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2009

Chemistry Faculty Publications

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Articles 1 - 30 of 45

Full-Text Articles in Physical Sciences and Mathematics

Highly Nitrated Cyclopropanes As New High Energy Materials: Dft Calculations On The Properties Of C3H6−N(No2)N (N=3–6), Aloysus K. Lawong, David W. Ball Dec 2009

Highly Nitrated Cyclopropanes As New High Energy Materials: Dft Calculations On The Properties Of C3H6−N(No2)N (N=3–6), Aloysus K. Lawong, David W. Ball

Chemistry Faculty Publications

As part of a continuing study of new potential high energy materials, here we present results of calculations on cyclopropane molecules with three or more nitro groups. DFT calculations suggest that all molecules can exist as minimum-energy stationary states. Energy calculations indicate that some nitrocyclopropanes have a specific enthalpy of decomposition in excess of 8kJg−1, suggesting that they be explored as new potential high energy materials.

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Double Superhelix Model Of High Density Lipoprotein, Zhiping Wu, Valentin Gogonea, Xavier Lee, Mathew A. Wagner Dec 2009

Double Superhelix Model Of High Density Lipoprotein, Zhiping Wu, Valentin Gogonea, Xavier Lee, Mathew A. Wagner

Chemistry Faculty Publications

High density lipoprotein (HDL), the carrier of so-called “good” cholesterol, serves as the major athero-protective lipoprotein and has emerged as a key therapeutic target for cardiovascular disease. We applied small angle neutron scattering (SANS) with contrast variation and selective isotopic deuteration to the study of nascent HDL to obtain the low resolution structure in solution of the overall time-averaged conformation of apolipoprotein AI (apoA-I) versus the lipid (acyl chain) core of the particle. Remarkably, apoA-I is observed to possess an open helical shape that wraps around a central ellipsoidal lipid phase. Using the low resolution SANS shapes of the protein …

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Lead Optimization Of Cox-2 Inhibitor Nimesulide Analogs To Overcome Aromatase Inhibitor Resistance In Breast Cancer Cells, Bin Su, Shiuan Chen Dec 2009

Lead Optimization Of Cox-2 Inhibitor Nimesulide Analogs To Overcome Aromatase Inhibitor Resistance In Breast Cancer Cells, Bin Su, Shiuan Chen

Chemistry Faculty Publications

A series of COX-2 selective inhibitor nimesulide derivatives were synthesized. Their anti-cell proliferation activities were evaluated with a long-term estrogen deprived MCF-7aro (LTEDaro) breast cancer cell line, which is the biological model of aromatase inhibitor resistance for hormone-dependent breast cancer. Compared to nimesulide which inhibited LTEDaro cell proliferation with an IC50 at 170.30 μM, several new compounds showed IC50 close to 1.0 μM.

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Synthesis And Cytotoxic Analysis Of Some Disodium 3Β,6Β-Dihydroxysterol Disulfates, Jianguo Cui, Hui Wang, Yi Xin, Aimin Zhou Dec 2009

Synthesis And Cytotoxic Analysis Of Some Disodium 3Β,6Β-Dihydroxysterol Disulfates, Jianguo Cui, Hui Wang, Yi Xin, Aimin Zhou

Chemistry Faculty Publications

Disodium 3β,6β-dihydroxy-5α-cholestane disulfate (1) was synthesized in 4 steps with a high overall yield from cholesterol. First, cholesterol (4a) was converted to cholest-4-en-3,6-dione (5a) via oxidation with pyridinium chlorochromate (PCC) and then 5a was reduced by NaBH4 in the presence of NiCl2 to produce cholest-3β,6β-diol (6a). The reaction of 6a with the triethylamine-sulfur trioxide complex generated diammonium 3β,6β-dihydroxy-5α-cholestane disulfate (7a) and the treatment of 7a by cation exchange resin 732 (sodium form)(Na+) yielded the target steroid 1. Disodium 24-ethyl-3β,6β-dihydroxycholest-22-ene disulfate (2) and disodium 24-ethyl-3β,6β-dihydroxycholestane disulfate (3) were synthesized using a similar method. The cytotoxicity of these compounds against Sk-Hep-1 (human …

