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Chemistry Faculty Publications

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Articles 1051 - 1080 of 1129

Full-Text Articles in Chemistry

The 5s Rrna Loop E: Chemical Probing And Phylogenetic Data Versus Crystal Structure, Neocles B. Leontis, Eric Westhof Jul 1998

The 5s Rrna Loop E: Chemical Probing And Phylogenetic Data Versus Crystal Structure, Neocles B. Leontis, Eric Westhof

Chemistry Faculty Publications

A significant fraction of the bases in a folded, structured RNA molecule participate in noncanonical base pairing interactions, often in the context of internal loops or multi-helix junction loops. The appearance of each new high-resolution RNA structure provides welcome data to guide efforts to understand and predict RNA 3D structure, especially when the RNA in question is a functionally conserved molecule. The recent publication of the crystal structure of the "Loop E" region of bacterial 5S ribosomal RNA is such an event [Correll CC, Freeborn B, Moore PB, Steitz TA, 1997, Cell 91:705-712]. In addition to providing more examples of …

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Distance Dependence Of Electron Transfer Along Artificial Β-Strands At 298 And 77 K, S. R. L. Fernando, Gennady V. Kozlov, Michael Y. Ogawa Apr 1998

Distance Dependence Of Electron Transfer Along Artificial Β-Strands At 298 And 77 K, S. R. L. Fernando, Gennady V. Kozlov, Michael Y. Ogawa

Chemistry Faculty Publications

Photoinduced electron-transfer rate constants were measured for a series of binuclear metallopeptides consisting of a [Ru(bpy)(2)(cmbpy)](2+) electron donor tethered to a Co-III(NH3)(5) electron acceptor by an oligovaline peptide chain (bpy = 2,2'-bipyridine, cmbpy = 4-carboxy-4'-methyl-2,2'-bipyridine). These compounds were shown by H-1 NMR to adopt the conformational properties found within the individual strands of a beta-pleated sheet in both aqueous and methanol solutions. Emission lifetime measurements and HPLC product analysis show that the binuclear donor/acceptor compounds undergo photoinduced electron transfer (ET). The values of k(et) decrease with increasing donor/acceptor distance according to the expression k(et) = k' exp[-beta(r(-)r(0))]. A distance attenuation …

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A Cell Cycle-Regulated Adenine Dna Methyltransferase From Caulobacter Crescentus Processively Methylates Gantc Sites On Hemimethylated Dna, Anthony J. Berdis, Irene Lee, James K. Coward, Craig Stephens, Rachel Wright, Lucy Shapiro, Stephen J. Benkovic Mar 1998

A Cell Cycle-Regulated Adenine Dna Methyltransferase From Caulobacter Crescentus Processively Methylates Gantc Sites On Hemimethylated Dna, Anthony J. Berdis, Irene Lee, James K. Coward, Craig Stephens, Rachel Wright, Lucy Shapiro, Stephen J. Benkovic

Chemistry Faculty Publications

The kinetic properties of an adenine DNA methyltransferase involved in cell cycle regulation of Caulobacter crescentus have been elucidated by using defined unmethylated or hemimethylated DNA (DNAHM) substrates. Catalytic efficiency is significantly enhanced with a DNAHM substrate. Biphasic kinetic behavior during methyl incorporation is observed when unmethylated or DNAHM substrates are used, indicating that a step after chemistry limits enzyme turnover and is most likely the release of enzyme from methylated DNA product. The enzyme is thermally inactivated at 30°C within 20 min; this process is substantially decreased in the presence of saturating concentrations of DNAHM, suggesting that the enzyme …

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Dissociation Energies Of The Ga2, In2, And Gain Molecules, G Balducci, G Gigli, Giovanni Meloni Jan 1998

Dissociation Energies Of The Ga2, In2, And Gain Molecules, G Balducci, G Gigli, Giovanni Meloni

Chemistry Faculty Publications

The group III metal dimers Ga2 and In2 and the newly identified intermetallic molecule GaIn were investigated in a Knudsen cell-mass spectrometric study of the vapors over gallium–indium alloys. From the all-gas equilibria analyzed by the second-law and third-law methods the following dissociation energies were derived; D00 (Ga2)=110.8±4.9 kJ mol−1, D00 (In2)=74.4±5.7 kJ mol−1, D00 (GaIn)=90.7±3.7 kJ mol−1. The value here measured for the dissociation energy of In2 is discussed and compared with a previous experimental determination and with the results of more recent theoretical investigations.

