated in music programs had average GPAs between 3.5 and 3.79 at graduation; whereas those who were not in music programs had GPAs between 3.0 and 3.19. A greater proportion of those who had been involved in an organized music group obtained their professional qualifications on their first attempt. The study also revealed that GPA correlated positively with number of years of music instruction (p < 0.01).

Conclusions. Organized music participation data is objective, quantifiable, and can be collected quickly and inexpensively as it is readily available on the ACT and SAT student profiles. Music in public schools is available to almost all students in the state of Texas and thereby mediates potential bias of race, ethnicity, or socio-economic status. When selecting students for a limited number of nursing, science, and engineering schools, valid predictive criteria are essential and musical educations seems to be highly useful tool in this regard.

 

General Laboratory Safety Training

Phyllis Lewis, Environmental Specialist, Environmental Health and Safety

Abstract: 

Hazardous Waste Management

  • Federal Regulation & University Policy
  • Types of waste handled by Environmental Health and Safety
    • Chemical, Bio-hazardous, Universal
  • Proper storage of wastes
  • Proper labeling of wastes
  • Filling out the waste pick-up request form
  • Fire Safety (10 minute video)
  • Spill Response

Laboratory Safety

  • General laboratory housekeeping
  • Safety policies
  • Common hazards in the laboratory
    • Chemicals, Bio-hazards, Radiation, Compressed Gas Cylinders
  • Labeling & Storage
  • Chemical inventory:  Chemtrack
  • Personal Protective Equipment
  • Emergency Response

 

Microwave Spectroscopy and the New Millenium: Advancing Technology in Two Directions

Garry S. Grubbs, Dept. of Chem., MS&T

Abstract: Microwave spectroscopy has long been a useful tool for studying and characterizing geometric and electronic structure of gas phase molecules and their interactions. This work describes the construction and implementation of two modern microwave instruments: the cavity Fourier transform microwave (FTMW) and chirped pulse Fourier transform microwave (CP-FTMW) spectrometers. These spectrometers have been equipped with a laser ablation, pulsed supersonic nozzle which allows for the study of many species, both typical and exotic. This technology has also opened the door to spectroscopically study materials useful in creating transistors and microchips in the gas phase with exquisite precision. This can also be used as a tool to investigate typical processes utilized in the manufacturing of these technologies. Specific examples of study and characterization will be discussed.

 

Cancer Biomarkers: From Large to Small Molecules

Prof. Michael Wang, Dept. of Pathology, University of Missouri-Coumbia

Abstract: Life is a self-sustaining chemical process in a given organism.  Cancer is the first killer of human life in medicine.  Although there are great progresses in cancer research and clinical sciences in the past decades, cancer kills approximately 580,000 American citizens and 7.6 million people worldwide each year. From the medical perspective, prevention and early diagnosis of cancer are currently the most feasible solutions to reduce cancer mortality.  In this presentation, I will use lung cancer as an example to discuss the current development of cancer biomarkers, an important tool for early diagnosis of cancer.

     A cancer biomarker can be defined as the biological molecules found in blood or other biofluids or tissues as an indicator of the presence of cancer in the human body. These molecules may be the specific products of cancer cells or a specific response of the body to the presence of cancer.  The molecules may be the mutated DNA fragments, abnormally elevated or reduced mRNA or microRNA, proteins or peptides, and even the small metabolites.  In my lab, we utilize real-time PCRs as a basic methodology to detect DNA mutation, DNA methylation and microRNA levels as biomarkers in patient blood samples for early detection of lung cancer.  We have identified several specific aberrant DNA methylation loci and abnormally elevated microRNA molecules in blood samples that could distinguish early stage of lung cancer patients from non-cancer controls.  The test may be used for lung cancer screening or confirmation in the future. To further increase the sensitivity and accuracy of early cancer detection with an integrated strategy, identifying “oncometabolite” as a new type of cancer biomarker by cancer metabolomic study is a very promising direction. Scientists in chemistry will play a major role for this new discovery.

 

Chemistry Resources in the C.L. Wilson Library

Christopher Jocius, Head of Reference Department C.L. Wilson Library, MS&T

Abstract: An overview of the resources available for chemistry graduate students at the Missouri University of Science and Technology library will be presented. This will include how to access and use the ACS based Scifinder to search the chemical scientific literature.

 

Occurrence and Removal Study of Perchlorate Levels in Missouri Natural and Drinking Waters by Using Ion Exchange Chromatography- Tandem Mass Spectrometry

Danielle West, Dept. of Chem., MS&T

Abstract: Perchlorate (ClO4-) has been utilized for a wide range of purposes: munitions, explosives, solid rocket propellant, pyrotechnics, fertilizers, airbag inflators, fireworks, and other industrial applications. Because perchlorate is highly soluble and chemically inert in water, it can be transported vast distances in groundwater or rivers. Therefore, perchlorate can exist in the natural water and drinking water due to its difficulty to be removed by the current water treatment processes. The US EPA has conducted perchlorate occurrence studies and found perchlorate contamination in both groundwater and surface waters serving as drinking water sources for more than 16 million people in at least 26 states nationwide in USA. Perchlorate has been detected in over 4% of public water systems nationally at the level of greater than or equal to 4 µg/L.  Missouri has large agricultural use of fertilizer, legal use of fireworks, and an U.S. army base, all of which could contribute to perchlorate contamination to our drinking water.  For these reasons, Missouri University of Science and Technology and the Missouri Department of Natural Resources have collaborated in developing a sensitive ion exchange chromatography – tandem mass spectrometry (IC-MS/MS) method for direct analysis of perchlorate without any preconcentration procedures.  The method has been applied to screen for the occurrence level of perchlorate in drinking water at 19 water facilities across the state of Missouri and the removal thereof.