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Modeling The Fluorescence Of Protein-Embedded Tryptophans With Ab Initio Multiconfigurational Quantum Chemistry: The Limiting Cases Of Parvalbumin And Monellin, Sara Pistolesi, Adalgisa Sinicropi, Rebecca Pogni, Riccardo Basosi, Nicolas Ferre, Massimo Olivucci Dec 2009

Modeling The Fluorescence Of Protein-Embedded Tryptophans With Ab Initio Multiconfigurational Quantum Chemistry: The Limiting Cases Of Parvalbumin And Monellin, Sara Pistolesi, Adalgisa Sinicropi, Rebecca Pogni, Riccardo Basosi, Nicolas Ferre, Massimo Olivucci

Chemistry Faculty Publications

We show that a quantum-mechanics/molecular-mechanics strategy based on ab initio (i.e., first principle) multiconfigurational perturbation theory can reproduce the spectral properties of a tryptophan residue embedded in the contrasting hydrophobic and hydrophilic environments of parvalbumin and monellin, respectively. We show that the observed absorption and emission energies can be reproduced with a less than 3 kcal mol(-1) error. The analysis of the computed emission energies based on a protein disassembly scheme and protein electrostatic potential mapping allows for a detailed understanding of the factors modulating the tryptophan emission. It is shown that for rnonellin, where the tryptophan is exposed to …

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Thermochromic Absorption And Photoluminescence In [Pt(Ppy)(Mu-Ph(2)Pz)](2), Aaron A. Rachford, Felix N. Castellano Dec 2009

Thermochromic Absorption And Photoluminescence In [Pt(Ppy)(Mu-Ph(2)Pz)](2), Aaron A. Rachford, Felix N. Castellano

Chemistry Faculty Publications

The temperature effects on the spectral properties and photophysics of a new d(8)-d(8) dinuclear Pt-II chromophore, [Pt(ppy)(mu-Ph(2)pz)](2) (ppy is 2-phenylpyridine and Ph(2)pz is 3,5-diphenylpyrazolate), have been investigated. The thermochromic shifts are tentatively ascribed to intramolecular sigma interactions between the two pseudocofacial d(Z2) orbitals. Substantial emission profile changes occur in the solid state, solution, and doped polymer films.

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Determination Of 6-Benzylthioinosine In Mouse And Human Plasma By Liquid Chromatography–Tandem Mass Spectrometry, Lan Li, Yan Xu, David N. Wald, William Tse Nov 2009

Determination Of 6-Benzylthioinosine In Mouse And Human Plasma By Liquid Chromatography–Tandem Mass Spectrometry, Lan Li, Yan Xu, David N. Wald, William Tse

Chemistry Faculty Publications

This paper described the development and validation of a liquid chromatography–tandem mass spectrometry (LC–MS/MS) method for the quantitative determination of 6-benzylthioinosine (6BT), a novel myeloid leukemia differentiation-inducing agent, in mouse and human plasma. In this method, 2-amino-6-benzylthioinosine (2A6BT) was used as internal standard and ethyl acetate was used as organic solvent for the extraction of 6BT and internal standard from plasma samples. The extracted samples were separated on YMC ODS-AQ® column (2.0 mm × 50 mm), and the eluates from the column were monitored by the positive-electrospray-ionization tandem mass spectrometer (ESI+-MS/MS). Quantification of 6BT by internal calibration with 2A6BT was …

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Synthesis And Evaluation Of Some Steroidal Oximes As Cytotoxic Agents: Structure/Activity Studies (Ii), Jianguo Cui, Lei Fan, Yanmin Huang, Yi Xin, Aimin Zhou Nov 2009

Synthesis And Evaluation Of Some Steroidal Oximes As Cytotoxic Agents: Structure/Activity Studies (Ii), Jianguo Cui, Lei Fan, Yanmin Huang, Yi Xin, Aimin Zhou

Chemistry Faculty Publications

Hydroximinosteroids isolated from marine sponges display a variety of biological functions including cytotoxicity and anti-virus. In this study, we synthesized a series of hydroximinosteroid derivatives with a different functional group on the ring A or B and various side chains at position 17, and analyzed the cytotoxicity of these compounds against sk-Hep-1, H-292, PC-3 and Hey-1B cancer cells. Our results revealed that although a cholesterol-type side chain at position 17 is required for the biological activity of the compounds as we previously confirmed, elimination of the 4,5-double bond augmented the cytotoxic activity for the steroidal oximes. In addition, the presence …

