Physical Sciences and Mathematics Commons^™

Quantum Chemical Studies Of Nucleic Acids Can We Construct A Bridge To The Rna Structural Biology And Bioinformatics Communities?, Jiri Sponer,, Judit Sponer, Anton I. Petrov, Neocles B. Leontis

Chemistry Faculty Publications

In this feature article we provide a side-by-side introduction for two research fields quantum chemical calculations of molecular interaction in nucleic acids and RNA structural bioinformatics Our main aim is to demonstrate that these research areas while largely separated in contemporary literature have substantial potential to complement each other that could significantly contribute to our understanding of the exciting world of nucleic acids We identify research questions amenable to the combined application of modern ab initio methods and bioinformatics analysis of experimental structures while also assessing the limitations of these approaches The ultimate aim is to attain valuable physicochemical insights …

Electrochemical Investigation Of Azurin Thermodynamic And Adsorption Properties At Monolayer-Protected Cluster Film Assemblies – Evidence For A More Homogeneous Adsorption Interface, Tran Doan, Morgan Lynn Vargo, John K. Gerig, Chris P. Gulka, Matthew L. Trawick, Jonathan D. Dattelbaum, Michael C. Leopold

Chemistry Faculty Publications

Thermodynamic and adsorption properties of protein monolayer electrochemistry (PME) are examined for Pseudomonas aeruginosa azurin (AZ) immobilized at an electrode modified with a networked film of monolayer-protected clusters (MPCs) to assess if nanoparticle films of this nature offer a more homogeneous adsorption interface compared to traditional self-assembled monolayer (SAM) modified electrodes. Specifically, electrochemistry is used to assess properties of surface coverage, formal potential, peak broadening, and electron transfer (ET) kinetics as a function of film thickness. The modification of a surface with dithiol-linked films of MPCs (Au225C675) provides a more uniform binding interface for AZ that results in voltammetry with …

Iota-Carrageenan Hydrolysis By Pseudoalteromonas Carrageenovora Ifo12985, Bernadette M. Henares, Erwin P. Enriquez, Fabian M. Dayrit, Nina Rosario L. Rojas

Chemistry Faculty Publications

We report iota-carrageenan hydrolysis by Pseudoalteromonas carrageenovora IFO 12985. Kappa-carrageenase and lambda-carrageenase were previously isolated from this organism, but iota-carrageenase activity had not been reported in the literature. P. carrageenovora was grown in iota-carrageenan-based liquid medium. Using the zone of depression assay, transfer of aliquots of the culture to solid medium with 2% iota- and kappa-carrageenan showed extensive hydrolysis of iota-carrageenan. Analysis of the hydrolysates by C-13 Nuclear Magnetic Resonance spectroscopy confirmed degradation of the iota-carrageenan. Hydrolytic activity of P. carrageenovora grown in iota-carrageenan was compared with that of the same organism grown in kappa-carrageenan. Cell-free supernatants from each yielded …

[Fe-Fe]-Hydrogenase Reactivated By Residue Mutations As Bridging Carbonyl Rearranges: A Qm/Mm Study, Stefan Motiu, Valentin Gogonea

Chemistry Faculty Publications

In this work, we found aqueous enzyme phase reaction pathways for the reactivation of the exogenously inhibited [Fe-Fe]-hydrogenases by O2, or OH−, which metabolizes to H2O (Dogaru et al., Int J Quantum Chem 2008, 108; Motiu et al., Int J Quantum Chem 2007, 107, 1248). We used the hybrid quantum mechanics/molecular mechanics (QM/MM) method to study the reactivation pathways of the exogenously inhibited enzyme matrix. The ONIOM calculations performed on the enzyme agree with experimental results (Liu et al., J Am Chem Soc 2002, 124, 5175), that is, wild-type [Fe-Fe]-hydrogenase H-cluster is inhibited by oxygen metabolites. An enzyme spherical region …

Dnmt1 Stability Is Regulated By Proteins Coordinating Deubiquitination And Acetylation-Driven Ubiquitination, Zhanwen Du, Jing Song, Yong Wang, Yiqing Zhao, Kishore Guda, Shuming Yang, Hung Ying Kao, Yan Xu, Joseph Willis, Sanford D. Markowitz, David Sedwick, Robert M. Ewing, Zhenghe Wang