 

An Overview of Patent Law and What to Expect when Preparing and Submitting a Patent

Rebecca Rich, Patent Attorney, Brewer Science Inc., Rolla, MO

Abstract: The patent process can be confusing for scientists, both in industry and academia. This presentation is intended help familiarize you with patent terminology, patent law, and the patent process, and the implications for your research, publications, and potential commercialization. We will cover when filing a patent is appropriate, what to do before your patent is filed, the parts and filing of the patent application, the patent prosecution process, and patent issuance. Patent inventorship, ownership, and rights granted in a patent will be presented, with an emphasis on universities and government-funded research. Recent changes in US patent law will be discussed, as well as an overview of international patent filing. A brief discussion of careers in patent law will be included.

 

Strong Magnetic COupling and Single-Molecule Magnet Behavior in Azophenine Radical-Bridged Dinuclear Complexes

David Harris, Rang Jeon, & Jesse Park, Dept. of Chem., Northwestern University

Abstract: This presentation will describe our efforts to synthesize single-molecule magnets with well-isolated spin ground states by employing radical bridging ligands. In particular, a series of dinuclear metal complexes of the bridging ligand azophenine has been synthesized. Chemical reduction of the iron congener affords a one-electron-reduced species. X-ray diffraction and Mössbauer spectroscopy confirm that the reduction occurs on azophenine to give an S= 1⁄2 radical bridging ligand. Dc magnetic susceptibility measurements demonstrate the presence of extremely strong direct antiferromagnetic exchange between S = 2 Fe(II) centers and azophenine radical in the reduced complex, giving an S = 7/2 ground state with an estimated coupling constant magnitude of |J| ≥ 900 cm–1. Mössbauer spectroscopy and ac magnetic susceptibility reveal that this complex behaves as a single-molecule magnet with a spin relaxation barrier of  Ueff = 50(1) cm–1. To our knowledge, this complex exhibits by far the strongest magnetic exchange coupling ever to be observed in a single molecule magnet.

 

Molecular Models for the Study of Spin Relaxation and Magnetic Anisotropy

Danna Freedman, Dept. of Chem., Northwestern University

Abstract: Quantum computation has the potential to break the most commonly employed encryption scheme and to accurately simulate quantum systems. For these reasons quantum computation is a highly active area of research with numerous qubit candidates proposed thus far. Intuitively, electronic spin can behave in a quantum fashion, therefore could serve as a candidate qubit. Yet thus far research in the area has been hampered by rapid spin decoherence. While synthetic chemists are adept at designing molecules with the ideal spin manifold the design principles for the synthesis of molecules with long coherence time have not been established. Research demonstrating progress towards the first set of unifying principles for quantum computation will be presented with future directions in employing these design principles to synthesize new candidate qubit molecules.

 

Ethical Writing and the Graduate Student

Elizabeth Roberson, Technical Editor, Office of Graduate Studies, MS&T

 

Investigation of Fluid Flow Behavior in Nano-scale Channels Using Single Molecule Imaging System

Qihua Wu, Dept. of Chem., MS&T

Abstract: Many of unconventional tight gas reservoirs contain micro-scale or even nano-scale pores and channels, which are significantly different from conventional reservoirs. However, the fluid flow behavior in the nano-scale pores and channels is not well understood. In this study, a lab-on-chip approach for direct visualization of gas/water two phase flow behavior in nano-scale channels is presented. The nanofluidic-chips were designed and fabricated, and experiments of two phase flow in nano-scale channels with various depths were conducted. Images were captured by using epi-fluorescence microscopy method. The fluids velocities and pressure drop in the nano-scale channels were recorded and flow patterns were characterized. Three different flow patterns, single, annular and stratified flow were observed and their special features are described. Flow regime map was summarized and compared with results in conventional-size channels.

The drainage/imbibition processes in the nano-scale channels were also investigated. The residual saturations of gas or water in the nanochannels with different dimensions were compared. This work provides valuable information for better understanding the single and two phase flow behavior in the nano-scale channels. This study was financially supported by Research Partnership to Secure Energy for America (RPSEA).

Structural, Electronic, and Catalytic Properties of Metal Complexes Bearing "P-N-P" Ligands

Prof. Panayotis Kyritsis, Dept. of Chem., National and Kapodistrian University of Athens, Athens, Greece

Abstract: A common theme in structural bioinorganic chemistry is the presence of sulfur-containing ligands in the active site of metalloenzymes, most commonly in the form of cysteine thiolate (RS-). Very rarely, Cys is replaced by selenocysteine, Se(Cys).

Synthesis of M(II)L2 complexes (M = Mn, Fe, Co, Ni, Cu), with “P-N-P”-type of bidentate LH ligands R2P(E)NHP(E)R2 (E = S, Se; R = Ph, iPr), affords M(II)E4 metal sites with either tetrahedral or square-planar geometry.1-3 That series of complexes was recently extended to include octahedral complexes of the general formula: [M{(OPPh2)(EPPh2)N}2(sol)2], M = Mn, Co, Ni; E = S, Se; sol = dmf, thf, dmso.4 All those tetrahedral and octahedral complexes are paramagnetic, and therefore amenable to physicochemical methods that directly probe the magnetic centers. Recent investigations by Electron Paramagnetic Resonance spectroscopy, as well as their implications for the active sites of specific metalloproteins, will be discussed.5-7

“P-N-P”-type ligands have been also employed for the synthesis of Rh(I), Ni(II) and Pd(II) complexes, showing activities towards hydroformylation,8 polymerization9 and C-C coupling reactions,10 respectively. With proper design of the “P-N-P” ligand framework, such catalysts can be immobilized onto silica, mesoporous molecular sieves and clay solid supports, affording active heteregeneous catalytic systems.

 

Geological Indicators of Earth's Climatic Conditions in the Past

Prof. Wan Yang, Dept. of Geological Sciences and Engineering, MS&T

Evolution of General Chemistry Instruction at MS&T

Travis McDowell, Dept. of Chem., MS&T

Abstract: During the last seven years the general chemistry course at Missouri S&T has undergone many changes to better serve the ever-changing incoming student body.  At this point, nearly every aspect of the course has undergone adjustments.  These adjustments have been necessary to facilitate an improved learning experience for the students and maintain relevance due to the growing list of alternatives for student learning.  On the learning side of things, changes made were to improve student communication, information delivery, the assessment methods employed.  With regards to all changes other factors, such as minimizing the cost of operation while also maximizing the time efficiency of graduate students and faculty involved, were observed.   