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How Does The Relocation Of Internal Water Affect Resonance Raman Spectra Of Rhodopsin? An Insight From Casscf/Amber Calculations, Tadeusz Andruniow, Massimo Olivucci Nov 2009

How Does The Relocation Of Internal Water Affect Resonance Raman Spectra Of Rhodopsin? An Insight From Casscf/Amber Calculations, Tadeusz Andruniow, Massimo Olivucci

Chemistry Faculty Publications

The effect of relocation of the W2 crystallographic water in bovine rhodopsin has been investigated by comparing and analyzing simulated resonance Raman spectra of I HZX-and 1U19-based quantum mechanics/molecular mechanics (CASSCF/MM) models. The main target is to explore the sensitivity of the simulated resonance Raman spectra to protein cavity change. In particular, we focus on a quantitative investigation of the changes in the vibrational activity of rhodopsin induced by modifications in the protein cavity structure and in the water position. Comparison of the simulated FIR spectra of the Rh-1U19 and Rh-1HZX models with the measured spectrum of rhodopsin reveals that …

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Improving Replica Exchange Using Driven Scaling, Steven W. Rick Nov 2009

Improving Replica Exchange Using Driven Scaling, Steven W. Rick

Chemistry Faculty Publications

Replica exchange is a powerful simulation method in which simulations are run at a series of temperatures, with the highest temperature chosen so phase space can be sampled efficiently. In order for swaps to be accepted, the energy distributions of adjacent replicas must have some overlap. This can create the need for many replicas for large systems. In this paper, we present a new method in which the potential energy is scaled by a parameter, which has an explicit time dependence. Scaling the potential energy broadens the distribution of energy and reduces the number of replicas necessary to span a …

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Structure Of The Photochemical Reaction Path Populated Via Promotion Of Cf2i2 Into Its First Excited State, Patrick Z. El-Khoury, Alexander N. Tarnovsky, Igor Schapiro, Mikhail N. Ryazantsev, Massimo Olivucci Oct 2009

Structure Of The Photochemical Reaction Path Populated Via Promotion Of Cf2i2 Into Its First Excited State, Patrick Z. El-Khoury, Alexander N. Tarnovsky, Igor Schapiro, Mikhail N. Ryazantsev, Massimo Olivucci

Chemistry Faculty Publications

The photochemical reaction path following the promotion of CF2I2 into its lowest-lying excited electronic singlet state has been modeled using ab initio multiconfigurational quantum chemical calculations. It is found that a conical intersection drives the electronically excited CF2I2* species either to the CF2I + I radical pair or back to the starting CF2I2 structure. The structures of the computed relaxation pathways explain the photoproduct selectivity previously observed in the gas phase. Furthermore, the results provide the basis for explaining the condensed-phase photochemistry of CF2I2.

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Distance Dependence Of Electron Transfer Kinetics For Azurin Protein Adsorbed To Monolayer Protected Nanoparticle Film Assemblies, Morgan Lynn Vargo, Chris P. Gulka, John K. Gerig, Christopher M. Manieri, Jonathan D. Dattelbaum, Carolyn B. Marks, Nathaniel T. Lawrence, Matthew L. Trawick, Michael C. Leopold Aug 2009

Distance Dependence Of Electron Transfer Kinetics For Azurin Protein Adsorbed To Monolayer Protected Nanoparticle Film Assemblies, Morgan Lynn Vargo, Chris P. Gulka, John K. Gerig, Christopher M. Manieri, Jonathan D. Dattelbaum, Carolyn B. Marks, Nathaniel T. Lawrence, Matthew L. Trawick, Michael C. Leopold

Chemistry Faculty Publications

The distance dependence and kinetics of the heterogeneous electron transfer (ET) reaction for the redox protein azurin adsorbed to an electrode modified with a gold nanoparticle film are investigated using cyclic voltammetry. The nanoparticle films are comprised of nonaqueous nanoparticles, known as monolayer-protected clusters (MPCs), which are covalently networked with dithiol linkers. The MPC film assembly serves as an alternative adsorption platform to the traditional alkanethiolate self-assembled monolayer (SAM) modified electrodes that are commonly employed to study the ET kinetics of immobilized redox proteins, a strategy known as protein monolayer electrochemistry. Voltammetric analysis of the ET kinetics for azurin adsorbed …

