Chemistry Commons^™

Wettability Of Pristine And Alkyl-Functionalized Graphane, Davide Vanzo, Dusan Bratko, Alenka Luzar

Chemistry Publications

Graphane is a hydrogenated form of graphene with high bandgap and planar structure insensitive to a broad range of chemical substitutions. We describe an atomistic simulation approach to predict wetting properties of this new material. We determine the contact angle to be 73°. The lower hydrophobicity compared to graphene is explained by the increased planar density of carbon atoms while we demonstrate that the presence of partial charges on carbonand hydrogen atoms plays only a minor role. We further examine the effects of graphane functionalization by alkyl groups of increasing chain lengths. The gradual increase in contact angle with chain …

Large-Scale Synthesis Of High Moment Feco Nanoparticles Using Modified Polyol Synthesis, Mehdi Zamanpour, Yajie Chen, Bolin Hu, Kyler Carroll, Zachary J. Huba, E. E. Carpenter, Laura H. Lewis, Vincent G. Harris

Chemistry Publications

Binary alloys of Fe and Co have among the highest magnetizations of any transition metal alloy systems, but their affinity to form oxides act to reduce the magnetization of nanoparticles as their size is reduced below ∼30 nm. Here, we demonstrate the synthesis of single phase, size-controlled FeCo nanoparticles having magnetization greater than 200 emu/g via a non-aqueous method in which ethylene glycol served as solvent and reducing agent as well as surfactant. Experiments indicated pure-phase FeCo nanoparticles, having saturationmagnetization up to 221 emu/g for sizes of 20–30 nm, in single batch processes resulting in > 2 g/batch. Post-synthesis oxidation of …

Size And Phase Control Of Cobalt-Carbide Nanoparticles Using Oh- And Cl- Anions In A Polyol Process, Zachary J. Huba, Everett E. Carpenter

Chemistry Publications

Exchange coupled cobalt–carbide nanocomposites and single-phase Co₂C nanoparticles were synthesized using the polyol process. Hydroxide and chloride anions were used to controlcarbide phase and particle shape. Synthesized Co _x C nanocomposites exhibited average diameters around 300 nm. Co _x C nanocomposites synthesized at 0.25 M [OH⁻] and [Cl⁻] formed clusters of capped nanorods, whereas synthesis at 0.37 M [OH⁻] and [Cl⁻] produced clusters of long blade-like particles. For single-phase Co₂C, an [OH⁻] and [Cl⁻] of 0.71 M was used and produced clusters of ellipsoidal …

Profiles In Science: John Bennett Fenn, Kimberly Brady, Roy Brown, Emily Johnson, Shannon D. Jones, Margaret Henderson, Dana Ladd, Irene Lubker, Jennifer A. Mcdaniel

VCU Libraries Faculty and Staff Publications

“Don’t ever try to be a scientist or engineer!” Had John Bennett Fenn listened to this advice given by his ninth grade teacher, he might not have gone on to pursue a career in analytical chemistry which would culminate in the attainment of the Nobel Prize in 2002. Gathered from interviews, publication analyses, glowing tributes, and his reminiscences, this paper outlines the academic and professional life of John Fenn from childhood through the end of his career in 2010.

Biochemical Actions Of A Novel Cis-Terpenone, Lin Zhang

Theses and Dissertations

Abstract BIOCHEMICAL ACTIONS OF A NOVEL CIS-TERPENONE By Lin Zhang, Ph.D. A dissertation submitted in partial fulfillment of the requirements for the degree of Doctor of Philosophy at Virginia Commonwealth University. Virginia Commonwealth University, 2012 Director: Qibing Zhou, Ph.D Assistant Professor Department of Chemistry

Quinone methides are reactive species due to their electrophilicity, and natural quinone methide analogs have broad biological activities. Based on known actions of cytochrome P450 enzymes, we hypothesized that trans-terpenones can be metabolized in cells to form a cascade of metabolite products, which may be biologically active due to the generation of quinine and quinone methide …

Synthesis And Characterization Of Highly Porous Borazine-Linked Polymers Via Dehydrogenation/Dehydrocoupling Of Borane-Amine Adducts And Their Applications To Gas Storage, Karl Jackson