Chemistry Faculty Publications

DNA methyltransferase 1 (DNMT1) is the primary enzyme that maintains DNA methylation. We describe a previously unknown mode of regulation of DNMT1 protein stability through the coordinated action of an array of DNMT1-associated proteins. DNMT1 was destabilized by acetylation by the acetyltransferase Tip60, which triggered ubiquitination by the E3 ligase UHRF1, thereby targeting DNMT1 for proteasomal degradation. In contrast, DNMT1 was stabilized by histone deacetylase 1 (HDAC1) and the deubiquitinase HAUSP (herpes virus–associated ubiquitin-specific protease). Analysis of the abundance of DNMT1 and Tip60, as well as the association between HAUSP and DNMT1, suggested that during the cell cycle the initiation …

Electronic Properties Of N(5)-Ethyl Flavinium Ion, Vincent Sichula, Pavel Kucheryavy, Renat Khatmullin, Ying Hu, Ekaterina Mirzakulova, Shubham Vyas, Samuel F. Manzer, Christopher M. Hadad, Ksenija D. Glusac

Chemistry Faculty Publications

We investigated the electronic properties of N(5)-ethyl flavinium perchlorate (Et-Fl(+)) and compared them to those of its parent compound, 3-methyllumiflavin (Fl). Absorption and fluorescence spectra of Fl and Et-Fl(+) exhibit similar spectral features, but the absorption energy of Et-Fl(+) is substantially lower than that of Fl. We calculated the absorption signatures of Fl and Et-Fl(+) using time-dependent density functional theory (TD-DFT) methods and found that the main absorption bands of Fl and Et-Fl(+) are (pi,pi*) transitions for the S(1) and S(3) excited states. Furthermore, calculations predict that the S(2) state has (n,pi*) character. Using cyclic voltammetry and a simplistic consideration …

Photoinduced Charge Separation In Platinum Acetylide Oligomers, Chen Liao, James E. Yarnell, Ksenija D. Glusac, Kirk S. Schanze

Chemistry Faculty Publications

The series of three donor-spacer-acceptor complexes, DPAF-Ptn-NDI, has been synthesized and characterized using time-resolved absorption spectroscopy In these complexes, the donor is a (diphenylamino)-2,7-fluorenylene (DPAF) unit, the acceptor is a naphthalene diimide (NDI), and the spacers are a series of platinum acetylides of varying lengths, [-Pt(PBu(3))(2)C C-Ph-C C-](n) (where Bu = n-butyl Ph = 1,4-phenylene and n = 1 2, and 3) Electrochemistry indicates that the DPAF-Ptn-NDI system has a charge transfer state at ca 1 5 eV above the ground state that is based on one electron transfer from the DPAF donor to the NDI acceptor Transient absorption spectroscopy …

Enhanced Electrochemistry Of Nanoparticle-Embedded Polyelectrolyte Films: Interfacial Electronic Coupling And Distance Dependence, Callie E. Dowdy, Michael C. Leopold

Chemistry Faculty Publications

Factors affecting the electronic communication believed to be responsible for the enhanced solution electrochemistry observed at electrodes modified with hybrid polyelectrolyte–nanoparticle (PE–NP) film assemblies were systematically investigated. Specifically, the faradaic current and voltammetric peak splitting recorded for cyclic voltammetry of ferricyanide redox species (Fe(CN)63−/4−) at films constructed with various architectures of citrate-stabilized gold NPs embedded in polyelectrolyte films composed of poly-l-lysine and poly-S-styrene were used to establish the relative importance of both distance and electronic coupling. Layer-by-layer construction of PE–NP films allowed for the position and density of NPs to be varied within the film to assess electronic coupling between …

Nanometer To Millimeter Scale Peptide-Porphyrin Materials, Daniil V. Zaytsev, Fei Xie, Madhumita Mukherjee, Alexey Bludin, Borries Demeler, Robert M. Breece, David L. Tierney, Michael Y. Ogawa