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Classification And Energetics Of The Base-Phosphate Interactions In Rna, Craig L. Zirbel, Judit E. Šponer, Jiri Šponer, Jesse Stombaugh, Neocles B. Leontis Aug 2009

Classification And Energetics Of The Base-Phosphate Interactions In Rna, Craig L. Zirbel, Judit E. Šponer, Jiri Šponer, Jesse Stombaugh, Neocles B. Leontis

Chemistry Faculty Publications

Structured RNA molecules form complex 3D architectures stabilized by multiple interactions involving the nucleotide base, sugar and phosphate moieties. A significant percentage of the bases in structured RNA molecules in the Protein Data Bank (PDB) hydrogen-bond with phosphates of other nucleotides. By extracting and superimposing base-phosphate (BPh) interactions from a reduced-redundancy subset of 3D structures from the PDB, we identified recurrent phosphate-binding sites on the RNA bases. Quantum chemical calculations were carried out on model systems representing each BPh interaction. The calculations show that the centers of each cluster obtained from the structure superpositions correspond to energy minima on the …

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Pinpointing The Extent Of Electronic Delocalization In The Re(I)-To-Tetrazine Charge-Separated Excited State Using Time-Resolved Infrared Spectroscopy, Guifeng Li, Kumar Parimal, Shubham Vyas, Christopher M. Hadad, Amar H. Flood, Ksenija D. Glusac Aug 2009

Pinpointing The Extent Of Electronic Delocalization In The Re(I)-To-Tetrazine Charge-Separated Excited State Using Time-Resolved Infrared Spectroscopy, Guifeng Li, Kumar Parimal, Shubham Vyas, Christopher M. Hadad, Amar H. Flood, Ksenija D. Glusac

Chemistry Faculty Publications

Femtosecond mid-IR transient absorption spectroscopy (TRIR) and time-dependent density functional theory (TD-DFT) calculations on Re(CO)(3)Cl(Me(2)BPTZ) [Me(2)BPTZ = 3,6-bis(5-methyl-2-pyridine)-1,2,4,5-tetrazine] are used to demonstrate that the lowest excited state of the complex is a triplet metal-to-ligand charge-transfer ((3)MLCT) state with a lifetime of 225 ps. The short excited-state lifetime is explained by the energy-gap taw. Vibrational cooling of the (3)MLCT state shows up as early-time dynamics (3.6 ps). The structural changes in the excited state are deduced from the frequency shifts in the TRIR vibrational bands. The vibrational frequencies of the CO groups increase upon excitation as a result of decreased back-bonding …

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Spiroadamantyl 1,2,4-Trioxolane, 1,2,4-Trioxane, And 1,2,4-Trioxepane Pairs: Relationship Between Peroxide Bond Iron(Ii) Reactivity, Heme Alkylation Efficiency, And Antimalarial Activity, Xiaofang Wang, Darren J. Creek, Yuxiang Dong, Jacques Chollet, Christian Scheurer, Sergio Wittlin, Susan A. Charman, Patrick H. Dussault, James K. Wood, Jonathan L. Vennerstrom Aug 2009

Spiroadamantyl 1,2,4-Trioxolane, 1,2,4-Trioxane, And 1,2,4-Trioxepane Pairs: Relationship Between Peroxide Bond Iron(Ii) Reactivity, Heme Alkylation Efficiency, And Antimalarial Activity, Xiaofang Wang, Darren J. Creek, Yuxiang Dong, Jacques Chollet, Christian Scheurer, Sergio Wittlin, Susan A. Charman, Patrick H. Dussault, James K. Wood, Jonathan L. Vennerstrom

Chemistry Faculty Publications

These data suggest that iron(II) reactivity for a set of homologous spiroadamantyl 1,2,4-trioxolane, 1,2,4-trioxane, and 1,2,4-trioxepane peroxide heterocycles is a necessary, but insufficient, property of animalarial peroxides. Heme alkylation efficiency appears to give a more accurate prediction of antimalarial activity than FeSO4-mediated reaction rates, suggesting that antimalarial activity is not merely dependent on peroxide bond cleavage, but also on the ability of reactive intermediates to alkylate heme or other proximal targets.