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Mea Culpa: Formal Education And The Dis-Integrated World., Brian P. Coppola, Douglas S. Daniels Jan 1998

Mea Culpa: Formal Education And The Dis-Integrated World., Brian P. Coppola, Douglas S. Daniels

Chemistry Faculty Publications

Formal education has removed itself so far from any truly integrated view of the Natural World that fragmentation and certainty are prevailing ethics. Technological progress has resulted in increased specialization within academic disciplines and their concurrent separation from each other. Knowledge is extracted from a fully integrated world, but is examined and defined by the 'dis-integrated' objectives.

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Nano-Engineering Of Molecular Films By Self-Assembly And Langmuir-Blodgett Techniques, Erwin P. Enriquez Jan 1998

Nano-Engineering Of Molecular Films By Self-Assembly And Langmuir-Blodgett Techniques, Erwin P. Enriquez

Chemistry Faculty Publications

The availability of sophisticated and ultra-sensitive analytical tools and the maturity of organic synthesis have opened new possibilities for fabrication of molecular materials designed at the nanometer scale. Presently, the most promising and widely investigated methodologies are the self-assembly and Langmuir-Blodgett procedures. The former relies on the strong, preferential affinity of specific functional groups to solid surfaces, whereas the latter involves transfer of pre-formed mono layers at the air-water interface onto solid substrates. These techniques and their recent applications are reviewed.

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Assembly And Disassembly Of Dna Polymerase Holoenzyme, Daniel J. Sexton, Anthony J. Berdis, Stephen J. Benkovic Oct 1997

Assembly And Disassembly Of Dna Polymerase Holoenzyme, Daniel J. Sexton, Anthony J. Berdis, Stephen J. Benkovic

Chemistry Faculty Publications

The complex task of genomic replication requires a large collection of proteins properly assembled within the close confines of the replication fork. The mechanism and dynamics of holoenzyme assembly and disassembly have been investigated using steady state and pre-steady state methods as opposed to structural studies, primarily due to the intrinsic transient nature of these protein complexes during DNA replication. The key step in bacteriophage T4 holoenzyme assembly involves ATP hydrolysis, whereas disassembly is mediated by subunit dissociation of the clamp protein in an ATP-independent manner.

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Electron Transfer Across A Peptide−Peptide Interface Within A Designed Metalloprotein, Gennady V. Kozlov, Michael Y. Ogawa Sep 1997

Electron Transfer Across A Peptide−Peptide Interface Within A Designed Metalloprotein, Gennady V. Kozlov, Michael Y. Ogawa

Chemistry Faculty Publications

Mechanistic studies of biological electron-transfer (ET) reactions have involved the use of surface-derivatized proteins, protein−protein complexes, and polypeptide-bridged donor−acceptor compounds. These latter studies seek to use well-defined model systems to better define the role of the intervening protein matrix in mediating biological electron transfers. However, whereas many in vivo ET reactions occur across a noncovalent protein−protein interface, the primary role of the peptide spacers found in current model systems is to provide a covalent link between the donor and acceptor sites. As such, these systems are poorly suited to probe the mechanisms of ET reactions occurring across a peptide−peptide interface.