Chemistry Faculty Publications

AQ-Pal14 is a 30-residue polypeptide that was designed to form an alpha-helical coiled coil that contains a metal-binding 4-pyridylalanine residue on its solvent-exposed surface. However, characterization of this peptide shows that it exists as a three-stranded coiled coil, not a two-stranded one as predicted from its design. Reaction with cobalt(III) protoporphyrin IX (Co-PPIX) produces a six-coordinate Co-PPIX(AQ-Pal 14)(2) species that creates two coiled-coil oligomerization domains Coordinated to opposite laces of the porphyrin ring. It is found that this species undergoes a buffer-dependent Self-assembly process: nanometer-scale globular materials were formed when these components were reacted in unbuffered H(2)O, while millimeter-scale, rod-like …

Cox-2 Inhibitor Nimesulide Analogs Are Aromatase Suppressors In Breast Cancer Cells, Bin Su, Xiaohan Cai, Yanyan Hong, Shiuan Chen

Chemistry Faculty Publications

Cyclooxygenase-2 (COX-2) inhibitor nimesulide derivatives compounds A and B decreased aromatase activity in breast cancer cells via a novel mechanism different to aromatase inhibitors (AIs), and were defined as “aromatase suppressors”. Breast carcinoma cells (MCF-7aro and T47Daro) transfected with aromatase full gene were used to explore the mechanisms of the two compounds. They dose and time-dependently suppressed aromatase activity in MCF-7aro and T47Daro cells in the nanomole range. However, they neither directly inhibited aromatase, nor improved aromatase degradation even at much higher concentrations. They could also suppress androgen stimulated cell growth, but did not affect estrogen enhanced cell proliferation. These …

Molecular Dynamics Simulations Suggest That Rna Three-Way Junctions Can Act As Flexible Rna Structural Elements In The Ribosome, Neocles B. Leontis, Ivana Beššová, Kamila Réblová, Jiří Šponer

Chemistry Faculty Publications

We present extensive explicit solvent molecular dynamics analysis of three RNA three-way junctions (3WJs) from the large ribosomal subunit: the 3WJ formed by Helices 90-92 (H90-H92) of 23S rRNA; the 3WJ formed by H42-H44 organizing the GTPase associated center (GAC) of 23S rRNA; and the 3WJ of 5S rRNA. H92 near the peptidyl transferase center binds the 3'-CCA end of amino-acylated tRNA. The GAC binds protein factors and stimulates GTP hydrolysis driving protein synthesis. The 5S rRNA binds the central protuberance and A-site finger (ASF) involved in bridges with the 30S subunit. The simulations reveal that all three 3WJs possess …

Spectroscopic And Computational Studies Of The Laser Photolysis Of Matrix Isolated 1,2-Dibromoethanes: Formation And Fate Of The Bromoethyl Radicals, A. Kalume, L. George, P. Z. El-Khoury, Alexander N. Tarnovsky, S. A. Reid

Chemistry Faculty Publications

We report experimental and computational studies of the photolysis of atmospherically important 1,2-dibromoethanes (1,2-C(2)X(4)Br(2); X = H, F) in Ar matrixes at 5 K. Using the pulsed deposition method, we find that significant conformational relaxation occurs for 1,2-C(2)H(4)Br(2) (EDB; observed anti/gauche ratio =30:1) but not for 1,2-C(2)F(4)Br(2) (TFEDB; anti/gauche = 3:1), which is traced to a larger barrier to rotation about the C-C bond in the latter. Laser photolysis of matrix-isolated EDB at 220 nm reveals the growth of infrared bands assigned to the gauche conformer and C(2)H(4)-Br(2) charge transfer complex (both as major products), and the C(2)H(4)Br radical and …

Acetic Acid Aldol Reactions In The Presence Of Trimethylsilyl Trifluoromethanesulfonate, C. Wade Downey, Miles W. Johnson, Daniel H. Lawrence, Alan S. Fleisher, Kathryn J. Tracy

Chemistry Faculty Publications

In the presence of TMSOTf and a trialkylamine base, acetic acid undergoes aldol addition to non-enolizable aldehydes under exceptionally mild conditions. Acidic workup yields the β-hydroxy carboxylic acid. The reaction appears to proceed via a three-step, one-pot process, including in situ trimethylsilyl ester formation, bis-silyl ketene acetal formation, and TMSOTf-catalyzed Mukaiyama aldol addition. Independently synthesized TMSOAc also undergoes aldol additions under similar conditions.

