Physical Sciences and Mathematics Commons^™

Analytic Derivative Couplings Between Configuration-Interaction-Singles States With Built-In Electron-Translation Factors For Translational Invariance, Shervin Fatehi, Ethan Alguire, Yihan Shao, Joseph Subotnik

Chemistry Faculty Publications and Presentations

We present a method for analytically calculating the derivative couplings between a pair of configuration-interaction-singles (CIS) excited states obtained in an atom-centered basis. Our theory is exact and has been derived using two completely independent approaches: one inspired by the Hellmann-Feynman theorem and the other following from direct differentiation. (The former is new, while the latter is in the spirit of existing approaches in the literature.) Our expression for the derivative couplings incorporates all Pulay effects associated with the use of an atom-centered basis, and the computational cost is minimal, roughly comparable to that of a single CIS energy gradient. …

Fabrication Of Mineralized Collagen From Bovine Waste Materials By Hydrothermal Method As Promised Biomaterials, Faheem A. Sheikh, M. A. Kanjwal, Javier Macossay-Torres, Muneeb A. Muhammad, Travis Cantu, Ioannis S. Chronakis, N. A. M. Barakat, Hak Yong Kim

Chemistry Faculty Publications and Presentations

In the present study, we aimed to produce mineralized-collagen by hydrothermal process. A simple method not depending on additional foreign chemicals has been employed to isolate the mineralized-collagen fibers from bovine waste. The process of extraction involves the use of hydrothermal method from available bovine bones. The structural and morphological properties of the collagen fibers were characterized by using scanning electron microscopy and transmission electron microscopy. These results indicated well received collagen fibers, having a diameter less than 1 μm and with established mineral content in the individual fibers. The X-ray diffraction showed the crystalline feature of the obtained nano-compounds. …

Polycyclic Aromatic Compounds As Anticancer Agents: Evaluation Of Synthesis And In Vitro Cytotoxicity, Debasish Bandyopadhyay, Jose C. Granados, John D. Short, Bimal K. Banik

Chemistry Faculty Publications and Presentations

Polycyclic aromatic hydrocarbons (PAHs) are considered to be significant environmental carcinogens. Additionally, various planar ring systems are capable of intercalating with DNA, leading to a number of drugs that possess chemotherapeutic activity. In this study, three new polyaromatic compounds with a side chain were synthesized, and spectroscopic as well as elemental analyses were performed. The addition of the long chains to either chrysene or pyrene caused a red-shift in the spectral emission when compared to the corresponding polycyclic aromatic hydrocarbons itself. Furthermore, the cytotoxicity of the three novel polyaromatic compounds was evaluated in vitro in a panel of cultured mammalian …

A Truly Green Synthesis Of A-Aminonitriles Via Strecker Reaction, Debasish Bandyopadhyay, Juliana M. Velazquez, Bimal K. Banik

Chemistry Faculty Publications and Presentations

Background: The classical Strecker reaction is one of the simplest and most economical methods for the synthesis of racemic a-aminonitriles (precursor of a-amino acids) and pharmacologically useful compounds.

Results: Indium powder in water is shown to act as a very efficient catalyst for one-pot, three-component synthesis of a-aminonitriles from diverse amines, aldehydes and TMSCN. This general rapid method is applicable to a wide range of amines and aldehydes and produces products in excellent yield.

Conclusions: The present one-pot, three-component environmentally benign procedure for the synthesis of aaminonitriles will find application in the synthesis of complex biologically active molecules.

Properties, Solution State Behavior, And Crystal Structures Of Chelates Of Dotma, Silvio Aime, Mauro Botta, Zoltán Garda, Benjamin E. Kucera, Gyula Tircso, Victor G. Young, Mark Woods

Chemistry Faculty Publications and Presentations

The chemistry of polyamino carboxylates and their use as ligands for Ln(3+) ions is of considerable interest from the point of view of the development of new imaging agents. Of particular interest is the chemistry of the macrocyclic ligand 1,4,7,10-tetraazacyclododecane-1,4,7,10-tetraacetic acid (DOTA) and its derivatives. Herein we report that the tetramethylated DOTA derivative, DOTMA, possess several properties that, from an imaging agent development point of view, are more advantageous than those of the parent DOTA. In particular, the Ln(3+) chelates of DOTMA exhibit a marked preference for the monocapped twisted square antiprismatic coordination isomer which imparts more rapid water exchange …

Bismuth Nitrate Pentahydrate-Induced Novel Nitration Of Eugenol, Luis Canales, Debasish Bandyopadhyay, Bimal K. Banik

Chemistry Faculty Publications and Presentations

Background: Eugenol, the main constituent of clove oil possesses a number of medicinal activities. To enhance the medicinal property, structural modification is required. On the other hand, bismuth nitrate pentahydrate has been established as an excellent eco-friendly nitrating agent for several classes of organic compounds.

