Chemistry Commons^™

Spectroscopic And Physico-Chemical Characterization Of Ir(I) And Ru(Iii) Complexes Of 32-Membered Unsymmetrical Dinucleating Macrocyclic Ligand, Mohammad Mansoob Khan Dr

Dr. Mohammad Mansoob Khan

No abstract provided.

Biogenic Synthesis, Photocatalytic, And Photoelectrochemical Performance Of Ag–Zno Nanocomposite, S. A. Ansari, Mohammad Mansoob Khan Dr, M. O. Ansari, J. Lee, M. H. Cho

Dr. Mohammad Mansoob Khan

The development of coupled photoactive materials (metal/semiconductor) has resulted in significant advancements in heterogeneous visible light photocatalysis. This work reports the novel biogenic synthesis of visible light active Ag–ZnO nanocomposite for photocatalysis and photoelectrode using an electrochemically active biofilm (EAB). The results showed that the EAB functioned as a biogenic reducing tool for the reduction of Ag+, thereby eliminating the need for conventional reducing agents. The as-prepared Ag–ZnO nanocomposite was characterized by X-ray diffraction, transmission electron microscopy, diffuse reflectance spectroscopy, photoluminescence spectroscopy, and X-ray photoelectron spectroscopy. The photocatalytic experiments showed that the Ag–ZnO nanocomposite possessed excellent visible light photocatalytic activity …

Vaporization Enthalpies And Vapor Pressures Of Two Insecticide Components, Muscalure And Empenthrin, By Correlation Gas Chromatography, Jessica Spencer, James Chickos

James Chickos

No abstract provided.

New Bis(Imino)Pyridine Complexes Of Iron(Ii) And Iron(Iii), And Their Catalytic­ Activity In The Mukaiyama Aldol Reaction, Pushkar Shejwalkar, Nigam P. Rath, Eike B. Bauer

Nigam Rath

P For Discussion: Naming Superheavy Halogen And Noble Elements, Shawn Burdette, Brett Thornton

Shawn C. Burdette

No abstract provided.

Crosslinked Polymer Sheaths For Dispersing Individual Single-Walled Carbon Nanotubes In Nonaqueous Solvents, L. Ojha, M. Tchoul, K. Bastola, K. Ausman

Kevin D. Ausman

Single-walled carbon nanotubes have been suspended individually in water by encasing them in a thin, uniform layer of the crosslinkable polymer poly (N-vinylpyrrolidone-co-allylamine). When this polymer is crosslinked under dilute conditions, the polymer sheath, formerly stabilized by the hydrophobic effect, becomes stable to changes in the solvent system.

Characterization Of Iso -Cf2 I2 In Frequency And Ultrafast Time Domains, Alexander N. Tarnovsky, Patrick Z. El-Khoury, Lisa George, Aimable Kalume, Scott A. Reid, Bruce S. Ault

Alexander Tarnovsky

The photolysis of diiododifluoromethane (CF2 I2) in condensed phases was studied by a combination of matrix isolation and ultrafast time-resolved spectroscopy, in concert with ab initio calculations. Photolysis at wavelengths of 355 or 266 nm of CF2 I2:Ar samples (1:5000) held at ∼8 K yielded iso -CF2 I2 (F2 C-I-I), a metastable isomer of CF2 I2, characterized here for the first time. The infrared (IR) spectra of this isomer were recorded in matrix experiments, and the derived positions of the C-F stretching modes are in very good agreement with the predictions of high level ab initio calculations, which show that …

Exploring The Mechanism Of Flexible Biomolecular Recognition With Single Molecule Dynamics, H. Peter Lu, Qiang Lu, Jin Wang

H. Peter Lu

Combining a single-molecule study of protein binding with a coarse grained molecular dynamics model including solvent (water molecules) effects, we find that biomolecular recognition is determined by flexibilities in addition to structures. Our single-molecule study shows that binding of CBD (a fragment of Wiskott-Aldrich syndrome protein) to Cdc42 involves bound and loosely bound states, which can be quantitatively explained in our model as a result of binding with large conformational changes. Our model identified certain key residues for binding consistent with mutational experiments. Our study reveals the role of flexibility and a new scenario of dimeric binding between the monomers: …