Theses and Dissertations

A new class of porous polymers has been designed and successfully synthesized by thermal dehydrogenation of several polytopic arylamine-borane adducts and has been designated Borazine-Linked Polymers (BLPs). The polymers reported are constructed of linear, triangular, and tetrahedral amine building units to form 2D and 3D frameworks. The boron sites of the pores are aligned with hydrogen atoms contrasted with the recently reported halogenated BLPs which consist of pore channels aligned with bromine or chlorine atoms. One of the reported BLPs, BLP-2(H), was proven to be crystalline by PXRD, matching the experimental pattern to theoretical patterns calculated from modeled structures. BLPs …

Designed Synthesis Of Halogenated Borazine-Linked Polymers And Their Applications In Gas Storage And Separation, Thomas Reich

Theses and Dissertations

The synthesis of highly porous organic polymers with predefined porosity has attracted considerable attention due to their potential in a wide range of applications. Of particular interest in porous organic polymers is their potential use in automotive applications as well as separation processes whereby advancements could result in a reduction in carbon dioxide emissions and the production of natural gas in a more economically friendly manner. Along these pursuits, seven borazine-linked polymers (BLPs) have been synthesized through the introduction of p-phenylenediamine, 1,3,5-tris-(4-aminophenyl)benzene, benzidine, or tetra-(4-aminophenyl)methane with boron tribromide or boron trichloride followed by the thermolysis reaction of the resulting in …

The Effect Of Oxidation And Support On Tio2(110)-Supported Pdn (N=1-7) Clusters, S. Vincent Ong

Theses and Dissertations

First principles theoretical studies based on a gradient-corrected density functional approach have been carried out on the atomic and electronic properties and oxidation of Pdn (n=1-7) clusters supported on the TiO2(110) surface. The studies are aimed to address some of the fundamental issues related to the properties of supported Pdn clusters used as catalysts in oxidation reactions. Of those issues are the following: What are the atomic structures of Pdn clusters on the TiO2 surface? Upon oxidation, do O atoms from a dissociated O2 molecule spill over onto the underlying TiO2 sup- port? How strongly does spillover oxygen bind? What …

Design Of Control Release Drug Delivery System (Dds) For Imaging And Therapeutic Applications, Sweta Naik

Theses and Dissertations

The main challenge in disease treatment is no more the discovery of new therapeutic drugs, but to provide targeted delivery of therapeutic drugs to specific sites without incurring systemic toxicity effects. An efficient way of reducing the toxicity is by encapsulating the drug with a biodegradable matrix that can provide controlled release of the drug along with local heating of the drug. Local heating can be obtained by incorporating magnetic iron oxide particles that heat upon exposure to AC electromagnetic fields. The magnetic iron oxide nanoparticles are also gaining much attention as MRI contrast agents. Thus it would be of …

Wetting Transitions At Nanostructured Surfaces, Yazdi Jamileh Seyed

Theses and Dissertations

Shape of a droplet atop a surface heterogeneity at a nanoscale. Small aqueous droplets on homogeneous surfaces, surrounded by a reservoir of vapor are inherently unstable. In contact with supersaturated vapor, the drops will keep growing until they coalesce and form a contiguous aqueous phase. Alternatively, if vapor pressure is below that of the droplets, the droplets gradually evaporate. Departing from this common picture, when nanoscale droplets sit above hydrophilic patches on a heterogeneous surface, at certain conditions they can maintain a stable volume, determined by the pertinent contact angle and the size of the patches. Only the region under …

Synthesis Of Cyclen Based Receptors And Their Use In Separations Biotechnology., Vivek Kaushik

Theses and Dissertations

A number of purification techniques such as adsorption, centrifugation, chromatography, extraction, distillation, filtration, precipitation etc. to name a few, are commonly used for the purification. However, due to a constant need of purification of even more complex crude mixtures, be it reaction mixtures, various proteins and DNA from cell extracts or medicinal compounds and fragrances from plant extracts, scientists needed to consistently develop new and improved techniques of purification. One such great advancement in the field of chromatography was the development of affinity chromatography. It revolutionized the field of bioseparations technology, and the dream of single stage purification of complex …

Growth Mechanisms Of Complex Organics In The Gas Phase And On Metal Nanoparticles Generated By A Laser Vaporization Process, Abdel Rahman Soliman

Theses and Dissertations

In this dissertation, the ion mobility mass spectrometry technique is used to study the possible mechanisms of formation of polyaromatic hydrocarbons (PAHs) and polyaromatic nitrogen-containing hydrocarbons (PANHs) via the ion-molecule reactions of acetylene neutrals with different aromatic cations, in order to infer the possible mechanisms of formation of PAHs and PANHs in different environments such as interstellar media under different ionizing conditions. Furthermore, this technique is used to probe structures, address the thermochemistry, and measure the kinetics of the product ions originated from these reactions. Reactions of benzene radical cations with acetylene produce styrene and naphthalene-type cations at high temperatures. …