Results: Bismuth nitrate pentahydrate-induced nitration of eugenol has been investigated very thoroughly. Twenty five different conditions have been studied. The microwave-induced solvent-free reaction has been identified as the best condition.

Conclusions: Spectral analyses confirm that 5-nitroeugenol is the sole product in all the cases. No oxidized or isomerized product could be detected.

Towards The Rational Design Of Mri Contrast Agents: Δ-Substitution Of Lanthanide(Iii) Nb-Dota-Tetraamide Chelates Influences But Does Not Control Coordination Geometry, Christiane E. Carney, Anh D. Tran, Jing Wang, Matthias C. Schabel, A. Dean Sherry, Mark Woods

Chemistry Faculty Publications and Presentations

LnDOTA-tetraamide chelates (DOTA=1,4,7,10-tetraazacyclododecane-1,4,7,10-tetraacetic acid) have received considerable recent attention as a result of their potential to act as PARACEST contrast agents for magnetic resonance imaging (MRI). Although PARACEST agents afford several advantages over conventional contrast agents they suffer from substantially higher detection limits; thus, improving the effectiveness of LnDOTA-tetraamide chelates is an important goal. In this study we investigate the potential to extend conformational control of LnDOTA-type ligands to those applicable to PARACEST. Furthermore, the question of whether δ- rather than α-substitution of the pendant arms could be used to control the chelate coordination geometry is addressed. Although δ-substitution does …

Positional Control Over Nanoparticle Deposition Into Nanoholes, Moshood K. Morakinyo, Shankar B. Rananavare

Chemistry Faculty Publications and Presentations

Controlled deposition of metal nanoparticles (NPs) into lithographic patterned nanoholes has been a major challenge. Electrostatic attraction was employed in directing gold NPs of precise size into e-beam lithographically patterned holes. Citrate stabilized gold NPs with a net negative surface charge were deposited on a positively charged well-bottom surface generated by adsorption of long-chain amino-terminated organosilane N-(2-aminoethyl)-11-aminoundecyltrimethoxy- silane (AATMS). Scanning electron microscopy (SEM) results indicate that deposition of NPs into patterned holes is a function of deposition time and NPs concentration. Other factors affecting NP fill fraction are thickness of silane and resist layer and spacing between the nanoholes.

Structural Basis For Sequence Specific Dna Binding And Protein Dimerization Of Hoxa13, Yonghong Zhang, Christine A. Larsen, H. Scott Stadler, James B. Ames

Chemistry Faculty Publications and Presentations

The homeobox gene (HOXA13) codes for a transcription factor protein that binds to AT-rich DNA sequences and controls expression of genes during embryonic morphogenesis. Here we present the NMR structure of HOXA13 homeodomain (A13DBD) bound to an 11-mer DNA duplex. A13DBD forms a dimer that binds to DNA with a dissociation constant of 7.5 nM. The A13DBD/DNA complex has a molar mass of 35 kDa consistent with two molecules of DNA bound at both ends of the A13DBD dimer. A13DBD contains an N-terminal arm (residues 324 - 329) that binds in the DNA minor groove, and a C-terminal helix (residues …

Synthesis And Characterization Of N- And P- Doped Tin Oxide Nanowires, Hoang Tran, Shankar B. Rananavare

Chemistry Faculty Publications and Presentations

Bulk-scale synthetic methods for preparing doped tin oxide (SnO₂) nanowires (NWs) are presented. n-and p-doping is achieved through insertion of Antimony and Lithium in tin oxide lattice, respectively. We also present a comparison of the structural and optical properties of SnO₂ nanoparticles (NPs), and SnO₂ NWs. Both n-type and p- type NWs display a characteristic red shift in their photoluminescence (PL) spectra. Surface plasmons observed in these systems imply high carrier concentrations. These corrosion resistant materials are useful in fabricating ultra-sensitive gas detectors and transparent electronics.