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Rounding Numbers: Why The "New System" Doesn't Work, W. Robert Midden Apr 1997

Rounding Numbers: Why The "New System" Doesn't Work, W. Robert Midden

Chemistry Faculty Publications

This paper explains a correction to the rounding rule previously publishedin this Journal. The earlier article reported that the best way to roundnumbers is to always round up when the first digit dropped is 5. However,this will lead to accumulation of error when errors are averaged. Arounding strategy that leads to less error is to round up when 5 isfollowed by any nonzero digits, but to round even when 5 is followed byzeros or no other digits. By rounding the last kept digit to an evennumber, half the time the digit is increased and half the time it is keptthe …

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Partitioning Of The Reactive Nitrogen Reservoir In The Lower Sratosphere Of The Southern Hemisphere: Observations And Modeling, R. S. Gao, D. W. Fahey, R. J. Salawitch, S. A. Lloyd, D. E. Anderson, R. Demajistre, C. T. Mcelroy, E. L. Woodbridge, R. C. Wamsley, S. G. Donnelly, L. A. Del Negro, M. H. Proffitt, R. M. Stimpfle, D. W. Kohn, S. R. Kawa, L. R. Lait, M. Loewenstein, J. R. Podolske, E. R. Keim, J. E. Dye, J. C. Wilson, K. R. Chan Feb 1997

Partitioning Of The Reactive Nitrogen Reservoir In The Lower Sratosphere Of The Southern Hemisphere: Observations And Modeling, R. S. Gao, D. W. Fahey, R. J. Salawitch, S. A. Lloyd, D. E. Anderson, R. Demajistre, C. T. Mcelroy, E. L. Woodbridge, R. C. Wamsley, S. G. Donnelly, L. A. Del Negro, M. H. Proffitt, R. M. Stimpfle, D. W. Kohn, S. R. Kawa, L. R. Lait, M. Loewenstein, J. R. Podolske, E. R. Keim, J. E. Dye, J. C. Wilson, K. R. Chan

Chemistry Faculty Publications

Measurements of nitric oxide (NO), nitrogen dioxide (NO2), and total reactive nitrogen (NOy = NO + NO2 + NO3 + HNO3 + ClONO2 + 2N2O5 + ...) were made during austral fall, winter, and spring 1994 as part of the NASA Airborne Southern Hemisphere Ozone Experiment/Measurements for Assessing the Effects of Stratospheric Aircraft mission. Comparisons between measured NO2 values and those calculated using a steady state (SS) approximation are presented for flights at mid and high latitudes. The SS results agree with the measurements to within 8%, suggesting that the kinetic rate coefficients and calculated NO2 photolysis rate used in …

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Conformations And Relative Stabilities Of The Cis And Trans Isomers In A Series Of Isolated N-Phenylamides, V. P. Manea, K. J. Wilson, John R. Cable Feb 1997

Conformations And Relative Stabilities Of The Cis And Trans Isomers In A Series Of Isolated N-Phenylamides, V. P. Manea, K. J. Wilson, John R. Cable

Chemistry Faculty Publications

The gas-phase conformations of a series of isolated N-phenylamides have been determined from vibrationally resolved electronic spectra obtained by resonant two-photon ionization in a supersonic jet expansion. Both the cis and trans isomers of formanilide were identified, with the cis isomer in 6.5% abundance. The spectral features displayed by this isomer are consistent with a nonplanar geometry which undergoes a large change in the phenyl torsional angle following electronic excitation. The more abundant trans isomer of formanilide adopts a planar structure and is stabilized by 2.5 kcal/mol with respect to the cis isomer. In the excited electronic state the relative …

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Enhancing The Performance Of Membrane Introduction Mass Spectrometry By Organic Carrier And Liquid Chromatographic Separation, Shi Ouyang, Yong Hong Chen, Yan Xu Jan 1997

Enhancing The Performance Of Membrane Introduction Mass Spectrometry By Organic Carrier And Liquid Chromatographic Separation, Shi Ouyang, Yong Hong Chen, Yan Xu

Chemistry Faculty Publications

A method of membrane introduction mass spectrometry with liquid chromatographic separation (LC/MIMS) for the analysis of volatile organic compounds (VOCs) in water has been developed. The method not only inherited all the advantages of membrane introduction mass spectrometry by flow-injection analysis (FIA/MIMS), but also expanded the application of MIMS to the determination of compounds with identical quantitation ions. Because the quantitation by LC/MIMS is based on two-dimensional identification (retention time (tr) and mass-to-charge ratio ()), it provides a tangible approach to the analysis of VOCs in complex aqueous samples. In this work, a C18 column and a mobile phase (methanol/water) …