New Quantitative NMR Techniques for Determining the Product Yield of Hydrothermal Biomass

Lingyu Chi, Dept. of Chem., MS&T

Abstract: Hydrothermal biomass-to-fuel reactions are a viable pathway for generating liquid biofuels. Newly developed, quantitative HNMR techniques are employed to identify reaction intermediates, understand the mechanisms, and study the kinetics of hydrothermal biomass reactions. The investigations are carried out in a 5-mm NMR tube with a 1-mm capillary tube insert filled with an integration reference standard, so that the aqueous sample drawn from the reactive solution is isolated from the D2O lock and the external integration and chemical-shift reference. The external integration reference standard can be used to accurately report mass percentages of biomass reaction products. This presentation will identify some of the practical aspects pertaining to HNMR-based quantitative analysis and highlights some of the limitations, uncertainties, and applications of this particular approach to the analyses of biomass reaction products.

2014

General Laboratory Safety Training

Phyllis Lewis, Environmental Specialist, Environmental Health and Safety

Abstract: 

Hazardous Waste Management

  • Federal Regulation & University Policy
  • Types of waste handled by Environmental Health and Safety
    • Chemical, Bio-hazardous, Universal
  • Proper storage of wastes
  • Proper labeling of wastes
  • Filling out the waste pick-up request form
  • Fire Safety (10 minute video)
  • Spill Response

Laboratory Safety

  • General laboratory housekeeping
  • Safety policies
  • Common hazards in the laboratory
    • Chemicals, Bio-hazards, Radiation, Compressed Gas Cylinders
  • Labeling & Storage
  • Chemical inventory:  Chemtrack
  • Personal Protective Equipment
  • Emergency Response

 

N-acetylcysteine Amide, a Thiol Antioxidant that Prevents Bleomycin-induced Toxicity

in Human Alveolar Basal Epithelial Cells

Maria Fan, Dept. of Chem., MS&T

Abstract: Bleomycin (BLM), a glycopeptide antibiotic from Streptomyces verticillus, is an effective antineoplastic drug. However, its clinical use is restricted due to the wide range of associated toxicities, especially pulmonary toxicity. Oxidative stress has been implicated as an important factor in the development of BLM-induced pulmonary toxicity. Previous studies have indicated disruption of thiol-redox status upon BLM treatment. Therefore, this study focused on (1) investigating the effects of BLM on A549 cells and (2) elucidating whether N-acetylcysteine amide (NACA) provides any protection against BLM-induced toxicity.  Oxidative stress parameters, such as glutathione (GSH), malondialdehyde (MDA), and antioxidant enzyme activities were altered upon BLM treatment. Loss of mitochondrial membrane potential, as assessed by fluorescence microscopy, indicated that cytotoxicity is possibly mediated through mitochondrial dysfunction. Pretreatment with the thiol antioxidant NACA reversed the oxidative effects of BLM. NACA decreased the reactive oxygen species (ROS) and MDA levels and restored the intracellular GSH levels. Our data showed that BLM induced A549 cell death by a mechanism involving oxidative stress and mitochondrial dysfunction. NACA had a protective role against BLM-induced toxicity by inhibiting lipid peroxidation, scavenging ROS, and preserving intracellular GSH and mitochondrial membrane potential. NACA can potentially be developed into a promising adjunctive therapeutic option for patients undergoing chemotherapy with bleomycin.

 

 

Electrokinetic and Rheological Study of CUPs

Ameya Natu, Dept. of Chem., MS&T

 

Mechanism Study of Zine Oxide Nanoparticles Cytotoxicity

Qingbo Yang, Dept. of Chem., MS&T

Synthesis, Characterization, and Application of Hydroxyl Acid Capped Oligopeptides as a Selective Substrate in a Trypsin Inhibitor Assay

Jinyu Du, Dept. of Chem., MS&T

Applications of Solid State NMR

Prof. Dewey Barich, Dept. of Chem., University of Kansas

Abstract: Solid State NMR (SSNMR) is a powerful analytical technique that offers multiple investigative avenues for studying a wide range of materials and properties.  Materials as varied as fine organics, catalysts, soils, lignins, carbonaceous materials, minerals, and biological materials have been studied using SSNMR.  This seminar will present several examples including quantitation of physical forms, structural information of complex materials, and conformational detail in crystalline materials.

 

Aerogels as Diverse Nanomaterials

Abhishek Bang, Dept. of Chem., MS&T

Abstract: 

A. Polyurea-crosslinked dysprosia aerogels for drug delivery applications. Aerogels are promising materials as multifunctional drug delivery carriers. In this context, we investigated bio-compatible polymer-crosslinked dysprosia (X-DyOx) aerogels as drug delivery vehicles and demonstrated storage and release of paracetamol, indomethacin and insulin in phosphate buffer (pH = 7.4) or 0.1 N HCl (pH = 1) at 37 OC. As controls we used: (a) orderly-mesoporous silica (n-SiOx-MP4-T045), (b) macroporous polymer-crosslinked silica (X-SiOx-MP4-T045),and (c) randomly mesoporous polymer-crosslinked amine-modified silica (X-TMOS-co-APTES) aerogels. Drug uptake was significantly higher with X-DyOx (up to 35% w/w) relative to n-SiOx-MP4-T045 and X-SiOx-MP4-T045 (16-19% w/w), and was comparable to that of X-TMOS-co-APTES aerogels (up to 30% w/w). X-DyOx aerogels have shown much slower release rates (100% release in ~60 h) than their counterparts, whereas very fast to moderate drug release behavior was observed (100% release in 0.5 to 24 h). Considering that dysprosia is strongly paramagnetic, hence, can be focused magnetically, and can be also neutron-activated, X-DyOx-based materials have the potential of becoming multifunctional drug delivery vehicles.