Analysis Of The Conformational Behavior And Stability Of The Sap And Tsap Isomers Of Lanthanide(Iii) Nb-Dota-Type Chelates, Gyula Tircso, Benjamin Charles Webber, Benjamin E. Kucera, Victor G. Young, Mark Woods

Chemistry Faculty Publications and Presentations

Controlling the water exchange kinetics of macrocyclic Gd(3+) chelates, a key parameter in the design of improved magnetic resonance imaging (MRI) contrast media, may be facilitated by selecting the coordination geometry of the chelate. The water exchange kinetics of the mono- capped twisted square antiprism (TSAP) being much closer to optimal than those of the mono capped square antiprism (SAP) render the TSAP isomer more desirable for high relaxivity applications. Two systems have been developed that allow for selection of the TSAP coordination geometry in 1,4,7,10-tetraazacyclododecane-1,4,7,10-tetraacetic acid (DOTA)-type Gd(3+) chelates, both based upon the macrocycle nitrobenzyl cyclen. In this paper …

Bis Photobase Generator, Hoang Tran, Shankar B. Rananavare

Chemistry Faculty Publications and Presentations

The extension of 193nm technology is desirable due to the magnitude of past investments. Since “optical” advancements are increasingly difficult, there is a strong demand for more sophisticated “smart” resists to increase pattern density. Many studies have proven double pattering can be used for the extension of 193nm lithography. In this study, a new class of two stage photo base generators will be introduced along with the synthetic procedure and molecular characterization. The characterizations for exposure study by NMR have shown typical characteristics to stage decomposition under the exposure of 254nm light as well as promising pitch division. GCMS was …

Hiv-1 Matrix Protein Binding To Rna, Ayna Alfadhli, Henry Mcnett, Seyram Tsagli, Hans Peter Bachinger, David H. Peyton

Chemistry Faculty Publications and Presentations

The matrix (MA) domain of the HIV-1 precursor Gag (PrGag) protein plays multiple roles in the viral replication cycle. One essential role is to target PrGag proteins to their lipid raft-associated phosphatidylinositol-(4,5)-bisphosphate (PI[4,5]P2) assembly sites at the plasma membranes (PMs) of infected cells. In addition to this role, several reports have implicated nucleic acid binding properties to retroviral MAs. Evidence indicates that RNA binding enhances the binding specificity of MA to PI(4,5)P2-containing membranes, and supports a hypothesis in which RNA binding to MA acts as a chaperone that protects MA from associating with inappropriate cellular membranes prior to PrGag delivery …

Investigations Into Whole Water, Prototropic And Amide Proton Exchange In Lanthanide(Iii) Dota-Tetraamide Chelates, Mark Woods, Azhar Pasha, Piyu Zhao, Gyula Tircso, Somdatta Chowdhury, Garry Kiefer, Donald E. Woessner, A. Dean Sherry

Chemistry Faculty Publications and Presentations

Lanthanide(III) chelates of DOTA-tetraamide ligands have been an area of particular interest since the discovery that water exchange kinetics are dramatically affected by the switch from acetate to amide side-chain donors. More recently these chelates have attracted interest as potential PARACEST agents for use in MRI. In this paper we report the results of studies using chemical exchange saturation transfer (CEST) and some more recently reported chelates to re-examine the exchange processes in this class of chelate. We find that the conclusions of Parker and Aime are, for the most part, solid; water exchange is slow and a substantial amount …

Tension Directly Stabilizes Reconstituted Kinetochore-Microtubule Attachments, Bungo Akiyoshi, Krishna K. Sarangapani, Andrew F. Powers, Christian R. Nelson, Steve Reichow, Hugo Arellano-Santoyo, Tamir Gonen, Jeffrey A. Ranish, Charles L. Asbury, Sue Biggins

Chemistry Faculty Publications and Presentations

Kinetochores are macromolecular machines that couple chromosomes to dynamic microtubule tips during cell division, thereby generating force to segregate the chromosomes. Accurate segregation depends on selective stabilization of correct ‘bi-oriented’ kinetochore-microtubule attachments, which come under tension due to opposing forces exerted by microtubules. Tension is thought to stabilize these bi-oriented attachments indirectly, by suppressing the destabilizing activity of a kinase, Aurora B. However, a complete mechanistic understanding of the role of tension requires reconstitution of kinetochore-microtubule attachments for biochemical and biophysical analyses in vitro. Here we show that native kinetochore particles retaining the majority of kinetochore proteins can be …

Asimafoetidnol: A New Sesquiterpenoid Coumarin From The Gum Resin Of Ferula Assa-Foetida, Debasish Bandyopadhyay, Manas Banerjee, Subrata Laskar, Bidyut Basak

Chemistry Faculty Publications and Presentations

Chemical investigation of the gum resin of Ferula assa-foetida L. resulted in the isolation of a new sesquiterpenoid coumarin, 7-(((E)-5-((1S,3S,6S)-3,6- dihydroxy-2,2,6-trimethylcyclohexyl)-3-methylpent-2-en-1-yl)oxy) -2H-chromen-2-one (asimafoetidnol), together with several other known compounds. The structure of asimafoetidnol was established on the basis of spectroscopic analyses. Geometry optimization of the compound has been carried out using a DFT/B3LYP/3-21G* method.