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Identification Of The Adp-L-Glycero-D-Manno-Heptose-6-Epimerase (Rfad) And Heptosyltransferase Ii (Rfaf) Biosynthesis Genes From Nontypeable Haemophilus Influenzae 2019, W A. Nichols, B W. Gibson, William Melaugh, N G. Lee, M Sunshine, M A. Apicella Jan 1997

Identification Of The Adp-L-Glycero-D-Manno-Heptose-6-Epimerase (Rfad) And Heptosyltransferase Ii (Rfaf) Biosynthesis Genes From Nontypeable Haemophilus Influenzae 2019, W A. Nichols, B W. Gibson, William Melaugh, N G. Lee, M Sunshine, M A. Apicella

Chemistry Faculty Publications

Haemophilus influenzae is an important human pathogen. The lipooligosaccharide (LOS) of H. influenzae has been implicated as a virulence determinant. To better understand the assembly of LOS in nontypeable H. influenzae (NtHi), we have cloned and characterized the rfaD and rfaF genes of NtHi 2019, which encode the ADP-L-glycero-D-manno-heptose-6-epimerase and heptosyltransferase II enzymes, respectively. This cloning was accomplished by the complementation of Salmonella typhimurium lipopolysaccharide (LPS) biosynthesis gene mutants. These deep rough mutants are novobiocin susceptible until complemented with the appropriate gene. In this manner, we are able to use novobiocin resistance to select for specific NtHi LOS inner core …

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Characterization Of A Transposon Tn916-Generated Mutant Of Haemophilus Ducreyi 35000 Defective In Lipooligosaccharide Biosynthesis, B W. Gibson, A A. Campagnari, William Melaugh, M A. Apicella, S Grass, Jing Wang, Katherine L. Palmer, R S. Munson Jan 1997

Characterization Of A Transposon Tn916-Generated Mutant Of Haemophilus Ducreyi 35000 Defective In Lipooligosaccharide Biosynthesis, B W. Gibson, A A. Campagnari, William Melaugh, M A. Apicella, S Grass, Jing Wang, Katherine L. Palmer, R S. Munson

Chemistry Faculty Publications

To define the role of the surface lipooligosaccharide (LOS) of Haemophilus ducreyi in the pathogenesis of chancroid, Tn916 mutants of H. ducreyi 35000 defective in expression of the murine monoclonal antibody (MAb) 3F11 epitope on H. ducreyi LOS were identified by immunologic screening. One mutant, designated 1381, has an LOS which lacks the MAb 3F11 epitope and migrates with an increased mobility on sodium dodecyl sulfate-polyacrylamide gel electrophoresis. The gene disrupted by the Tn916 element in strain 1381 was identified by cloning the sequences flanking the Tn916 element. The sequences were then used to probe a lambda DASHII genomic library. …

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Properties And Macromolecular Structure Of Unacetylated And Acetylated Nata De Coco, Ma. Assunta C. Cuyegkeng, Ma. Amy L. Dimalanta Jan 1997

Properties And Macromolecular Structure Of Unacetylated And Acetylated Nata De Coco, Ma. Assunta C. Cuyegkeng, Ma. Amy L. Dimalanta

Chemistry Faculty Publications

This study aims to gain more insight into the supramolecular structure of the cellulose in nata de coco, and to compare its ability to be modified with the known types of cellulose. The investigations were done using IR spectroscopy and thennal analysis. The IR spectra of microcrystalline cellulose were identical to cellulose spectra. However, those of dried nata de coco cellulose showed additional peaks that indicated a loss of inter- and intra-sheet hydrogen bonding, usually extensive in other cellulose forms where sheets are the prevalent secondary structures. This kind of structure would be consistent with the necessary framework for gel …