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Fluorenylidene-Pyrroline Biomimetic Light-Driven Molecular Switches, Laura Rivado-Casas, Diego Sampedro, Pedro J. Campos, Stefania Fusi, Vinicio Zanirato, Massimo Olivucci Jul 2009

Fluorenylidene-Pyrroline Biomimetic Light-Driven Molecular Switches, Laura Rivado-Casas, Diego Sampedro, Pedro J. Campos, Stefania Fusi, Vinicio Zanirato, Massimo Olivucci

Chemistry Faculty Publications

A new family of biomimetic photoactivated molecular switches based in the retinal chromophore is described. Expedient synthesis allows a library of compounds with a different substitution pattern, including chiral substituents, to be obtained. The effect of substitution, solvent, and light source on the photoisomerization step has been assessed. The absorption maximum has been red-shifted ca. 50 nm with respect to related systems and rotation is now easily achieved by using visible light.

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Probing Single-Molecule Interfacial Geminate Electron-Cation Recombination Dynamics, Yuanmin Wang, Xuefei Wang, H. Peter Lu Jul 2009

Probing Single-Molecule Interfacial Geminate Electron-Cation Recombination Dynamics, Yuanmin Wang, Xuefei Wang, H. Peter Lu

Chemistry Faculty Publications

Interfacial electron-cation recombination in zinc-tetra (4-carboxyphenyl) porphyrin (ZnTCPP)/TiO(2) nanoparticle system has been probed at the single-molecule level by recording and analyzing photon-to-photon pair times of the ZnTCPP fluorescence. We have. developed a novel approach to reveal the hidden single-molecule interfacial electron-cation recombination dynamics by analyzing the autocorrelation function and a proposed convoluted single-molecule interfacial electron-cation recombination model. Our results suggest that the fluctuations of the interfacial electron transfer (ET) reactivity modulate the ET cycles as well as the interfacial electron-cation recombination dynamics. On the basis of this model, the single-molecule electron-cation recombination time of ZnTCPP/-TiO(2) system is deduced to be …

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The Role Of Adenine In Fast Excited-State Deactivation Of Fad: A Femtosecond Mid-Ir Transient Absorption Study, Guifeng Li, Ksenija D. Glusac Jul 2009

The Role Of Adenine In Fast Excited-State Deactivation Of Fad: A Femtosecond Mid-Ir Transient Absorption Study, Guifeng Li, Ksenija D. Glusac

Chemistry Faculty Publications

We present a study of excited-state dynamics of two flavin cofactors: flavin-adenine dinucleotide (FAD) and flavin-mononucleotide (FMN). We used femtosecond mid-R transient absorption spectroscopy to study the effect of FAD conformation oil its excited-state behavior. The conformation of FAD was modulated by changing the solvent polarity: in D(2)O, FAD is present predominantly in the "stacked" conformation, in which flavin and adenine moieties are in close proximity to each other, whereas the increased amount of DMSO led to an increased amount of the "open" conformer. FMN served as a model system which lacks adenine. We found that the "stacked" conformer undergoes …

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A Cox-2 Inhibitor Nimesulide Analog Selectively Induces Apoptosis In Her2 Overexpressing Breast Cancer Cells Via Cytochrome C Dependent Mechanisms, Bin Chen, Bin Su, Shiuan Chen Jun 2009

A Cox-2 Inhibitor Nimesulide Analog Selectively Induces Apoptosis In Her2 Overexpressing Breast Cancer Cells Via Cytochrome C Dependent Mechanisms, Bin Chen, Bin Su, Shiuan Chen

Chemistry Faculty Publications

Epidemiological and animal model studies have suggested that non-steroidal anti-inflammatory drugs (NSAIDs) can act as chemopreventive agents. The cyclooxygenase-2 (COX-2) inhibitor nimesulide shows anti-cancer effect in different type of cancers. In the current study, five breast carcinoma cell lines were used to explore the anti-cancer mechanisms of a nimesulide derivative compound 76. The compound dose dependently suppressed SKBR-3, BT474 and MDA-MB-453 breast cancer cell proliferation with IC50 of 0.9 μM, 2.2 μM and 4.0 μM, respectively. However, it needs much higher concentrations to inhibit MCF-7 and MDA-MB-231 breast cancer cell growth with IC50 at 22.1 μM and 19.6 μM, respectively. …