Fabrication Of Poly(Vinylidene Fluoride) (Pvdf) Nanofibers Containing Nickel Nanoparticles As Future Energy Server Materials, Faheem A. Sheikh, Travis Cantu, Javier Macossay-Torres, Hern Kim

Chemistry Faculty Publications and Presentations

In the present study, we introduce Poly(vinylidene fluoride) (PVDF) nanofibers containing nickel (Ni) nanoparticles (NPs) as a result of an electrospinning. Typically, a colloidal solution consisting of PVDF/Ni NPs was prepared to produce nanofibers embedded with solid NPs by electrospinning process. The resultant nanostructures were studied by SEM analyses, which confirmed well oriented nanofibers and good dispersion of Ni NPs over them. The XRD results demonstrated well crystalline feature of PVDF and Ni in the obtained nanostructures. Physiochemical aspects of prepared nano-structures were characterized for TEM which confirmed nanofibers were welloriented and had good dispersion of Ni NPs. Furthermore, the …

Organometallic Iron(Iii)-Salophene Exerts Cytotoxic Properties In Neuroblastoma Cells Via Mapk Activation And Ros Generation, Kyu Kwang Kim, Rakesh K. Singh, Robert M. Strongin, Richard G. Moore, Laurent Brard, Thilo S. Lange

Chemistry Faculty Publications and Presentations

The objective of the present study was to investigate the specific effects of Iron(III)-salophene (Fe-SP) on viability, morphology, proliferation, cell cycle progression, ROS generation and pro-apoptotic MAPK activation in neuroblastoma (NB) cells. A NCI-DTP cancer screen revealed that Fe-SP displayed high toxicity against cell lines of different tumor origin but not tumor type-specificity. In a viability screen Fe-SP exhibited high cytotoxicity against all three NB cell lines tested. The compound caused cell cycle arrest in G1 phase, suppression of cells progressing through S phase, morphological changes, disruption of the mitochondrial membrane depolarization potential, induction of apoptotic markers as well as …

Strategies For Labeling Proteins With Paracest Agents, Olga Vasalatiy, Piyu Zhao, Mark Woods, Andrei Marconescu, Aminta Castillo-Muzquiz, Philip Thorpe, Garry Kiefer, A. Dean Sherry

Chemistry Faculty Publications and Presentations

Reactive surface lysine groups on the chimeric monoclonal antibody (3G4) and on human serum albumin (HSA) were labeled with two different PARACEST chelates. Between 7.4 – 10.1 chelates were added per 3G4 molecule and between 5.6 – 5.9 chelates per molecule of HSA, depending upon which conjugation chemistry was used. The immunoreactivity of 3G4 as measured by ELISA assays was highly dependent upon the number of attached chelates: 88% immunoreactivity with 7.4 chelates per antibody versus only 17% immunoreactivity with 10.1 chelates per antibody. Upon conjugation to 3G4, the bound water lifetime of Eu-1 increased only marginally, up from …

Sythesis Of Glucose Peracetate Via Bismuth Nitrate-Induced Reaction, Jose Lerma, Bimal K. Banik

Chemistry Faculty Publications and Presentations

Simple synthesis peracetylated glucose has been achieved starting from glucose and acetic anhydride in the absence of solvent via bismuth nitrate-catalyzed reaction. This method does not need large excess of acetic anhydride.

Microwave-Induced Bismuth Nitrate-Mediated Selective Hydrolysis Of Amide, Debasish Bandyopadhyay, Rene Solano Fonseca, Bimal K. Banik

Chemistry Faculty Publications and Presentations

Microwave-induced selective hydrolysis of amide to the corresponding amine has been achieved with bismuth nitrate and montmorillonite KSF clay.

Microwave-Induced N-Bromosuccinimide-Mediated Novel Synthesis Of Pyrroles Via Paal-Knorr Reaction, Rosemarie Andoh-Baidoo, Roberto Danso, Sanghamitra Mukherjee, Debasish Bandyopadhyay, Bimal K. Banik

Chemistry Faculty Publications and Presentations

An expeditious rapid synthesis of N-substituted pyrroles using microwave-induced Nbromosuccinimide- mediated solventless reaction of 2,5-hexanedione and primary amine has been accomplished.