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The Role Of HoX In Super- And Subsonic Aircraft Exhaust Plumes, T. F. Hanisco, P. O. Wennberg, R. C. Cohen, J. G. Anderson, D. W. Fahey, E. R. Keim, R. S. Gao, R. C. Wamsley, Stephen G. Donnelly Ph.D., L. A. Del Negro, R. J. Salawitch, K. K. Kelly, M. H. Proffitt Jan 1997

The Role Of HoX In Super- And Subsonic Aircraft Exhaust Plumes, T. F. Hanisco, P. O. Wennberg, R. C. Cohen, J. G. Anderson, D. W. Fahey, E. R. Keim, R. S. Gao, R. C. Wamsley, Stephen G. Donnelly Ph.D., L. A. Del Negro, R. J. Salawitch, K. K. Kelly, M. H. Proffitt

Chemistry Faculty Publications

The generation of sulfuric acid aerosols in aircraft exhaust has emerged as a critical issue in determining the impact of supersonic aircraft on stratospheric ozone. It has long been held that the first step in the mechanism of aerosol formation is the oxidation of SO2 emitted from the engine by OH in the exhaust plume. We report in situ measurements of OH and HO2 in the exhaust plumes of a supersonic (Air France Concorde) and a subsonic (NASA ER-2) aircraft in the lower stratosphere. These measurements imply that reactions with OH are responsible for oxidizing only a small fraction of …

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The Effects Of Exercise Training On Resting Prostacyclin And Thromboxane A(2) In Older Adults, R D. Kauffman, G S. Sforzo, Blaise Frost, M K. Todd Jan 1997

The Effects Of Exercise Training On Resting Prostacyclin And Thromboxane A(2) In Older Adults, R D. Kauffman, G S. Sforzo, Blaise Frost, M K. Todd

Chemistry Faculty Publications

Ten adult volunteers participated in 16 weeks of cardiovascular exercise training (EG) to determine the effects of training on resting prostacyclin (PGI(2)) and thromboxane A(2) (TXA(2)). Six volunteers of similar age served as sedentary controls (CG). Blood was collected in tubes after training and eicosanoids were measured by standard I-125 RIA methods. Over the 16 weeks of the study, PGI(2) decreased 48% for EG and 33% for CG. There were no between-group differences for PGI(2) values. No significant within-group changes in TXA(2) were found, whereas between-group pretraining TXA(2) values were significantly different. A time main effect for PGI(2) may indicate …

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Efficient And General Synthesis Of Novel Β-Polyfluoroalkoxy Vinamidinium Salts, Koichiro Kase, Mitsuyoshi Katayama, Takashi Ishihara, Hiroki Yamanaka, John T. Gupton Jan 1997

Efficient And General Synthesis Of Novel Β-Polyfluoroalkoxy Vinamidinium Salts, Koichiro Kase, Mitsuyoshi Katayama, Takashi Ishihara, Hiroki Yamanaka, John T. Gupton

Chemistry Faculty Publications

Novel β-polyfluoroalkoxy vinamidinium salts 3 and/or 4 were synthesized in good yields by the reaction of N-(2- polyfluoroalkoxy-3 ,3-difluoro-1-propenyI)trimethylammonium iodides (2), prepared from N-(2,3,3-trifluoro-1-propenyl)trimethylammonium iodide (1), with secondary amines in MeCN at 70 °C for 1 h. The salts were also obtainable in comparable yields by the one-pot reaction of 1 with sodium polyfluoroalkoxide followed by treatment with amines.

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Protein-Protein And Protein-Dna Interactions At The Bacteriophage T4 Dna Replication Fork. Characterization Of A Fluorescently Labeled Dna Polymerase Sliding Clamp, Daniel J. Sexton, Theodore E. Carver, Anthony J. Berdis, Stephen J. Benkovic Nov 1996

Protein-Protein And Protein-Dna Interactions At The Bacteriophage T4 Dna Replication Fork. Characterization Of A Fluorescently Labeled Dna Polymerase Sliding Clamp, Daniel J. Sexton, Theodore E. Carver, Anthony J. Berdis, Stephen J. Benkovic