Development Of Free-Label Sensing In Plastic Microfluidic Platforms Using Pulsed Streaming Potentials (Psp), Vera Fernando Luna

Theses and Dissertations

This work deals with the development of a new label-free detection technique called Pulsed Streaming Potential (PSP). Its novelty relies on the adaptation of a classical electrokinetic phenomenon (streaming potential) into a tool which can evaluate molecular interplay in label-free fashion. Implementation of PSP to microfluidic platforms allowed the label-free sensing of binding events to plastic (modified and unmodified) surfaces. It was demonstrated the use of real time PSP in plastic microfluidic platforms for determination of kinetic parameters of the interaction of proteins and plastic surfaces. Moreover, initial change of PSP after adsorption of proteins showed to be proportional to …

Drug Design, Biological Activity, And Metabolic Consequences Of Cytotoxic Platinum Compounds: Utilizing Fluorescent Tagging To Understand Drug Action And Metabolism, Brad Benedetti

Theses and Dissertations

Platinum drugs are among the most commonly used chemotherapeutics for the treatment of testicular, head and neck, ovarian, small cell lung, and colorectal carcinomas. Although the current set of platinum chemotherapeutics has proven somewhat successful, the overall success of platinum based drugs is limited due to acquired drug resistance and a limited range of tumor types that are treatable with the current regime. The development of novel cytotoxic platinum based compounds, both trans- and polynuclear, provides for the promising treatment of clinical platinum drug resistant tumors. While the cytotoxic activity of platinum drugs provides for a hopeful outlook, the ultimate …

Synthesis Of High Magnetization Feco Alloys Prepared By A Modified Polyol Process, Zachary J. Huba, Kyler J. Carroll, Everett E. Carpenter

Chemistry Publications

High magnetization, soft ferromagnetic FeCo alloy nanoparticles were synthesized at various Fe to Co ratios using a modified polyol process. Transmission electron microscopy images revealed that Fe-rich particles had a cubic shape with a mean particle size of 100 nm, while Co-rich particles had a spherical shape. A maximum saturation magnetization of 212 emu/g was recorded for both Fe₆₀Co₄₀ and Fe₇₅Co₂₅ particles. X-ray diffraction scans at room temperatureof synthesized particles were characteristic of body-centered-cubic single-phase FeCo. Variabletemperature x-ray diffraction scans under N₂ gas revealed an order–disorder transition at 600 °C and a transition …

Spin Transition In Gd3n@C-80, Detected By Low-Temperature On-Chip Squid Technique, L. Chen, E. E. Carpenter, C. S. Hellberg, H. C. Dorn, M. Schultz, W/ Wernsdorfer, I. Chiorescu

Chemistry Publications

We present a magnetic study of the Gd₃N@C₈₀ molecule, consisting of a Gd-trimer via a nitrogen atom, encapsulated in a C₈₀ cage. This molecular system can be an efficient contrast agent for magnetic resonance imaging (MRI) applications. We used a low-temperature technique able to detect small magnetic signals by placing the sample in the vicinity of an on-chip SQUID. The technique implemented at the National High Magnetic Field Laboratory has the particularity of being able to operate in high magnetic fields of up to 7 T. The Gd₃N@C₈₀shows a paramagnetic behavior and …

Characterization Of Oxidation Resistant Fe@M (M=Cr, Ni) Core@Shell Nanoparticles Prepared By A Modified Reverse Micelle Reaction, Sweta H. Naik, Kyler J. Carroll, Everett E. Carpenter

Chemistry Publications

Iron-based nanoparticles are the forerunners in the field of nanotechnology due to their high magnetizationsaturation and biocompability which affords them use in a variety of applications. However, iron-based nanoparticles, due to a high surface-to-volume ratio, suffer from oxidation and limit its practicality by lowering the magnetic moment significantly. To avoid this oxidation, the surfaces of the particles have to be passivated. One such way to accomplish this passivation is to synthesize core@shell nanoparticles that have a surface treatment of chromium or nickel. These core@shell nanoparticles have been synthesized using a reverse micelle technique. The Cr and Ni passivated ironnanoparticles were …

Structure And Hydration Of The C4h4 •+ Ion Formed By Electron Impact Ionization Of Acetylene Clusters, Paul O. Momoh, Ahmed Hamid, Samuel A. Abrash, M. Samy El-Shall