B. Flexible polyurethane-acrylate aerogels for thermal insulation and environmental remediation. Flexible aerogels are particularly attractive materials for thermal insulation of sub-sea oil pipes, cryogenic tanks and oil-spill absorption, whereas a high degree of foldability is desirable. Herein, we report flexible aerogels via polyurethane-acrylate chemistry. For this, we designed a star shape monomer possessing urethane linkages of a triphenylmethane core with acrylate moieties. For comparison reasons, ethylene glycol dimethacrylate or 1,6-hexanediol diacrylate are used as variable length chain extenders, and their effect on the material properties of the resulting polyurethane-acrylate aerogels was investigated. Lower density polyurethane-acrylate aerogels (~0.14 g cm-3)were macroporous and flexible (by 3-point bending test), while higher density samples (0.66 g cm-3) were rigid and mechanically strong (by compression testing). Those properties were independent of the chain length of the extender, pointing to a nanoscopic origin for their flexibility, rather than to a molecular one.

C. Polydicyclopentadiene (pDCPD) aerogels: Nanostructure control via ring opening metathesis polymerization (ROMP) induced with Grubbs catalysts I and II.  pDCPD polymers synthesized via ROMP are emerging as attractive materials for diverse applications ranging from separation media to body armor. They are synthesized from readily available dicyclopentadiene (DCPD), an inexpensive byproduct of petroleum refinery. Here, we developed pDCPD-based aerogels using two different Grubbs catalysts (GC-I and GC-II) with different catalytic activity towards ROMP. pDCPD based wet-gels synthesized from GC-II show excessive swelling in toluene (up to 200% v/v) followed by de-swelling and uneven shrinkage in acetone, resulting in severely deformed aerogels. However, wet-gels using GC-I retain their shape throughout processing. Percent crosslinking calculated via solid state 13C NMR shows that GC-II-catalyzed pDCPD aerogels undergo only 4-5% crosslinking as compared to 17-23% when GC-I is used. Microscopically, pDCPD aerogels derived from GC-I and GC-II catalysts show different morphology (fibrous and particulate, respectively).

General Laboratory Safety Training

Phyllis Murphy, Environmental Specialist, Environmental Health and Safety

Abstract: 

Hazardous Waste Management

  • Federal Regulation & University Policy
  • Types of waste handled by Environmental Health and Safety
    • Chemical, Bio-hazardous, Universal
  • Proper storage of wastes
  • Proper labeling of wastes
  • Filling out the waste pick-up request form
  • Fire Safety (10 minute video)
  • Spill Response

Laboratory Safety

  • General laboratory housekeeping
  • Safety policies
  • Common hazards in the laboratory
    • Chemicals, Bio-hazards, Radiation, Compressed Gas Cylinders
  • Labeling & Storage
  • Chemical inventory:  Chemtrack
  • Personal Protective Equipment
  • Emergency Response

Recent Advances on Pebble Bed Nuclear Reactor Dynamics by Developing Advanced Measurement and Computational Techniques

Prof. Muthanna Al-Dahhan, Dept. of Chemical and Biochemical Engineering, MS&T

Structure-Property Studies in Photoresponsive Cyanometalates

Stephen M. Holmes, Dept. of Chem. & Biochem., UMSL

Polyacrylamide Microgels via Water-Free Inverse Emulsion Polymerization

Zun Chen, Dept. of Chem., MS&T

 Abstract: Crude oil is an internationally important commodity raw material for energy and chemical industries. After primary, by natural pressure, and secondary, by water and gas driven, stages of oil recovery from a well field source, more than two thirds of the original oil remain in the reservoir. In these tertiary reservoirs, the directly water- or even polymer-flooding assisted recovery of reservoir resources are not efficient for displacing resource fluid due to severe heterogeneity of the geologic formations.  The displacing agents, e.g., water, prefer low resistance wide pore channel flow of low pressure resistance compared to narrow pore, high pressure resistance flow. Therefore, excess water production becomes a major problem, which leads to early abandonment of otherwise unrecoverable hydrocarbon resources. To solve this problem, polymer gel treatments of the injection wells are being developed to preferentially limit flow through the ‘thief’ zones.  Polymer gels can be cost-effective methods to improve sweep efficiency to reduce excess water production during oil recovery. We describe a novel polyacrylamide microgel synthesis by a pseudo-inverse emulsion polymerization in the absence of water. Two different crosslinkers are employed in this study to give the particle ‘smart’ properties, e.g., 2 stages of size expansion that are temperature sensitive. When put into water, the original dry particle can swell by as much as 25 times in size under low temperature (e.g., 40 ? C).  Exposure to a harsh reservoir environment, for instance, the stimuli of high temperature (e.g., 90 ? C), can induce cleavage of one of the two crosslinking types to enable further expansion. The microgel access to targeted pore channels is thus controlled to realize changes in the reservoir flow profile within the geologic formation.

Conversion of Electrodeposited Co(OH)2 to CoOOH and Co3O4 and a Comparison of their Catalytic Activity for the Oxygen Evolution Reaction

Ying-Chau Liu, Dept. of Chem., MS&T

Accelerating Functional Genomics Using Mass Spectrometry

Dr. Trent R. Northen, Lawrence Berkeley National Laboratory, Berkely, CA

Abstract: Microorganisms exhibit complex metabolism and metabolic interactions with their environment, large parts of which remain unknown. Deficiencies in functional annotations of microbial genomes as well as incomplete knowledge of small molecule repertoires (metabolomes) of microorganisms limit the understanding of their metabolism. This talk will introduce mass spectrometry based metabolomics and approaches to link these to microbial genomics. Including recent work connecting genes to the utilization of specific metabolites in bacteria by profiling metabolite utilization in libraries of mutant strains. Here, untargeted mass spectrometry-based metabolomics was used to identify metabolites utilized by soil microbes. Targeted high-throughput metabolite profiling of spent media of 8042 individual mutant strains was performed to link utilization to specific genes. Using this approach we identified genes of known function as well as those required for the metabolism of ‘novel’ metabolites. This work is being extended for the high throughput characterization of novel natural products using acoustic printing of nanoliter volumes coupled to nanostructure initiator mass spectrometry (NIMS). 