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Electronic Properties Of 4-Substituted Naphthalimides, Pavel Kucheryavy, Guifeng Li, Shubham Vyas, Christopher Hadad, Ksenija D. Glusac Jun 2009

Electronic Properties Of 4-Substituted Naphthalimides, Pavel Kucheryavy, Guifeng Li, Shubham Vyas, Christopher Hadad, Ksenija D. Glusac

Chemistry Faculty Publications

This paper describes a study of excited-state properties of naphthalmide (NI) and four 4-substituted derivatives: 4-chloronaphthalimide (Cl-NI), 4-methylthionaphthalmide (MeS-NI), 4-nitronaphthalimide (O(2)N-NI), and 4-(N,N-dimethylaminonaphthalimide (Me(2)N-NI). Steady-state absorption and fluorescence spectra were collected in solvents of varying polarity to determine the excited-state character of NI derivatives. Furthermore. the excited-state dynamics were studied Using femtosecond transient absorption spectroscopy. The experimental findings were compared to calculated data obtained using time-dependent density functional (TD-DFT) methods. We found that light absorption by all NI derivatives leads to the production of the second excited state (S(2)), which was found to have a n,pi* character. Within similar to …

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Phenylbenzimidazole-Based New Bipolar Host Materials For Efficient Phosphorescent Organic Light-Emitting Diodes, Shin-Ya Takizawa, Victor A. Montes, Pavel Anzenbacher Jr. Jun 2009

Phenylbenzimidazole-Based New Bipolar Host Materials For Efficient Phosphorescent Organic Light-Emitting Diodes, Shin-Ya Takizawa, Victor A. Montes, Pavel Anzenbacher Jr.

Chemistry Faculty Publications

Two new bipolar host materials based on a 1,3,5-tris(N-phenylbenzimidazol-2-yl)benzene (TPBI) core with the carbazole and diphenylamine groups were designed, synthesized, and applied in phosphorescent organic light-emitting diodes (PhOLEDs). The DFT calculations indicated desirable distribution of HOMO and LUMO densities, suggesting potential for bipolar charge transport. In addition, the electrochemical and phosphorescence studies revealed that neither the LUMO level nor the triplet energies differ significantly from the parent TPBI suggesting that the new materials would be suitable as hosts capable of both electron and hole transport and suitable for harvesting green electrophosphorescence. As a result of broader charge recombination zone resulting …

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Cholesterol Levels And Activity Of Membrane Bound Proteins: Characterization By Thermal And Electrochemical Methods, Noufissa Zanati, Michael Ellen Mathews, Perera N. Indika, John J. Moran, Jean A. Boutros, Alan T. Riga, Mekki Bayachou Jun 2009

Cholesterol Levels And Activity Of Membrane Bound Proteins: Characterization By Thermal And Electrochemical Methods, Noufissa Zanati, Michael Ellen Mathews, Perera N. Indika, John J. Moran, Jean A. Boutros, Alan T. Riga, Mekki Bayachou

Chemistry Faculty Publications

The long-term goal of this investigation is to study the effects of increased cholesterol levels on the molecular activity of membrane-bound enzymes such as nitric oxide synthase, that are critical in the functioning of the cardiovascular system. In this particular investigation, we used differential scanning calorimetry (DSC) and dielectric thermal analysis (DETA) to study the effect of added cholesterol on melting/recrystallization and dielectric behavior, respectively, of phosphatidylcholine (PC) bilayered thin films. We also used electrochemical methods to investigate the effect of added cholesterol on the redox behavior of the oxygenase domain of nitric oxide synthase as a probe embedded in …

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Biocatalytic Synthesis Of Diethanolamide Surfactants Under Mild Reaction Conditions, Galilee Uy Semblante, Modesto Tan Chua, Soma Chakraborty Jun 2009

Biocatalytic Synthesis Of Diethanolamide Surfactants Under Mild Reaction Conditions, Galilee Uy Semblante, Modesto Tan Chua, Soma Chakraborty