Chemistry Publications

Here we report ion mobility experiments and theoretical studies aimed at elucidating the identity of the acetylene dimer cation and its hydrated structures. The mobility measurement indicates the presence of more than one isomer for the C4H4 ^•+ ion in the cluster beam. The measured average collision cross section of the C4H4 ^•+ isomers in helium (38.9 ± 1 Ų) is consistent with the calculated cross sections of the four most stable covalent structures calculated for the C4H4 ^•+ ion [methylenecyclopropene (39.9 Ų), 1,2,3-butatriene (41.1 Ų), cyclobutadiene (38.6 Ų), and vinyl acetylene …

The Synthesis, Characterization, And Upconverting Properties Of Erbium Doped; Ytterbium, Erbium Co-Doped Yttrium Oxysulfide Phosphors Under 808, 980, And 1560 Nm Excitation, James Wilkins

Theses and Dissertations

Bulk yttrium oxysulfide phosphors were prepared using the polysulfide flux method. The morphology and structure was characterized using transmission electron microscopy and x-ray powdered diffraction. Visible emissions occurring near 530 and 550 nm and 660 - 670 nm consistent with the 2H11/2, 4S3/2 → 4I15/2 and 4F9/2 → 4I15/2 transitions, respectively, were observed under 808, 980, and 1560 nm excitation. The upconverting mechanisms excited at 808, 980, and 1560 nm have been investigated in detail. The power dependent behavior of the upconverted emission intensities for singly doped erbium phosphors excited at 808 and 980 nm indicated a two-photon excitation process. …

Electronic Structure Based Classification Of Neurotransmitters And Related Drugs, Amrita Jha

Theses and Dissertations

A fundamental understanding of the relationship between structure and activity of neurotransmitters in the human brain is of vital importance for the design targeted drugs. Using density functional theory and hybrid exchange correlation energy functionals we have studied the structure-activity-relationships of some important neurotransmitters and selected drugs by calculating their absolute hardness (η) and absolute electronegativity (χ). A plot of the η- χ diagram allowed us to assign them into three distinct groups, namely, (i) Acetylcholine analogs (positively charged structure), (ii) GABA analogs (zwitterionic structures) and (iii) monoamines. The results suggest that brain stem is chemically soft because of distribution …

Ribosomal Synthesis Of N-Methylated Peptides, Sara Ahadi

Theses and Dissertations

Natural peptide products isolated from various organisms often contain N-methylated backbones. Such a modification of backbone of the peptide changes its conformational rigidity. This modification improves the biological properties of the peptide, such as improved target affinity, proteolytic stability or membrane permeability. Therefore synthesis of N-methylated peptide libraries is valuable in screening for drug-like peptides suitable for therapeutic uses. Protein synthesis using recombinant elements (PURE) and Flexizyme were used in order to reassign specific codons to N-methyl amino acids. mRNA-dependent translation system enable us to make our desired peptides with N-methyl amino acids. This technology is a convenient tool for …

Adsorption Studies By Pulsed Streaming Potentials In Microfluidic Channels, Thutrang Nguyen

Theses and Dissertations

In this work, an instrument for measuring pulsed streaming potentials was constructed and optimized for analytical and teaching applications. This thesis is divided in three chapters, the first one deals with the construction of the instrument, the second describes a microfluidic experiment designed for undergraduate and high school students using this instrument, and the third one shows an application of pulsed streaming potential measurements in the detection of heparin. Streaming potential is the electric field generated when a liquid is forced to flow by a pressure gradient through a channel or other stationary charged surfaces.1,2 These measurements were done in …

Synthesis, Functionalization And Characterization Of Dual Mode Nanoparticles For Biomedical Applications, Farah Radwan

Theses and Dissertations

Three different approaches were used to prepare dual mode nanoparticles using a previously described reverse micelle technique. Superparamagnetic Fe@FeOx core shell nanoparticles were chosen to be the magnetic component for all three dual mode systems. In the first type of particles, 2- amino-1,3- propane diol (APD) was used as a functionalization ligand to stabilize the surface of the particles and its functional amino group also provided a binding site for the attachment of a fluorescent probe. The TEM analysis showed that the APD coated particles have a size range of 8-13 nm while XPS and MALDI measurements confirmed the presence …