Chemistry Faculty Publications

The T4 DNA polymerase holoenzyme is composed of the polymerase enzyme complexed to the sliding clamp (the 45 protein), which is loaded onto DNA by an ATP-dependent clamp loader (the 44/62 complex). This paper describes a new method to directly investigate the mechanism of holoenzyme assembly using a fluorescently labeled cysteine mutant of the 45 protein. This protein possessed unaltered function yet produced substantial changes in probe fluorescence intensity upon interacting with other components of the holoenzyme. These fluorescence changes provide insight into the role of ATP hydrolysis in holoenzyme assembly. Using either ATP or the non-hydrolyzable ATP analog, adenosine …

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The Carboxyl Terminus Of The Bacteriophage T4 Dna Polymerase Is Required For Holoenzyme Complex Formation, Anthony J. Berdis, Patrice Soumillion, Stephen J. Benkovic Nov 1996

The Carboxyl Terminus Of The Bacteriophage T4 Dna Polymerase Is Required For Holoenzyme Complex Formation, Anthony J. Berdis, Patrice Soumillion, Stephen J. Benkovic

Chemistry Faculty Publications

To further elucidate the mechanism and dynamics of bacteriophage T4 holoenzyme formation, a mutant polymerase in which the last six carboxyl-terminal amino acids are deleted, was constructed, overexpressed, and purified to homogeneity. The mutant polymerase, designated ΔC6 exo−, is identical to wild-type exo− polymerase with respect to kcat, kpol, and dissociation constants for nucleotide and DNA substrate. However, unlike wild-type exo− polymerase, the ΔC6 exo− polymerase is unable to interact with the 45 protein to form the stable holoenzyme. A synthetic polypeptide corresponding to the carboxyl terminus of the wild-type exo− polymerase was tested as an in vitro inhibitor of …

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Electronic Spectroscopy Of Jet-Cooled Benzylidenecyclobutane, A Sterically Hindered Styrene, John R. Cable, V. P. Manea Oct 1996

Electronic Spectroscopy Of Jet-Cooled Benzylidenecyclobutane, A Sterically Hindered Styrene, John R. Cable, V. P. Manea

Chemistry Faculty Publications

The electronic spectrum of the styrene derivative, benzylidenecyclobutane, seeded in a supersonic jet expansion has been recorded using resonantly enhanced two-photon ionization spectroscopy. The main vibronic features in the spectrum are associated with a low frequency progression assigned to the torsional motion of the phenyl ring. Analysis of the observed torsional levels reveals an excited state potential energy surface characteristic of a planar equilibrium geometry which undergoes large amplitude motion and a ground state surface having a minimum at a torsional angle of 25° between the phenyl and vinyl groups. Ab initio calculations of the ground state torsional potential surface …

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The Role Of Written And Verbal Expression In Improving Communication Skills For Students In An Undergraduate Chemistry Program, Brian P. Coppola, Douglas S. Daniels Aug 1996

The Role Of Written And Verbal Expression In Improving Communication Skills For Students In An Undergraduate Chemistry Program, Brian P. Coppola, Douglas S. Daniels

Chemistry Faculty Publications

Proofreading, editing, and critique, the customary assessment tools scientists use to evaluate professional journal articles, grant applications, and any other writing, can be applied equally well in introductory science instruction. Such feedback is, in fact, crucial to growth and development. When learning anything new, students and faculty alike rely heavily on sources other than themselves (‘external editors’) to assess their understanding as they develop self-assessment skills (or ‘internal editors’). Although they rarely describe it in these terms, faculty nonetheless assume that students have developed and refined their internal skills by the time they take examinations and write term papers. Unfortunately, …

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Indirect Ultraviolet Detection Of Biologically Relevant Organic Acids By Capillary Electrophoresis, Hong Chen, Yan Xu, Frederick Van Lente, Michael P.C. Ip Apr 1996

Indirect Ultraviolet Detection Of Biologically Relevant Organic Acids By Capillary Electrophoresis, Hong Chen, Yan Xu, Frederick Van Lente, Michael P.C. Ip