Steady-State Aerosol Distributions In The Extra-Tropical, Lower Stratosphere And The Processes That Maintain Them, J. Wilson, Shan-Hu Lee, J. Reeves, C. Brock, H. Jonsson, B. Lafleur, M. Loewenstein, J. Podolske, E. Atlas, K. Boering, G. Toon, D. Fahey, T. Bui, G. Diskin, F. Moore

Shan-Hu Lee

Measurements of aerosol, N2O and OCS made in the Northern Hemisphere below 21 km altitude following the eruption of Pinatubo are presented and analyzed. After September 1999, the oxidation of OCS and sedimentation of particles in the extra-tropical overworld north of 45 N are found to maintain the aerosol in a steady state. This analysis empirically links precursor gas to aerosol abundance throughout this region. These processes are tracked with age-of-air which offers advantages over tracking as a function of latitude and altitude. In the extra-tropical, lowermost stratosphere, normalized volume distributions appear constant in time after the fall of 1999. …

Isoprene Suppression Of New Particle Formation In A Mixed Deciduous Forest, V. P. Kanawade, B. T. Jobson, A. B. Guenther, M. E. Erupe, S. N. Pressley, S. N. Tripathi, Shan-Hu Lee

Shan-Hu Lee

Production of new particles over forests is an important source of cloud condensation nuclei that can affect climate. While such particle formation events have been widely observed, their formation mechanisms over forests are poorly understood. Our observations made in a mixed deciduous forest with large isoprene emissions during the summer displayed a surprisingly rare occurrence of new particle formation (NPF). Typically, NPF events occur around noon but no NPF events were observed during the 5 weeks of measurements. The exceptions were two evening ultrafine particle events. During the day, sulfuric acid concentrations were in the 106 cm−3 range with very …

The Effect Of Trimethylamine On Atmospheric Nucleation Involving H2so4, M. E. Erupe, A. A. Viggiano, Shan-Hu Lee

Shan-Hu Lee

Field observations and quantum chemical calculations have shown that organic amine compounds may be important for new particle formation involving H₂SO₄. Here, we report laboratory observations that investigate the effect of trimethylamine (TMA) on H₂SO₄-H₂O nucleation made under aerosol precursor concentrations typically found in the lower troposphere ([H₂SO₄] of 10⁶−10⁷ cm⁻³; [TMA] of 180–1350 pptv). The threshold [H₂SO₄] needed to produce the unity J was from 10⁶−10⁷ cm⁻³ and the slopes of Log …

A Chemical Ionization Mass Spectrometer For Ambient Measurements Of Ammonia, D. R. Benson, A. Markovich, M. Al-Refai, Shan-Hu Lee

Shan-Hu Lee

his study presents a chemical ionization mass spectrometer (CIMS) for fast response, in-situ measurements of gas phase ammonia (NH₃). The NH₃ background level detected with the CIMS ranged between 0.3–1 ppbv, with an uncertainty of 30 pptv under optimized conditions. The instrument sensitivity varied from 4–25 Hz/pptv for >1 MHz of reagent ion signals (protonated ethanol ions), with a 30% uncertainty estimated based on variability in calibration signals. The CIMS detection limit for NH₃ was ~60 pptv at a 1 min integration time (3 sigma). The CIMS time response was <30 s. This new NH₃-CIMS has been used for …

Laboratory Studies Of H2so4/H2o Binary Homogeneous Nucleation From The So2+Oh Reaction: Evaluation Of The Experimental Setup And Preliminary Results, L. Young, D. Benson, F. Kameel, J. Pierce, H. Junninen, M. Kulmala, Shan-Hu Lee

Shan-Hu Lee

Binary homogeneous nucleation (BHN) of sulphuric acid and water (H2SO4/H2O) is one of the most important atmospheric nucleation processes, but laboratory observations of this nucleation process are very limited and there are also large discrepancies between different laboratory studies. The difficulties associated with these experiments include wall loss of H2SO4 and uncertainties in estimation of H2SO4 concentration ([H2SO4]) involved in nucleation. We have developed a new laboratory nucleation setup to study H2SO4/H2O BHN kinetics and provide relatively constrained [H2SO4] needed for nucleation. H2SO4 is produced from the SO2+OH→HSO3 reaction and OH radicals are produced from water vapor UV absorption. The …