Residue Mutations In [Fe-Fe]-Hydrogenase Impedes O 2 Binding: A Qm/Mm Investigation, Daniela Dogaru, Stefan Motiu, Valentin Gogonea

Chemistry Faculty Publications

[Fe-Fe]-hydrogenases are enzymes that reversibly catalyze the reaction of protons and electrons to molecular hydrogen, which occurs in anaerobic media. In living systems, [Fe-Fe]-hydrogenases are mostly used for H(2) production. The [Fe-Fe]-hydrogenase H-cluster is the active site, which contains two iron atoms. The latest theoretical investigations1,2 advocate that the structure of di-iron air inhibited species are either Fe(p) (II)-Fe(d) (II)-O-H(-), or Fe(p) (II)-Fe(d) (II)-O-O-H, thus O(2) has to be prevented from binding to Fe(d) in all di-iron subcluster oxidation states in order to retain a catalytically active enzyme. By performing residue mutations on [Fe-Fe]-hydrogenases, we were able to weaken O(2) …

Mechanism Of N(5)-Ethyl-Flavinium Cation Formation Upon Electrochemical Oxidation Of N(5)-Ethyl-4a-Hydroxyflavin Pseudobase, Vincent Sichula, Ying Hu, Ekaterina Mirzakulova, Samuel F. Manzer, Shubham Vyas, Christopher M. Hadad, Ksenija D. Glusac

Chemistry Faculty Publications

We investigated the oxidation behavior of 5-ethyl-4a-hydroxy-3-methy1-4a,5-dihydrolumitlavin (pseudobase Et-FlH) in acetonitrile with the aim of determining if the two-electron oxidized Et-FlOH(2+) undergoes a release of hydroxyl cation and the production of 5-ethyl-3methyllumiflavinium cation (Et-Fl(+)). The focus of this work is to investigate the possibility of using Et-FlOH as a catalyst for water oxidation. The cyclic voltammetry demonstrates that Et-FlOH exhibits two one-electron oxidation potentials at +0.95 and +1.4 V versus normal hydrogen electrode (NHE), with the second oxidation potential being irreversible. The production of Et-FY' is observed in the cyclic voltammetry of Et-FlOH and has been previously assigned to the …

Modeling, Preparation, And Characterization Of A Dipole Moment Switch Driven By Z/E Photoisomerization, Alfonso Melloni, Riccardo Rossi Paccani, Donato Donati, Vinicio Zanirato, Adalgisa Sinicropi, Maria Laura Parisi, Elena Martin, Mikhail Ryazantsev, Wan Jian Ding, Luis Manuel Frutos, Riccardo Basosi, Stefania Fusi, Loredana Latterini, Nicolas Ferre, Massimo Olivucci

Chemistry Faculty Publications

We report the results of a multidisciplinary research effort where the methods of computational photochemistry and retrosynthetic analysis/synthesis have contributed to the preparation of a novel N-alkylated indanylidene-pyrroline Schiff base featuring an exocyclic double bond and a permanent zwitterionic head. We show that, due to its large dipole moment and efficient photoisomerization, such a system may constitute the prototype of a novel generation of electrostatic switches achieving a reversible light-induced dipole moment change on the order of 30 D. The modeling of a peptide fragment incorporating the zwitterionic head into a conformationally rigid side chain shows that the switch can …

Synthesis Of Pbs/Tio2 Colloidal Heterostructures For Photovoltaic Applications, Krishna P. Acharya, Nishshanka N. Hewa-Kasakarage, Taiwo R. Alabi, Ian Nemitz, Elena Khon, Bruno Ullrich, Pavel Anzenbacher Jr., Mikhail Zamkov