Chromic Phenomena- Reversible Color Change Chemistry

Dr. Harlan J. Byker, Chief Executive Officer, Pleotint, LLC

Abstract: Electrochromic, thermochromic, and photochromic technologies have been used in many intensive and expensive attempts at commercial product development over the last 50 years. The chemistry and materials behind chromic technologies are described and a discussion of the commercialization attempts is given. A particular focus is given to the use of thermochromic materials for sunlight responsive, dynamic, energy saving windows which are now starting to be commercialized.

The Challenges and the Fun of Internal Rotation in Rotational Spectroscopy

Dr. Peter Groner, Dept. of Chem., UMKC

Abstract: Internal rotation and other large-amplitude motions (LAMs) in molecules affect rotational, vibrational and electronic energy levels and their respective spectra. Manifestations of the interactions between internal rotation and these other degrees of freedom are the appearance of spectra of conformers and shifts or splittings of spectral lines. A short review of the basics of rotational and vibrational spectroscopy is followed by explanations and illustrations of these effects. They become more interesting and more challenging in the presence of two or more LAMs. Significant progress has been made over the last two decades in instrumental and experimental techniques (sensitivity, resolution), data analysis and theoretical developments to study and understand the effects of internal rotation. For molecules with one or two methyl group internal rotors, it is now possible most of the time to assign and fit thousands of spectral lines to experimental precision and to high rotational quantum numbers. Thorough analysis of spectra may provide information about torsional potential functions, heights of barriers to internal rotation, and conformational energy differences. Barriers determinable by rotational spectroscopy are lower than barriers determinable by NMR. The spectroscopy of molecules with internal rotation has found applications in radio-astronomy and the planetary sciences.

 

New Cathode Materials for Li-ion Batteries

Hooman Yaghoobnejad Asl, Dept. of Chem., MS&T

Abstract: Li-ion batteries play an essential role for powering-up a variety of equipment, from small portable electronic devices to heavy Electric vehicles (EVs). Research and development in this field is actively proposing new and alternative chemistries in cathode design from transition metal oxides in the first generation of these batteries to polyanion-based (PO4, SO4, SiO4, and BO3/BO4) compounds. In this context we are utilizing new synthesis routes to make novel compounds with combinations of different polyanions and transition metal compounds. The advantage of using polyanions rather than pure oxide in cathode composition is the added safety feature that comes from the strong covalency between the oxygen atom and the central main group element (P, S, B, or Si) in the polyanion. The presentation will focus on three new compositions Li3Fe2(HPO3)3Cl, LiFePO4NO3 and LiFeB(PO4)2(H2O)2, recently discovered in our laboratory that show promising electrochemical activity for Li-ion battery. The details of synthesis, structure determination employing X-ray diffraction (single-crystal and powder) and results of electrochemical studies in Li-ion cells towards reductive lithiation and oxidative delithiation will be discussed. This presentation will also cover how fluoride substitution can tune the cell voltage in a particular structure type, namely tavorite, LiFePO4(OH)xF1-x where 0≤x≤1. In the conclusion a discussion relating the structure to the cell performance and also a comparison with some of other known cathode materials will be presented.

Innovative Applications of Polymeric Materials in Microelectronic Devices- An Overview of Brewer Science Technologies

Dr. Tony D. Flaim, Brewer Science Inc., Rolla, MO

 

Synthesis and Characterization of Vanadium Oxide Nanomaterials for Li-ion Battery Cathodes

Tyler Fears, Dept. of Chem., MS&T

 

Effects of the Novel Thiol Antioxidant N-acetylcysteineamide Eyedrops on Reversing Sodium Selenite-induced Cataracts in Wistar Rats

Sri Krishna Yasaswi Maddirala, Dept. of Chem., MS&T

The Design and Application of a TPD Based Photorefractive Composite to Aberrated Image Restoration

Yichen Liang, Dept. of Chem., MS&T

Abstract: Organic photorefractive (PR) material has shown its considerable potential in practical applications due to its high figure of merits including low fabrication-cost, possibility of properties tuning by changing its composition and faster response time, etc [1]. In our approach, [1,1’-Biphenyl]-4.4’-diamine-N,N’-bis(3-methylphenyl)-N,N’-diphenyl (TPD) was used as the charge transfer matrix for the PR composite due to its high value of charge mobility among organic charge transporting materials. In addition, C60 and 4-azacycloheptylbenzylidene-malononitrile were included in the composites as photo-sensitizer and nonlinear chromophore, respectively. To improve the performance of PR material, quantum dots (QDs) were doped inside the composites, which results in a dramatic improvement of response time. By surface modification process, a charge transfer ligands capped QDs were synthesized and it showed a significant enhancement of photoconductivity in the TPD based composites. The designed PR material has shown its ability in phase aberration elimination. This demonstrates the value of PR material in optical communication applications.

 

 

2015

Theoretical Tools to Study Dynamics of Planetary Atmospheres

Moumita Majumder, Dept. of Chem., MS&T

Abstract: The evolution of planetary atmospheres speaks to the history of the creation of the universe. The physical and chemical environments of planetary atmospheres vary greatly between different planets, moons and other celestial objects. The types of life found on Earth rely on a limited range of conditions. Understanding the physical and chemical behavior of atmospheres requires tools to treat collisional reaction dynamics in the gas phase. This talk presents methods to compute accurate potential energy surfaces needed to predict the spectroscopy and dynamics of small species.