New Particle Growth And Shrinkage Observed In Subtropical Environments, L. H. Young, Shan-Hu Lee, V. P. Kanawade, T-C. Hsiao, Y. L. Lee, B-F. Hwang, Y-J. Liou, H-T. Hsu, P-J. Tsai

Shan-Hu Lee

We present the first systematic analysis for new particle formation (NPF), growth and shrinkage of new particles at four different sites in subtropical central Taiwan. A total of 14 NPF events were identified from 137 days of ambient measurements during a cold and warm season. The measured formation rates of 10 nm particles (J₁₀) and growth rates were in the range of 4.4–30 cm⁻³s⁻¹ and 7.4–24 nm h⁻¹, respectively. The onset of NPF events coincided with decreases of condensation sink (CS) and increases of SO₂ under enhanced atmospheric mixing and dilution. …

Ternary Homogeneous Nucleation Of H2so4, Nh3, And H2o Under Conditions Relevant To The Lower Troposphere, D. Benson, J. Yu, A. Markovich, Shan-Hu Lee

Shan-Hu Lee

Ternary homogeneous nucleation (THN) of H2SO4, NH3 and H2O has been used to explain new particle formation in various atmospheric regions, yet laboratory measurements of THN have failed to reproduce atmospheric observations. Here, we report first laboratory observations of THN made under conditions relevant to the lower troposphere ([H2SO4] of 106–107 cm−3, [NH3] of 0.08–20 ppbv, and a temperature of 288 K). Our observations show that NH3 can enhance atmospheric H2SO4aerosol nucleation and the enhancement factor (EF) in nucleation rate (J) due to NH3 (the ratio of Jmeasured with vs. without NH3) increases linearly with increasing [NH3] and increases with …

The Effects Of Airmass History On New Particle Formation In The Free Troposphere: Case Studies, D. Benson, Li-Hao Young, Shan-Hu Lee, T. Campos, D. Rogers, J. Jensen

Shan-Hu Lee

Recent aircraft studies showed that new particle formation (NPF) is very active in the free troposphere. And, these observations lead to a new question: when does NPF not occur? Here, we provide case studies to show how different meteorological parameters affect NPF in the upper troposphere, using the aerosol size distributions measured at latitudes from 18° N–52° N and altitudes up to 14 km during the NSF/NCAR GV Progressive Science Missions. About 95% of the total samples showed the NPF feature with median number concentrations of particles with diameters from 4 to 9 nm (N4–9), 288±199 cm−3, and the total …

An Experimental And Modeling Study Of Formaldehyde And 1,3,5-Trioxane Flame Chemistry, Jeffrey S. Santner, Francis M. Haas, Frederick L. Dryer, Yiguang Ju

Francis (Mac) Haas

Characterizing The Promiscuity Of Ligab, A Lignin Catabolite Degrading Extradiol Dioxygenase From Sphingomonas Paucimobilis Syk-6, Kevin P. Barry, Erika A. Taylor

Erika A. Taylor, Ph.D.

LigAB from Sphingomonas paucimobilis SYK-6 is the only structurally characterized dioxygenase of the largely uncharacterized superfamily of Type II extradiol dioxygenases (EDO). This enzyme catalyzes the oxidative ring-opening of protocatechuate (3,4-dihydroxybenzoic acid or PCA) in a pathway allowing the degradation of lignin derived aromatic compounds (LDACs). LigAB has also been shown to utilize two other LDACs from the same metabolic pathway as substrates, gallate, and 3-O-methyl gallate; however, kcat/KM had not been reported for any of these compounds. In order to assess the catalytic efficiency and get insights into the observed promiscuity of this enzyme, steady-state kinetic analyses were performed …

3d Single-Walled Carbon Nanotube Networks Encased In Crosslinked Polymer Monolayers: Toward Robust Nanotube Aerogels, Kevin Ausman, Andrew Adams, Lawanya Ojha, Maxim Tchoul, Krishna Bastola

Kevin D. Ausman

A thin, uniform coating of a polymer can suspend single-walled carbon nanotubes in water. The polymer coating is stabilized by the hydrophobic effect. Upon crosslinking this system under dilute conditions, the polymer sheath becomes stable to changes in solvent system. Upon crosslinking the system under semi-dilute conditions, robust three-dimensional networks are formed. Progress toward generating aerogels from these monolayer-coated nanotubes is reported.