Core-Shell Nanoparticles: Synthesis, Design, And Characterization, Kyler Carroll

Theses and Dissertations

The design of core/shell nanoparticles is of great interest for a wide range of applications. The primary focus of this dissertation is on the design and optimization of two synthetic routes. The first one is an aqueous reduction method using sodium borohydride and sodium citrate. This method was extended to design two types of core/shell nanoparticles, both of which have many applications in bio-sensing, magnetic resonance imaging, and magnetically guided SERS for the identification of environmental threats. The first, Fe/Ag core/shell nanoparticles were designed using a novel one-pot method by varying the AgNO₃ addition time in the system. For …

Impact Of Nickel Doping On Hydrogen Storage In Porous Metal-Organic Frameworks, Tanushree Banerjee

Theses and Dissertations

A supply of clean, carbon neutral and sustainable energy is the most scientific and technical challenge that humanity is facing in the 21st century. Though there is enough fossil fuels available for a few centuries, their use would increase the level of CO2 in the atmosphere. This would lead to global warming and may pose serious threats such as rising of sea level, change in hydrological cycle, etc. Hence there is a need for an alternative source of fuel that is clean and sustainable. Among the many resources considered as an alternative power source, hydrogen is considered one of the …

Mechanistic Studies On The Electrochemistry Of Proton Coupled Electron Transfer And The Influence Of Hydrogen Bonding, Timothy Alligrant

Theses and Dissertations

This research has investigated proton-coupled electron transfer (PCET) of quinone/hydroquinone and other simple organic PCET species for the purpose of furthering the knowledge of the thermodynamic and kinetic effects due to reduction and oxidation of such systems. Each of these systems were studied involving the addition of various acid/base chemistries to influence the thermodynamics and kinetics upon electron transfer. It is the expectation that the advancement of the knowledge of acid/base catalysis in electrochemistry gleaned from these studies might be applied in fuel cell research, chemical synthesis, the study of enzymes within biological systems or to simply advance the knowledge …

Characterization Of Stabilized Palladium Nanocatalysts, Meghann Broderick

Theses and Dissertations

Metal nanoparticles have received much interest for their application in catalysis due to high surface-to-volume ratios resulting in more available active sites. Ideally these catalysts are heterogeneous and allow for facile separation from the catalytic reaction mixture making them ideal for industrial application. Dispersed metal nanoparticles are explored due to their high reactivity in solution and are stabilized by surfactants and polymers. However, it is difficult to determine whether or not a catalyst is truly heterogeneous as a certain degree of leaching from the metal nanoparticle is inevitable. Determining the mechanisms involved in nanocatalysis is also a challenge. In this …

Density Functional Studies Of The Stability Of Clusters, Penee Clayborne

Theses and Dissertations

Theoretical studies using the Kohn-Sham density functional formalism have been carried out to identify and investigate the stability of a variety of atomic clusters for their use in cluster assembled materials. The stable behavior found in a cluster system provides a way to classify inorganic clusters. The clusters in this study can be categorized in one of the following, jellium, all-metal aromatic, Zintl analogue or as a covalent metal-carbide. By understanding the electronic structure and ultimately the stable nature of a cluster first, it is proposed one can construct assemblies based on the stable cluster. The methodology presented is a …

Electrodeposited Silica Thin Films, Debbie Campbell-Rance

Theses and Dissertations

Sol-gel derived silica thin film synthesis has gained prominence because of the mild processing conditions and widespread understanding of the chemistry of the process. Traditionally, silicate films are prepared by spin- and dip-coating but these materials lack the desired porosity for sensing, separations and catalysis applications. Electrochemical deposition was proposed to improve the porosity of silicate films. The main aims of this work were threefold. First we wanted to elucidate what parameters influenced film formation during electrodeposition. Then we wanted to understand how these parameters affected the morphology of the materials prepared. These films were characterized by profilometry, AFM, and …

Electrospray Ionization Mass Spectrometry For The Characterization Of Covalent And Noncovalent Polynuclear Platinum Compounds Interacting With Bio-Molecules, John Mangrum

Theses and Dissertations

Polynuclear platinum compounds represent a new class of potential platinum anticancer therapeutics. Derived from the most widely used platinum anticancer drug, cisplatin, these novel compounds are distinct in their interactions with bio-molecules. The effectiveness of platinum anticancer agents is influenced by three pharmacological factors: (i) their resistance to deactivating sulfur nucleophiles, (ii) the ability to gain cellular entry and efficient cellular uptake, and (iii) the ability to form stable and specific complexes with DNA. BBR 3464, the first multinuclear platinum compound to reach phase II clinical trials, has created a new approach to cancer drug design. Large, highly charged platinum …