Quantum Dynamics of Small and Medium Sized Molecules: Applications to Atmospheric Chemistry, Astrophysics, and Combustion

Steve Ndengue, Dept. of Chem., MS&T

Simultaneous Determination of Additives and Contaminants for a Comprehensive Characterization of Dielectric Fluids

Carlo M. Roggero, Dept. of Chem., MS&T

DNA Engineering: from Structure to Application

Risheng Wang, Dept. of Chem., MS&T

Abstract: Deoxyribonucleic acid (DNA) is the carrier of generic information in living cells, which can replicate itself through Watson-Crick base paring.  Over the past three decades, researchers in the emerging field of DNA nanotechnology are using the DNA as structural nanomaterials to build addressable artificial nanostructures in one, two and three dimensions. These self-assembled nanostructures have been used to precisely organize functional components into deliberately designed patterns which have a wide applications in material science, biomedical, electronic and environmental fields. The development of DNA nanotechnology and its potential application will be covered.  Then my talk will discuss the design and construction of several DNA nanostructures including: self-assembly of DNA six-helix nanotubes from two half-tube components; Using DNA origami template to organize semiconducting quantum dots (QDs) and gold nanoparticles (AuNPs) and discussing the methods to integrate “top-down” nanofabrication technique with “bottom-up” self-assembly. 

Constructing Global Potential Energy Surfaces

Phalgun Lolur, Dept. of Chem., MS&T

 

In Vitro Study of Wound-healing Capabilities of Bioactive Glass Nanofibers under Various Culture Conditions

Sisi Chen, Dept. of Chem., MS&T

 Abstract: Bioactive glass materials have been developed and widely used for biomedical applications such as hard or soft tissue repair and regeneration. Recently developed borate-based, nanometer-scale, fiber-shaped glasses integrated many promising features and study results have shown that borate bioglass can promote both osteogenesis and angiogenesis, and thus triggered increasing interest in future wound-healing applications especially on soft tissues. However, the underlying biochemical mechanism is still largely unknown. In this study, three different micro- or nano-fibers, one silicate-based (45S5) and one bioactive borate glasses (13-93B3), and one copper/zinc (Cu/Zn) doped borate glass (1605), were examined to investigate their stimulation of vascular endothelial growth factor (VEGF) under varied culture conditions. An in vitro dynamic flow control system that mimics the niche environment of the vascular depletion and hyperplasia area in wound-healing regions was used to demonstrate the actual biological compatibility and functionality of the borate glass nanofibers. Cell growth and the secretion of VEGF were monitored along with the release of boron and other nanofiber constituents. The detailed experimental conditions and results under both static condition and dynamic flow condition will be presented and discussed at the seminar.  

 

Terrestrial and Extraterrestrial Studies of Nonexistent Compounds

Dennis J. Clouthier, Dept. of Chem., University of Kentucky

 Abstract: Powerful laser-based techniques have been developed over the last two decades for detecting transient and very reactive molecules in very low concentrations. With these methods we have been able to thoroughly characterize species which had previously been classified as "nonexistent" and unlikely to be observable. This talk will describe the technology and experimental techniques for preparing and studying such compounds including our first determination of the length of the carbon-silicon triple bond and the detection of a new phosphorus carbide in the laboratory and in outer space. Practical applications in the characterization of semiconductor growth intermediates, upper atmospheric chemistry, and the chemistry of the interstellar medium will also be discussed.  

 

Biomarker Discovery and Detection for Early Cancer Detection

Casey F. Burton, Dept. of Chem., MS&T

  

 

An Introduction to the Field of Explosives and Pyrotechnics

John Bowles, UTEC Corporation, Riverton, KS

  

 

Toward Automating Two-Dimensional Electrophoresis- a Hybrid Chip Devise for Protein/Peptide Separation

Prof. Shaorong Liu, Dept. of Chem. & Biochem., University of Oklahoma

Abstract: In this presentation, we introduce a chip-capillary hybrid device to integrate capillary isoelectric focusing (CIEF) with parallel capillary sodium dodecyl sulfate – polyacrylamide gel electrophoresis (SDS-PAGE) or capillary gel electrophoresis (CGE) toward automating two-dimensional (2D) protein separations. The hybrid device consists of three chips that are butted together. The middle chip can be moved between two positions to re-route the fluidic paths, which enables the performance of CIEF and injection of proteins partially resolved by CIEF to CGE capillaries for parallel CGE separations in a continuous and automated fashion. Capillaries are attached to the other two chips to facilitate CIEF and CGE separations and to extend the effective lengths of CGE columns. Specifically, we illustrate the working principle of the hybrid device, develop protocols for producing and preparing the hybrid device, and demonstrate the feasibility of using this hybrid device for automated injection of CIEF-separated sample to parallel CGE for 2D protein separations. Potentials and problems associated with the hybrid device are also discussed.

Untitled I

Stephanie L. Brock, Dept. of Chem., Wayne State University

 

Cytotoxicitiy is a Function of Multiple Chemical and Physical Properties of Engineered Nanomaterials

Prof. Yue-Wern Huang, Dept. of Biological Science, MS&T

 Abstract: It is estimated that by 2017, this field will represent a $48.9 billion market. As engineered nanoparticles (NPs) currently occupy a significant portion of the market and are anticipated to proliferate commercially, there is an urgent need to study their potential impact on human health and the environment.  In this seminar, I will present information with regard to what physicochemical properties of nanomaterials influence cytotoxicity. The properties investigated include band-gap energy, surface charge, relative available particle surface binding site, and metal dissolution. Furthermore, I will also present our recent findings in altered cell cycle and inhibition of cell proliferation. Collectively, this information could inform design of safer engineered nanomaterials.

Give Vitamin E Another Chance

Prof. Nukhet Aykin-Burns, Division of Radiation Health UAMS-College of Pharmacy, Little Rock, AR

 Abstract: Radiation therapy is frequently used to treat malignant conditions either alone or concomitant with other modalities. 95% of patients who have had radiotherapy suffer from both acute and chronic side effects. Thus, despite discoveries in radiation biology and improvements in radiation technology, there is still a significant need for a safe and effective radio-protector/radiomitigator compound to alleviate the side effects of radiotherapy on normal tissues.