The Vaporization Enthalpies And Vapor Pressures Of Some Primary Amines Of Pharmaceutical Importance By Correlation Gas Chromatography, Chase Gobble, Nigam Rath, James Chickos

James Chickos

No abstract provided.

Evolution Of Enzymatic Activities In The Enolase Superfamily: L-Rhamnonate Dehydratase, John Rakus, Alexander Fedorov, Elena Fedorov, Margaret Glasner, Brian Hubbard, Joseph Delli, Patricia Babbitt, Steven Almo, John Gerlt

John F. Rakus

The L-rhamnonate dehydratase (RhamD) function was assigned to a previously uncharacterized family in the mechanistically diverse enolase superfamily that is encoded by the genome of Escherichia coli K-12. We screened a library of acid sugars to discover that the enzyme displays a promiscuous substrate specificity: L-rhamnonate (6-deoxy-L-mannonate) has the “best” kinetic constants, with L-mannonate, L-lyxonate, and D-gulonate dehydrated less efficiently. Crystal structures of the RhamDs from both E. coli K-12 and Salmonella typhimurium LT2 (95% sequence identity) were obtained in the presence of Mg2+; the structure of the RhamD from S. typhimurium was also obtained in the presence of 3-deoxy-L-rhamnonate …

Molecular Orbitals And Organic Chemical Reactions (Book Review), Jeffrey H. Glans

Jeffrey H. Glans

Book review by Jeffrey Glans. Fleming, Ian. Molecular Orbitals and Organic Chemical Reactions. Wiley-Blackwell, 2010, c2009. ISBN: 9780470746608; 9780470746592 (pbk.)

Compendium Of Polymer Terminology And Nomenclature: Iupac Recommendations, 2008 (Book Review), Jeffrey H. Glans

Jeffrey H. Glans

Book review by Jeffrey Glans. Polymer Division, International Union of Pure and Applied Chemistry. Compendium of Polymer Terminology and Nomenclature: IUPAC Recommendations, 2008. Royal Society of Chemistry, 2009.

C60 Oxide As A Key Component Of Aqueous C60 Colloidal Suspensions, Kevin Ausman, Befrika Murdianti, Joshua Damron, Martha Hilburn, Randall Maples, Rangika Hikkaduwa Koralege, Satish Kuriyavar

Kevin D. Ausman

The [6,6]-closed epoxide derivative (C60O) of buckminsterfullerene (C60) is found to stabilize aqueous fullerene colloidal suspensions (nC60). This pervasive derivative is often unrecognized, but present in small quantities in nearly all C60 starting materials due to a reaction with air. In nC60 formation from organic solvent solutions, C60O partitions preferentially to the colloid, significantly enriching the C60O content of the particles relative to the starting material. Because this partitioning is significantly retarded in nC60 synthesis methods that do not use organic solvents, such as long-term stirring in water, such methods instead rely on trace levels of ozone in the ambient …

Integrated Mathematica™-Based Physical Chemistry Curriculum: Bringing The Science To The Forefront, Kevin Ausman

Kevin D. Ausman

Undergraduate- and graduate-level physical chemistry classes are often so mathematically intensive that they often (a) dissuade qualified students from pursuing the field, (b) require more homework, testing, and grading time be devoted to tracking down hidden mathematical errors than is devoted to working with the subject matter, and (c) limit the complexity, and therefore real-world applicability, of assigned problems. In this talk, the integration of the general-purpose mathematical tool MathematicaTM throughout the second semester of undergraduate physical chemistry will be discussed. Examples provided will demonstrate the feasibility of introducing the MathematicaTM language gradually over the course of the semester, allowing …

Preparation And Characterization Of 3 Nm Magnetic Niau Nanoparticles, Bethany Auten, Benjamin Hahn, Ganesh Vijayaraghavan, Keith Stevenson, Bert Chandler