Chemistry Faculty Publications

Synthesis of fatty acid diethanolamide was carried out by the condensation of diethanolamine with lauric acid, decanoic acid and octanoic acid in the presence of Novozym 435. The influence of solvent, time, temperature and agitation on the reaction rate was studied. Formation of lauroyl diethanolamide was complete in 6h in acetonitrile at 50° C whereas in toluene the reaction was not complete in 6h. Increase of reaction temperature from 50° C to 70° C increased the reaction rate. Proper agitation of the reaction mixture enhanced the reaction rate. Reaction in solution appeared to be more efficient than the reaction in …

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Evaluation Of Silica Sol-Gel Microcapsule For The Controlled Release Of Insect Repellent, N,N-Diethyl-2-Methoxybenzamide, On Cotton, Ann Shireen Chan, Judy Del Valle, Kendricks Lao, Christian Malapit, Modesto Tan Chua, Regina C. So Jun 2009

Evaluation Of Silica Sol-Gel Microcapsule For The Controlled Release Of Insect Repellent, N,N-Diethyl-2-Methoxybenzamide, On Cotton, Ann Shireen Chan, Judy Del Valle, Kendricks Lao, Christian Malapit, Modesto Tan Chua, Regina C. So

Chemistry Faculty Publications

N,N-diethyl-2-methoxybenzamide, an insect repellent compound, was incorporated into cotton textile using the sol-gel method. Evaluation of the results of four different sol-gel formulations showed that a lower condensation rate resulted in significantly better encapsulation. Also investigated was the encapsulation in the presence of other polymers like polymethylmethacrylate (PMMA), polystyrene (PS) and polyvinyl alcohol (PVA) that prolong the release of the repellent. The sol-gel formulation, SiO2 : polymethylmethacrylate (PMMA) (1:0.8), gave smooth fabric and good encapsulation of the insect repellent compound. PS and PVA resulted in cloths which are aesthetically undesirable. Cloths coated with sol-gel PVA gave the best repellent release …

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Reductive Decomposition Of A Diazonium Intermediate By Dithiothreitol Affects The Determination Of Nos Turnover Rates, Perera N. Indika, Talal Sabbagh, Jean A. Boutros, Mekki Bayachou May 2009

Reductive Decomposition Of A Diazonium Intermediate By Dithiothreitol Affects The Determination Of Nos Turnover Rates, Perera N. Indika, Talal Sabbagh, Jean A. Boutros, Mekki Bayachou

Chemistry Faculty Publications

Accurate determination of nitrite either as such or as the breakdown product of nitric oxide (NO) is critical in a host of enzymatic reactions in various settings addressing structure–function relationships, as well as mechanisms and kinetics of molecular operation of enzymes. The most common way to quantify nitrite, for instance in nitric oxide synthase (NOS) mechanistic investigations, is the spectrophotometric assay based on the Griess reaction through external standard calibration. This assay is based on a two-step diazotization reaction, in which a cationic diazonium derivative of sulfanilamide is formed as intermediate before the final absorbing azo-product. We show that this …

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Frequency And Isostericity Of Rna Base Pairs, Craig L. Zirbel, Jesse Stombaugh, Eric Westhof Apr 2009

Frequency And Isostericity Of Rna Base Pairs, Craig L. Zirbel, Jesse Stombaugh, Eric Westhof

Chemistry Faculty Publications

Most of the hairpin, internal and junction loops that appear single-stranded in standard RNA secondary structures form recurrent 3D motifs, where non-WatsonCrick base pairs play a central role. Non-WatsonCrick base pairs also play crucial roles in tertiary contacts in structured RNA molecules. We previously classified RNA base pairs geometrically so as to group together those base pairs that are structurally similar (isosteric) and therefore able to substitute for each other by mutation without disrupting the 3D structure. Here, we introduce a quantitative measure of base pair isostericity, the IsoDiscrepancy Index (IDI), to more accurately determine which base pair substitutions can …

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The Design And Synthesis Of Farnesyl "Tail" Analogues Incorporating Aromatic Rings: A Comparison Of Wittig And Grignard Reaction Sequences, Mark F. Mechelke, Lisa Motschke, Todd Nichols, Sarah Albrecht Apr 2009

The Design And Synthesis Of Farnesyl "Tail" Analogues Incorporating Aromatic Rings: A Comparison Of Wittig And Grignard Reaction Sequences, Mark F. Mechelke, Lisa Motschke, Todd Nichols, Sarah Albrecht