Chemistry Faculty Publications

We report on heteroepitaxial growth of nearly monodisperse PbS nanocrystals onto the surface of TiO2 nanoparticles via colloidal hot-injection routes. Fabricated PbS/TiO2 nanocomposites can be dispersed in nonpolar solvents, which enables an easy solution processing of these materials into mesoporous films for use as light-absorbing layers in nanocrystal-sensitized solar cells. High-temperature deposition of the sensitizer material allows controlling both the size and the number of PbS domains grown onto TiO2 nanoparticles, whereby providing synthetic means for tuning the absorbance spectrum of PbS/TiO2 nanocomposites and simultaneously enhancing their photocatalytic response in the visible and near-infrared. Compared with conventional ionic bath deposition …

An Antimicrobial Peptide Regulates Tumor-Associated Macrophage Trafficking Via The Chemokine Receptor Ccr2, A Model For Tumorigenesis, Ge Jin, Hameem I. Kawsar, Stanley A. Hirsch, Chun Zeng, Xun Jia, Zhimin Feng, Santosh K. Ghosh, Qing Yin Zheng, Aimin Zhou, Thomas M. Mcintyre, Aaron Weinberg

Chemistry Faculty Publications

Background: Tumor-associated macrophages (TAMs) constitute a significant part of infiltrating inflammatory cells that are frequently correlated with progression and poor prognosis of a variety of cancers. Tumor cell-produced human β-defensin-3 (hBD-3) has been associated with TAM trafficking in oral cancer; however, its involvement in tumor-related inflammatory processes remains largely unknown. Methodology: The relationship between hBD-3, monocyte chemoattractant protein-1 (MCP-1), TAMs, and CCR2 was examined using immunofluorescence microscopy in normal and oral carcinoma in situ biopsy specimens. The ability of hBD-3 to chemoattract host macrophages in vivo using a nude mouse model and analysis of hBD-3 on monocytic cell migration in …

Dna Polymerases: Perfect Enzymes For An Imperfect World, Anthony J. Berdis

Chemistry Faculty Publications

This Special Thematic Issue explores the molecular properties of DNA polymerases as extraordinary biological catalysts. In this short introductory chapter, I briefly highlight some of the most important concepts from the articles contained within this Special Issue. The contents of this Special Issue are arranged into distinct sub-categories corresponding to mechanistic studies of faithful DNA polymerization, studies of "specialized" DNA polymerases that function on damaged DNA, and DNA polymerases that are of therapeutic importance against various diseases. Emphasis is placed on understanding the dynamic cellular roles and biochemical functions of DNA polymerases, and how their structure and mechanism impact their …

Non-Natural Nucleotides As Probes For The Mechanism And Fidelity Of Dna Polymerases, Irene Lee, Anthony J. Berdis

Chemistry Faculty Publications

DNA is a remarkable macromolecule that functions primarily as the carrier of the genetic information of organisms ranging from viruses to bacteria to eukaryotes. The ability of DNA polymerases to efficiently and accurately replicate genetic material represents one of the most fundamental yet complex biological processes found in nature. The central dogma of DNA polymerization is that the efficiency and fidelity of this biological process is dependent upon proper hydrogen-bonding interactions between an incoming nucleotide and its templating partner. However, the foundation of this dogma has been recently challenged by the demonstration that DNA polymerases can effectively and, in some …

Terminal Deoxynucleotidyl Transferase: The Story Of A Misguided Dna Polymerase, Edward A. Motea, Anthony J. Berdis

Chemistry Faculty Publications

Nearly every DNA polymerase characterized to date exclusively catalyzes the incorporation of mononucleotides into a growing primer using a DNA or RNA template as a guide to direct each incorporation event. There is, however, one unique DNA polymerase designated terminal deoxynucleotidyl transferase that performs DNA synthesis using only single-stranded DNA as the nucleic acid substrate. In this chapter, we review the biological role of this enigmatic DNA polymerase and the biochemical mechanism for its ability to perform DNA synthesis in the absence of a templating strand. We compare and contrast the molecular events for template-independent DNA synthesis catalyzed by terminal …

Bunching Effect In Single-Molecule T4 Lysozyme Nonequilibrium Conformational Dynamics Under Enzymatic Reactions, Yuanmin Wang, H. Peter Lu