Chemistry Faculty Publications

Indirect UV detection of fourteen short-chain organic acids (e.g., oxalic acid, citric acid, malonic acid, tartaric acid, methylmalonic acid, α-ketoglutaric acid, succinic acid, ethylmalonic acid, methylsuccinic acid, glutaric acid, apidic acid, methylglutaric acid, lactic acid and pyruvic acid) by capillary electrophoresis is described. The method used phthalate as the UV-absorbing additive in carbonate buffer and the non-absorbing analytes were detected indirectly at 230 nm. The influences of buffer pH, ionic strenght, concentration of phthalate and organic modifier on indirect signal response and migration behavior of the organic acids were investigated. Comparisons of reproducibility on migration time, limit of detection and …

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Computation Of Electron Affinities Of O And F Atoms, And Energy Profile Of F-H2 Reaction By Density Functional Theory And Ab Initio Methods, Branko S. Jursic Mar 1996

Computation Of Electron Affinities Of O And F Atoms, And Energy Profile Of F-H2 Reaction By Density Functional Theory And Ab Initio Methods, Branko S. Jursic

Chemistry Faculty Publications

The validity of hybrid and nonlocal DFT methods are tested on examples of systems which are difficult to model by way of quantum chemistry techniques. The electron affinities for the oxygen and fluorine atoms were calculated. The exothermicity, the barrier for the fluorine atom reaction with the hydrogen molecule, and the energy of the H–F bond and its distance were computed with DFT methods, as well as, with ROHF, MPn, and QCISD ~T! ab initio methods. The computations were performed by using various basis sets, with 6-311 11G(3d f ,3pd as the largest. The obtained results are compared …

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Photoinduced Electron Transfer Along A Β-Sheet Mimic, Alexei B. Gretchikhine, Michael Y. Ogawa Feb 1996

Photoinduced Electron Transfer Along A Β-Sheet Mimic, Alexei B. Gretchikhine, Michael Y. Ogawa

Chemistry Faculty Publications

Electron energy-loss spectroscopy (EELS) is used to determine the energies of low-lying singlet and triplet states of the title compound. The EELS measurements give a splitting of 0.45 eV between the two lowest π f π* singlet states, as confirmed by optical absorption measurements, but do not give a discernable splitting between the corresponding triplet states. The experimental results are interpreted with the aid of ab initio electronic structure calculations using the CIS and CASPT2 methods. The calculations are consistent with the experiments, giving a much larger splitting between the π f π* singlet as compared to the π f …

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The Lipooligosaccharides Of Haemophilus Ducreyi Are Highly Sialylated, William Melaugh, A A. Campagnari, B W. Gibson Jan 1996

The Lipooligosaccharides Of Haemophilus Ducreyi Are Highly Sialylated, William Melaugh, A A. Campagnari, B W. Gibson

Chemistry Faculty Publications

The major lipooligosaccharides of the sexually transmitted pathogen Haemophilus ducreyi 35000 have been previously found to terminate in N-acetyllactosamine and sialyl-N-acetyllactosamine, Neu5Ac alpha 2-->3Gal beta 1-->4GlcNAc (W. Melaugh, N. J. Phillips, A. A. Campagnari, M. V. Tullius, and B. W. Gibson, Biochemistry 33: 13070-13078, 1994). In this study, mass spectrometry and composition analyses have shown that the lipooligosaccharides from three other H. ducreyi strains also contain N-acetyllactosamine and are highly sialylated (approximately 30 to 50%), although one African strain was found to contain neither of these structural features.

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Synthesis And Characterization Of A Water Soluble Metallopeptide That Resembles A Parallel Β-Pleated Sheet, Michael Y. Ogawa, Alexei B. Gretchikhine, Sunil-Datta Soni, Steven M. Davis Dec 1995

Synthesis And Characterization Of A Water Soluble Metallopeptide That Resembles A Parallel Β-Pleated Sheet, Michael Y. Ogawa, Alexei B. Gretchikhine, Sunil-Datta Soni, Steven M. Davis

Chemistry Faculty Publications

The title metallopeptide consists of two divalinyl peptides attached to the carboxylate groups of the ruthenium polypyridyl complex. [Ru(bpy)(2)L](2+): bpy = 2,2'-bipyridine; L = 3,5-dicarboxy-2,2'-bipyridine. The charged ruthenium complex is water soluble and is shown by variable temperature, and 2-D NMR to consist a parallel arrangement of interacting, extended peptide strands that ir reminiscent of the beta-sheet structure. Circular dichroism results support this assignment.