Among the few most promising alternatives are the vitamin E analogs δ-tocotrienol (DT3) and g-tocotrienol (GT3). These compounds have shown significant radioprotectant and radiomitigator activities with minimal side effects. However, the expense of purification limits their potential use.  Two inexpensive natural sources with abundant tocotrienol content have shown protection against radiation induced mitochondrial dysfunction and oxidative stress in human cells and in a murine model, suggesting they are viable sources for tocotrienols that can be used as radioprotectors.

General Laboratory Safety Training: Safety

Environmental Health and Safety, MS&T

 Abstract: 

  • General Safety
    • Environmental Health and Safety Department
    • General Rules/Policies and Prudent Practices
    • Fire Safety
    • Emergency Response
    • Hazard Communication
    • Engineering/Administrative Controls, and Personal Protective Equipment
    • Injury / Incident Reporting
  • Hazardous Material Safety and Management
    • Chemical/Biological/Radiological Hazards
    • Compressed Gas Cylinders / Cryogenics
    • Physical Hazards
    • Chemtrack Inventory System

General Laboratory Safety Training: Environmental Compliance

Environmental Health and Safety, MS&T

 Abstract: 

  • Environmental Management System
    • ISO 14001
    • Corrective action
  • Hazardous Waste Management
    • Federal Regulations
    • Chemical Waste – proper storage and labeling
    • Chemical Waste – pick-up request
    • Biological Waste
    • Universal Waste
    • Spill Response

Continuous Flow Reactor for Carbonic Acid Hydrolysis of Biomass

Nicholas Dudenhoeffer, Dept. of Chem., MS&T

 Abstract: The increasing need for renewable fuels sources has led to the investigation of different methods that can maximize the bioethanol production from the fermentation of carbohydrate-rich biomass.

      The two most commonly used hydrolysis methods for carbohydrate-rich biomass are enzymatic hydrolysis and mineral acid hydrolysis.  However, enzymatic hydrolysis is a slow process and mineral acid hydrolysis requires neutralization and generates a waste stream.  In this study high temperature water and carbonic acid was used as an alternative to the common mineral acid hydrolysis.  Unlike mineral acids, carbonic acid generated from dissolved CO2 does not require neutralization and eliminates the production of waste. A high pressure continuous flow reactor designed for the treatment of wet biomass using pressurized carbon dioxide was used for the hydrolysis of microalgae biomass. The reaction conditions such as resident time and temperature were optimized for the formation of simple sugars and degradation byproducts.  The yield of simple sugars from the direct treatment of whole biomass for 5 minutes reaction at 210°C using 7 MPa CO2 was very low, but increased to levels similar to the dilute mineral acid hydrolysis when a small amount (0.05%) of sulfuric acid was added.  The amount of thermal degradation byproducts such as 5-HMF and furfural was approximately one order higher, however, no inhibition was observed during the subsequent fermentation of hydrolysis substrates to ethanol. 

 

Applications of Single Particle Inductively Coupled Plasma-Mass Spectrometry

Yongbo Dan, Dept. of Chem., MS&T

 

From Standard NMR Relaxation Experiments to High-resolution Relaxometry

Klaus Woelk, Dept. of Chem., MS&T

 

Nanostructured Catalysts Prepared by Atomic/Molecular Layer Deposition

Xinhua Liang, Dept. of Chemical & Biochemical Engineering, MS&T

Abstract: Catalysts are responsible for the production of over 60% of all chemicals and are used in some 90% of all chemical processes worldwide. Heterogeneous catalysts enable many chemical transformations of fossil resources (natural gas, methane, liquid petroleum, coal, etc.) into useful products. Normally, heterogeneous catalysts consist of small metal particles dispersed on a high surface area porous oxide support. Traditional methods, such as wet-chemical processing, can produce metal particle catalysts as small as several nanometers, but these methods cannot precisely control the size of the catalytic nanoparticles and disperse them homogeneously within the porous substrates. In addition, heterogeneous catalysts cannot selectively convert specific molecules in the reactant mixture to catalyze only desired reactions. Novel approaches are required to synthesize and characterize stable metal nanoparticles catalysts with tightly controlled sizes to further advance the knowledge of their unique size-dependent catalytic behavior. Recently, atomic layer deposition (ALD) has been used to prepare highly active, highly dispersed metal nanoparticles. ALD is a thin film growth technique based on sequential, self-limiting surface chemical reactions, and has focused principally on the formation of thin film oxides with precise atomic layer control. Molecular layer deposition (MLD), which is similar to ALD, can be utilized to deposit pure polymer films or hybrid organic/inorganic polymer films using suitable precursors. Highly porous metal oxide films with well-defined porous structures and precisely controlled thickness down to several angstroms can be prepared from dense organic/inorganic hybrid metal alkoxide films grown by MLD. These ultra-thin films can be used for catalyst encapsulation. In this presentation, I will introduce ALD/MLD chemistry, particle surface functionalization by ALD/MLD, and examples of nanostructured catalysts prepared by ALD/MLD, such as thermally stable size-selective catalysts.