Chemistry Faculty Publications

The bunching effect, implying that conformational motion times tend to bunch in a finite and narrow time window, is observed and identified to be associated with substrate enzyme complex formation in T4 lysozyme conformational dynamics under enzymatic reactions. Using single-molecule fluorescence spectroscopy, we have probed T4 lysozyme conformational motions under the hydrolysis reaction of polysaccharide of E. coli 13 cell walls by monitoring the fluorescence resonant energy transfer (FRET) between a donor acceptor probe pair tethered to T4 lysozyme domains involving open close hinge-bending motions. On the basis of the single-molecule spectroscopic results, molecular dynamics simulation, and a random walk …

Nanostructured Poly(3,4-Ethylenedioxythiophene)–Metalloporphyrin Films: Improved Catalytic Detection Of Peroxynitrite, Serban Peteu, Pubudu Peiris, Ermias Gebermichael, Mekki Bayachou

Chemistry Faculty Publications

We investigated in this paper the sensing performance of inherently conductive polymer, poly(3,4-ethylenedioxythiophene) (PEDOT), functionalized with hemin (iron protoporphyrin) as an electrocatalytic reporter. The sensing platform is prepared by electrodeposition of a composite film of hemin–PEDOT on a 30-μm diameter carbon fiber electrode (CFE). The polymerized films were characterized by field emission scanning electron microscopy (FESEM), which pointed to nanostructured films with tortuous pores. The electrocatalytic oxidation of peroxynitrite was characterized by cyclic voltammetry as well as other electrochemical methods. The catalytic current is proportional to the analyte's concentration. Optimized hemin–PEDOT modified CFEs were utilized for the first time to …

Ultrafast Carrier Dynamics In Type Ii Znse/Cds/Znse Nanobarbells, Nishshanka N. Hewa-Kasakarage, Patrick Z. El-Khoury, Alexander N. Tarnovsky, Maria Kirsanova, Ian Nemitz, Alexander Nemchinov, Mikhail Zamkov

Chemistry Faculty Publications

We employ femtosecond transient absorption spectroscopy to get an insight into ultrafast processes occurring at the interface of type II ZnSe/CdS heterostructured nimocrystals fabricated via colloidal routes and comprising a barbell-like arrangement of ZnSe tips and CdS nanorods. Our study shows that resonant excitation of ZnSe tips results in an unprecedently fast transfer of excited Electrons into CdS domains of nanobarbells (<0.35 ps), whereas selective pumping of CdS components loads to a relatively slow injection of photoinduced holes into ZnSe tips (tau(h) = 95 ps). A qualitative thermodynamic description of observed electron processes within the classical limit of Marcus theory was used to identify a specific charge transfer regime associated with the ultrafast electron injection into CdS. Potential photocatalytic applications of the observed fast separation of carriers along the main axis of ZnSe/CdS barbells are discussed.

Effects Of Uvb-Induced Oxidative Stress On Protein Expression And Specific Protein Oxidation In Normal Human Epithelial Keratinocytes: A Proteomic Approach, Marzia Perluigi, Fabio Di Domenico, Carla Blarzino, Cesira Foppoli, Chiara Cini, Alessandra Giorgi, Caterina Grillo, Federico De Marco, D. Allan Butterfield, Maria E. Schininà, Raffaella Coccia

Chemistry Faculty Publications

BACKGROUND: The UVB component of solar ultraviolet irradiation is one of the major risk factors for the development of skin cancer in humans. UVB exposure elicits an increased generation of reactive oxygen species (ROS), which are responsible for oxidative damage to proteins, DNA, RNA and lipids. In order to examine the biological impact of UVB irradiation on skin cells, we used a parallel proteomics approach to analyze the protein expression profile and to identify oxidatively modified proteins in normal human epithelial keratinocytes.