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Relative Stabilities Of Dna 3-Way, 4-Way And 5-Way Junctions (Multi-Helix Junction Loops) - Unpaired Nucleotides Can Be Stabilizing Or Destabilizing, Neocles B. Leontis, Julie L. Kardmas, Amy J. Ravin Jun 1995

Relative Stabilities Of Dna 3-Way, 4-Way And 5-Way Junctions (Multi-Helix Junction Loops) - Unpaired Nucleotides Can Be Stabilizing Or Destabilizing, Neocles B. Leontis, Julie L. Kardmas, Amy J. Ravin

Chemistry Faculty Publications

Competition binding and UV melting studies of a DNA model system consisting of three, four or five mutually complementary oligonucleotides demonstrate that unpaired bases at the branch point stabilize three- and five-way junction loops but destabilize four-way junctions. The inclusion of unpaired nucleotides permits the assembly of five-way DNA junction complexes (5WJ) having as few as seven basepairs per arm from five mutually complementary oligonucleotides. Previous work showed that 5WJ, having eight basepairs per arm but lacking unpaired bases, could not be assembled I[Wang,Y.L., Mueller,J.E., Kemper,B. and Seeman,N.C. (1991) Biochemistry, 30, 5667-5674]. Competition binding experiments demonstrate that four-way junctions (4WJ) …

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Acid-Base Chemical Mechanism Of Aspartase From Hafnia Alvei, Moon Young Yoon, Kim A. Thayer-Cook, Anthony J. Berdis, William E. Karsten, Klaus D. Schnackerz, Paul F. Cook Jun 1995

Acid-Base Chemical Mechanism Of Aspartase From Hafnia Alvei, Moon Young Yoon, Kim A. Thayer-Cook, Anthony J. Berdis, William E. Karsten, Klaus D. Schnackerz, Paul F. Cook

Chemistry Faculty Publications

An acid-base chemical mechanism is proposed for Hafnia alvei aspartase in which a proton is abstracted from C-3 of the monoanionic form of L-aspartate by an enzyme general base with a pK of 6.3-6.6 in the absence and presence of Mg2+. The resulting carbanion is presumably stabilized by delocalization of electrons into the β-carboxyl with the assistance of a protonated enzyme group in the vicinity of the β-carboxyl. Ammonia is then expelled with the assistance of a general acid group that traps an initially expelled NH3 as the final NH+4 product. In agreement with the function of the general acid …

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Electrochemical Carbonylation Of Organoiron Methyl Complex: A Study Of Reaction Intermediates, C. Amatore, Mekki Bayachou, J. N. Verpeaux, L. Pospisil, J. Fiedler May 1995

Electrochemical Carbonylation Of Organoiron Methyl Complex: A Study Of Reaction Intermediates, C. Amatore, Mekki Bayachou, J. N. Verpeaux, L. Pospisil, J. Fiedler

Chemistry Faculty Publications

The one-electron reduction of CpFe(CO)2CH3 has been investigated by voltammetry and Fourier transform IR spectroelectrochemistry. The reduction initiates the insertion of CO ligand in the FeCH3 bond. The dissociation of a CO group proceeds in a parallel reaction. Reaction intermediates, the acyl derivative and released CO, form the radical anion of a complex CpFe(CO)2(COCH3) which is able to reduce the parent compound. The reversible redox potential − 1.8 V of CpFe(CO)2(COCH3) allows the regeneration of its radical anion which drives a catalytic cycle. The lifetime of intermediates is shortened by side reactions, one of which is the migration of the …

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