 

Introducing a Blended Laboratory Component in the General Chemistry Course

Shayna B. Burchett, Dept. of Chem., MS&T

 

Accelerated Discovery of Materials 

Prof. Kenneth Poeppelmeier, Dept. of Chem., Northwestern University 

 

The Chemistry Set Revisted after Fifty Years

Dennis Whitney, American Airlines, Retired

 

Engineered Nanostructures for Regulation and Investigation of Cellular Signaling Processes

Prof. Gang-yu Liu, Dept. of Chem., University of California, Davis

 

Conversion of Glasses into Biologically Useful Products

Prof. Mohamed N. Rahaman, Dept. of Materials Science & Engineering Director, Center for Biomedical Science and Engineering, MS&T

Abstract: There is growing interest in glasses for use in healthcare. Glasses have the advantage of ease of fabrication and compositional modification. The reactivity of a glass can be controlled over a wide range, from nearly inert to highly reactive, by controlling its composition. While bioinert glasses are used in some medical applications, glasses that react in an aqueous solution such as the body fluid (referred to as bioactive glasses) are There is growing interest in glasses for use in healthcare. Glasses have the advantage of ease of fabrication and compositional modification. The reactivity of a glass can be controlled over a wide range, from nearly inert to highly reactive, by controlling its composition. While bioinert glasses are used in some medical applications, glasses that react in an aqueous solution such as the body fluid (referred to as bioactive glasses) are receiving more research and development interest for medical and dental applications. Bioactive glasses degrade and convert to hydroxyapatite (the mineral constituent of bone) in an aqueous phosphate solution such as the body fluid, releasing ions in the process which can stimulate the gene expression of cells and, thus, enhance bone regeneration and soft tissue healing. The reaction of certain glasses in a phosphate solution can also be used to create phosphate materials near room temperature which have unique architectures, such as hollow hydroxyapatite microspheres being researched for drug and growth factor delivery. This presentation will describe methods for creating biomedical glasses and converting them into a variety of compositions and architectures for use in applications such as bone regeneration, wound healing and drug delivery.   

 

How Chemistry Promotes Modern Medical Imaging: a Bench-to-Bedside Story about Chemical Exchange Saturation Transfer MRI

Prof. Guanshu Liu, Kennedy Krieger Institute & Russel H. Morgan Dept. of Radiology and Radiological Science, John Hopkins Medical School

Abstract: MRI has become one of the most important medical imaging modalities and is playing indispensable roles in the diagnosis and treatment of many diseases. MRI detection can be further advanced from the anatomical level to the molecular level, with the help of specific molecular probes.  Recently, along with the development of MR molecular imaging, Chemical Exchange Saturation Transfer (CEST) has emerged as an attractive MRI contrast mechanism. The CEST MRI contrast is generated simply by transferring the modulated magnetization from water-exchanging protons (OH, NH, or NH2) to their surrounding water molecules (the source of MRI signal), which makes it possible to directly use MRI to detect many diamagnetic molecules in as low as mM concentration range. Thus CEST opens a new gate to accomplish MR molecular imaging with biodegradable and biocompatible compounds, including those already approved for clinical use and even many endogenous biomolecules.  In this talk, a brief introduction of CEST MRI mechanism will be first provided, followed by several examples showing its biomedical applications, which are either being tested or ready to be used in the clinic.  The importance of chemistry in the development of modern MR imaging will be then discussed.

Taking the Best of Two Worlds: A Combined Experimental and Computations Study of New Materials

Vadym Mochalin, Dept. of Chem., MS&T

 

Functional Nanoporous Polymeric Aerogels: Polyurea and Polyamides

Malik Adnan Saeed, Dept. of Chem., MS&T

 Abstract:

Part A: Nanoporous Polyurea from Triisocyanates Reacting with Mineral Acids

     Isocyanates react with carboxylic acids and yield amides. What is reported herewith is that transferring that reaction to a range of mineral acids, (anhydrous H3BO3, H3PO4, H3PO3, H2SeO3, H6TeO6, H5IO6 and H3AuO3) yields urea. The model system for this study was a triisocyanate, tris(4-isocyanatophenyl)methane (TIPM), reacting with boric acid in DMF at room temperature yielding nanoporous polyurea networks that were dried with supercritical fluid CO2 to robust aerogels. Residual boron in the model system was quantified with prompt gamma neutron activation analysis (PGNNA). It was found very low (≤0.05 % w/w) and was shown to come primarily from B2O3 (by 11B NMR). Thus, any mechanism for systematic incorporation of boric acid in the polymeric chain, by analogy to carboxylic acids, was ruled out. Retrospectively, it was fortuitous that this work was conducted with aerogels, and the model system utilized H3BO3, whereas the byproduct, B2O3, could be removed easily from the porous network leaving behind pure polyurea. With other mineral acids results could have been misleading, because the corresponding oxides are insoluble and remain within the polymer (via skeletal density determinations and EDS). On the positive side, the latter is a convenient method for in situ doping robust porous polymeric networks with oxide or pure metal nanoparticles (Au in the case of H3AuO3) for possible applications in catalysis.

 

Part B: Ferrocene-based Polyamide Aerogels: Graphitization, Transmetalation,

and Use in Heterogeneous Catalysis

     Ferrocene-polyamide aerogels (Fc-PA) incorporating one ferrocene moiety in every polymer repeat unit were prepared in one pot via an underutilized reaction between a triisocyanate and ferrocene dicarboxylic acid. Fc-PA aerogels have high porosities (up to 92% v/v of empty space) and surface areas (up to 456 m2g-1). Upon pyrolysis (800-1400 °C / H2), Fc-PA aerogels decompose to Fe(0) and carbon but remain monolithic. Fe(0) catalyzes low-temperature graphitization in its vicinity, thus the resulting materials consist of Fe(0) nanoparticles (20-25 nm in diameter, wrapped in graphitic ribbons (4-5 nm thick), and the whole assemblies are embedded in the nanoporous matrix of amorphous/graphitic carbon (C-) aerogels. Such monolithic Fe(0)-doped C-aerogels (Fe@C) were transmetalated (tm-) quantitatively with several noble metals without sacrificing the intricate C-aerogel nanostructure. Surface areas and porosities of transmetalated C-aerogels (tm-M@C, M: Au, Pt, Pd) remain high (about 100 m2g-1 and 90% v/v, respectively), and their open structure facilitates rapid diffusion of reactants to the metal particles, rendering those materials particularly attractive as heterogeneous catalysts. The latter was demonstrated with reduction of nitrobenzene (Fe@C), oxidation of alcohols (tm-Pt@Cand tm-Pt@C) and Heck couplings (tm-Pd@C). Conversions were consistently high (80-100%), and at the end of each reaction the monolithic tm-M@C catalyst was harvested and reused several times without noticeable loss of activity.