Microwave-Induced Bismuth Nitrate-Catalyzed Electrophilic Substitution Of Indole With Keto Ester Under Slovent-Free Conditions, Sonya Rivera, Laura Iglesias, Debasish Bandyopadhyay, Bimal K. Banik

Chemistry Faculty Publications and Presentations

Microwave-induced preparation of bis(indollyl)methane derivative has been developed through a bismuth nitrate-catalyzed reaction of indole with diethylketomalonate under solventfree conditions.

An Easy And Straightforward Route For The Synthesis Of Disubstituted Imidazoles, Debasish Bandyopadhyay, Yvette Mora, Jesus A. Trevino-Cantu, Bimal K. Banik

Chemistry Faculty Publications and Presentations

A simple and high-yielding procedure has been developed to synthesize disubstituted imidalozes using phenyl glyoxal monohydrate, ammonium acetate and aldehydes. This synthetic protocol allows the preparation of a variety of 2,4 (s)-disubstituted imidalozes without using any catalyst, expensive or sensitive reagents. A corresponding 2-aroyl-4(s) disubstituted imidalozes derivative has also been isolated as byproduct. The effects of solvents have also been studied.

Microwave-Induced Indium-Catalyzed Synthesis Of Pyrrole Fused With Indoline In Water, Dina Abrego, Debasish Bandyopadhyay, Bimal K. Banik

Chemistry Faculty Publications and Presentations

An expeditious microwave-induced indium metal-catalyzed synthesis of pyrrole fused with indoline in water is developed by reacting isatin and 4-hydroxyproline.

Microwave-Induced Stereoselectivity Of Β-Lactam Formation: Effects Of Solvents, Debasish Bandyopadhyay, Marco Yanez, Bimal K. Banik

Chemistry Faculty Publications and Presentations

Synthesis of 3, 4-disubstituted 2-azetidinones has been achieved following Staudinger reaction under microwave-induced conditions. The stereoselectivity of β-lactam formation depends on the nature of the solvents used in the reaction.

Antimicrobial Activity Of Eugenol Derivatives, George Eyambe, Luis Canales, Bimal K. Banik

Chemistry Faculty Publications and Presentations

The antibacterial properties of the clove plant are due to the presence of eugenol, an aromatic phenolic compound. Eugenol was isolated from clove by stem distillation. The alkene group in eugenol was epoxidized resulting in the synthesis of epoxide-eugenol. The heterocyclic ring in epoxide was cleaved to a bromoalcohol derivative. The compounds synthesized epoxideeugenol, bromo alcohol and euginol were tested for antimicrobial activity against Staphylococcus aureus (ATCC 25923). Epoxide-eugenol was found to be the most effective antimicrobial agent among the three compounds tested.

Microwave-Induced Bismuth Nitrate-Catalyzed Expeditious Enamination Of Β-Dicarbonyl Compounds Under Solvent-Free Conditions, Debasish Bandyopadhyay, Bimal K. Banik

Chemistry Faculty Publications and Presentations

Bismuth nitrate-catalyzed, automated microwave-assisted expeditious synthesis of β- enaminones and β-enaminoesters has been carried out in an efficient manner under solvent-free condition. The reaction is general for primary, secondary (cyclic, heterocyclic and acyclic), benzylic as well as aromatic amines.

Detecting Specific Saccharides Via A Single Indicator, Soojin Lim, Jorge O. Escobedo, Mark Lowry, Robert M. Strongin

Chemistry Faculty Publications and Presentations

An improved synthesis of a rhodamine boronic acid indicator is reported. This compound is used in an optimized data collection protocol for wavelength- and time-dependent selectivity of sugars such as fructose and ribose derivatives. One indicator is thus used to selectively distinguish structurally related sugar analytes.

Microwave-Induced Bismuth Nitrate-Catalyzed Electrophilic Substitution Of 7-Aza Indole With Activated Carbonyl Compound Under Solvent-Free Conditions, Sonya Rivera, Debasish Bandyopadhyay, Bimal K. Banik

Chemistry Faculty Publications and Presentations

An expeditious microwave-induced synthetic method for the preparation of bis(azaindollyl)methane derivative has been developed through a bismuth nitrate-catalyzed reaction of 7-azaindole with diethylketomalonate under solvent-free conditions.