RESULTS: The expression levels of fifteen proteins - involved in maintaining the cytoskeleton integrity, removal of damaged proteins …

Selective Regulation Of Aromatase Expression For Drug Discovery, Robert W. Brueggemeier, Bin Su, Michael V. Darby, Yasuro Sugimoto

Chemistry Faculty Publications

Aromatase is a particularly attractive drug target in the treatment of hormone-responsive breast cancer, and aromatase activity in breast cancer patients is greater in or near the tumor tissue compared with the normal breast tissue. Complex regulation of aromatase expression in human tissues involves alternative promoter sites that provide tissue-specific control. Previous studies in our laboratories suggested a strong association between aromatase (CYP19) gene expression and the expression of cyclooxygenase (COX) genes. Additionally, COX selective inhibitors can suppress CYP19 gene expression and decrease aromatase activity. Our current hypothesis is that pharmacological regulation of aromatase can act locally to decrease the …

Combined Single-Molecule Photon-Stamping Spectroscopy And Femtosecond Transient Absorption Spectroscopy Studies Of Interfacial Electron Transfer Dynamics, Lijun Guo, Yuanmin Wang, H. Peter Lu

Chemistry Faculty Publications

The inhomogeneous interfacial electron transfer (IET) dynamics of 9-phenyl-2,3,7-trihydroxy-6-fluorone (PF)-sensitized TiO2 nanoparticles (NPs) has been probed by a single-molecule photon-stamping technique as well as ensemble-averaged femtosecond transient absorption spectroscopy. The forward electron transfer (FET) time shows a broad distribution at the single-molecule level, indicating the inhomogeneous interactions and ET reactivity of the PF/TiO2 NP system. The broad distribution of the FET time is measured to be 0.4 ± 0.1 ps in the transient absorption and picoseconds to nanoseconds in the photon-stamping measurements. The charge recombination time, having a broad distribution at the single-molecule level, clearly shows a biexponential dynamic behavior …

Proton Disorder And The Dielectric Constant Of Type Ii Clathrate Hydrates, Steven W. Rick

Chemistry Faculty Publications

Computational studies are presented examining the degree of proton disorder in argon and molecular hydrogen sII clathrate hydrates. Results are presented using a variety of model potentials for the dielectric constant, the proton order parameter, and the molecular volume for the clathrate systems. The dielectric constant for the clathrate systems is found to be lower than the dielectric constant of ice in all models. The ratio of the clathrate to ice dielectric constant correlates well with the ratio of the densities, which is not the case for comparisons to the liquid, so that differences in the dielectric constants between ice …

Spectrophotometric And Colorimetic Methodology To Detect And Quantify Hydrazide Based Chemotherapeutic Drugs, Ronald Bartzatt

Chemistry Faculty Publications

Pharmaceuticals having the hydrazide functional group are an important division within anti-tuberculosis, anti-parasitic, anti-cancer, and anti-radiation chemotherapeutics. This work presents a colorimetric methodology to detect and quantify hydrazide based pharmaceuticals. Processes for rapid spot test, qualitative colorimetric assay, and spectrophotometric quantitative assay are presented. The reagent 2,6-dichloroquinon-4-chloroimine (Gibb's reagent) is utilized to accomplish the various analytical objectives. The rapid spot test and qualitative colorimetric assay enables a detection of hydrazide drugs to a level of 0.0037 grams per milliliter. Quantitative spectrophotometric detection of hydrazide drugs is sensitive to a level of 128.2 micrograms permilliliter. The molar absorptivity () is calculated …

Homozygous Frameshift Mutation In Tmco1 Causes A Syndrome With Craniofacial Dysmorphism, Skeletal Anomalies, And Mental Retardation, Baozhong Xin, Erik G. Puffenberger, Susan Turben, Haiyan Tan, Aimin Zhou, Heng Wang

Chemistry Faculty Publications

We identified an autosomal recessive condition in 11 individuals in the Old Order Amish of northeastern Ohio. The syndrome was characterized by distinctive craniofacial dysmorphism, skeletal anomalies, and mental retardation. The typical craniofacial dysmorphism included brachycephaly, highly arched bushy eyebrows, synophrys, long eyelashes, low-set ears, microdontism of primary teeth, and generalized gingival hyperplasia, whereas Sprengel deformity of scapula, fusion of spine, rib abnormities, pectus excavatum, and pes planus represented skeletal anomalies. The genome-wide homozygosity mapping using six affected individuals localized the disease gene to a 3.3-Mb region on chromosome 1q23.3-q24.1. Candidate gene sequencing identified a homozygous frameshift mutation, c.139_140delAG, in …