Bert D Chandler

Using PAMAM dendrimers as nanoparticle templates, a synthetic route to prepare 3 nm magnetic NiAu nanoparticles was developed. Aqueous solutions of hydroxyl-terminated generation 5 PAMAM dendrimers in 25 mM NaClO4 were shown to bind aqueous NiII. Coreduction of NiII and AuIII salts yielded bimetallic dendrimer stabilized nanoparticles, which were extracted into toluene with decanethiol. Characterization of the resulting monolayer protected clusters (MPCs) with transmission electron microscopy and UV-visible, atomic absorption, and X-ray photoelectron spectroscopies suggested that the MPCs had substantial surface enrichment in Au. Superconducting quantum interference device (SQUID) measurements at 5 K show the bimetallic MPCs to have low …

Synthesis And Characterization Of Dendrimer Templated Supported Bimetallic Pt-Au Nanoparticles, Huifang Lang, Stephen Maldonado, Keith Stevenson, Bert Chandler

Bert D Chandler

Bimetallic dendrimer-stabilized nanoparticles (DSNs) were used to prepare supported Pt-Au catalysts within the bulk miscibility gap for this binary system. Hydroxy-terminated generation 5 PAMAM dendrimers were used to prepare Cu0 nanoparticles (NPs). The Cu0 NPs were subsequently used to reduce K2PtCl4 and HAuCl4, preparing stabilized bimetallic Pt-Au NPs with a 1:1 stoichiometry. The stabilized NPs were adsorbed onto a high surface area silica support and thermally activated to remove the dendrimers. Transmission electron microscopy (TEM), energy dispersive spectroscopy (EDS), and infrared spectroscopy of adsorbed CO showed that this preparation route resulted in NPs in which the two metals are intimately …

Dendrimer-Encapsulated Nanoparticle Precursors To Supported Platinum Catalysts, Huifang Lang, R Alan May, Brianna L. Iversen, Bert D. Chandler

Bert D Chandler

In this contribution, we report the successful preparation of supported metal catalysts using dendrimer-encapsulated Pt nanoparticles as metal precursors. Polyamidoamine (PAMAM) dendrimers were first used to template and stabilize Pt nanoparticles prepared in solution. These dendrimer-encapsulated nanoparticles were then deposited onto a commercial high surface area silica support and thermally activated to remove the organic dendrimer. The resulting materials are active oxidation and hydrogenation catalysts. The effects of catalyst preparation and activation on activity for toluene hydrogenation and CO oxidation catalysis are discussed.

Adsorption Of Co On Supported Gold Nanoparticle Catalysts: A Comparative Study, Heather Hartshorn, Christopher Pursell, Bert Chandler

Bert D Chandler

The adsorption of CO on three different gold nanoparticle catalysts supported on high surface area TiO2 was studied using infrared transmission spectroscopy at room temperature and CO pressures typically used in CO oxidation reactions. The three, real-world catalysts were Au catalysts synthesized in our laboratory from thiol monolayer protected clusters (MPCs) and two commercial catalysts from the World Gold Council (WGC and AuTEK). Within experimental reproducibility, the adsorption data for the three catalysts are indistinguishable. While showing approximately Langmuir behavior, the adsorption data also show coverage dependence, as others have observed for many catalyst systems. Two approaches were used to …

Tuning Supported Catalyst Reactivity With Dendrimer-Templated Pt-Cu Nanoparticles, Natalie N. Hoover, Bethany J. Auten, Bert D. Chandler

Bert D Chandler

The effects of particle composition on heterogeneous catalysis were studied using dendrimer-encapsulated nanoparticles (DENs) as precursors to supported Pt-Cu catalysts. Bimetallic Pt-Cu DENs with varying Pt/Cu ratios were prepared in an anaerobic aqueous solution and deposited onto a high-purity commercial alumina support. The dendrimer template was then thermally removed to yield supported nanoparticle catalysts, which were studied with toluene hydrogenation and CO oxidation catalysis as well as infrared spectroscopy of adsorbed CO. Incorporating Cu into Pt nanoparticles had opposite effects on the two test reactions. Cu acted as a mild promoter for CO oxidation catalysis, and the promoting effect was …