Chemistry Faculty Publications

Mutant RAS proteins have been linked to over 30 of all human cancers. It has been shown that mutant RAS proteins that cannot be farnesylated do not induce malignant transformation. Therefore, farnesyl protein transferase (FPTase) inhibitors have become attractive targets as potential chemotherapeutic agents. Two farnesyl "tail" analogues have been prepared that incorporate aromatic rings. One of the compounds, trans-9-phenyl-8-nonen-1-ol, could only be prepared pure using a Grignard reaction sequence. This sequence is compared to the initially attempted Wittig reaction sequence that results in an inseparable mixture of cis/trans isomers. It is anticipated thatwhen coupled with poal diphosphate "head" …

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Inactivation Of [Fe-Fe]-Hydrogenase By O2. Thermodynamics And Frontier Molecular Orbitals Analyses, Daniela Dogaru, Stefan Motiu, Valentin Gogonea Mar 2009

Inactivation Of [Fe-Fe]-Hydrogenase By O2. Thermodynamics And Frontier Molecular Orbitals Analyses, Daniela Dogaru, Stefan Motiu, Valentin Gogonea

Chemistry Faculty Publications

The oxidation of H-cluster in gas phase, and in aqueous enzyme phase, has been investigated by means of quantum mechanics (QM) and combined quantum mechanics–molecular mechanics (QM/MM). Several potential reaction pathways (in the above-mentioned chemical environments) have been studied, wherein only the aqueous enzyme phase has been found to lead to an inhibited hydroxylated cluster. Specifically, the inhibitory process occurs at the distal iron (Fed) of the catalytic H-cluster (which isalso the atom involved in H2 synthesis). The processes involved in the H-cluster oxidative pathways are O2 binding, e− transfer, protonation, and H2O removal. We found that oxygen binding is …

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Polyelectrolyte-Linked Film Assemblies Of Nanoparticles And Nanoshells: Growth, Stability, And Optical Properties, Anne A. Galyean, Justin Malinowski, Robert W. Day, Kevin W. Kittredge, Michael C. Leopold Mar 2009

Polyelectrolyte-Linked Film Assemblies Of Nanoparticles And Nanoshells: Growth, Stability, And Optical Properties, Anne A. Galyean, Justin Malinowski, Robert W. Day, Kevin W. Kittredge, Michael C. Leopold

Chemistry Faculty Publications

Multi-layer films of nanoparticles and nanoshells featuring various polymeric linkage molecules have been assembled and their optical properties characterized. The growth dynamics, including molecular weight effects, and stability of the various nanoparticle film constructions, using both single polymer as well as combinations of alternating charge polyelectrolytes as linking mechanisms, are presented. The polymeric linkers studied include poly-L-lysine, poly-L-arginine, poly(allylamine hydrochloride), and polyamidoamine dendrimers. Significantly air stable films were achieved with the use of multi-layered polymeric bridges between the nanoparticles and nanoshells. Optical sensitivity normally observed with these nanomaterials in solution was observed for their corresponding film geometries, with the nanoshell …

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Synthesis Of Magnetic Porous Hollow Silica Nanotubes For Drug Delivery, H. Ma, J. Tarr, M. A. Decoster, J. Mcnamara, D. Caruntu, J. F. Chen, Charles J. O'Connor, Weilie Zhou Mar 2009

Synthesis Of Magnetic Porous Hollow Silica Nanotubes For Drug Delivery, H. Ma, J. Tarr, M. A. Decoster, J. Mcnamara, D. Caruntu, J. F. Chen, Charles J. O'Connor, Weilie Zhou

Chemistry Faculty Publications

In this paper, we report a synthesis of magnetic porous hollow silica nanotubes (MPHSNTs) using sol-gel method. The MPHSNTs were fabricated by coating Fe(3)O(4) nanoparticles and silica on surfactant hexadecyltrimethylammonium bromide (CTAB) modified CaCO(3) nanoneedles surface under alkaline condition. CaCO(3) nanoneedles and surfactant CTAB are introduced as nanotemplates to form the hollow and porous structures, respectively. After removing CTAB by calcination and etching CaCO(3) nanoneedles away in diluted acetic acid, magnetic porous hollow silica nanotubes with Fe(3)O(4) nanoparticles embedded in the silica shell were achieved. The products were characterized by scanning electron microscopy, transmission electron microscopy, and N(2) adsorption-desorption isotherms. …

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