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Description: Evidence is presented which points to (at least) two bound forms of bacteriochlorophyll present in chromatophores of Rhodospirillum rubrum, both of them readily converted to unbound bacteriochlorophyll (abs. max. 770 mu) when the chromatophores are extracted with acetone or ethanol. Controlled oxidation of the chromatophores with Ir(IV) or with Zn(II) and ferricyanide preferentially destroys the more strongly absorbing pigment (abs. max. 880 mu) but brings about only a slight decrease in the magnitude of the photoinduced absorption changes at 810 and 792 mu. Such oxidations yield a new pigment, absorbing at 715 mu in the aqueous preparation and, more strongly, at 680-684 mu when the pigment is extracted into organic solvents. This pigment is formed irreversibly and is therefore different from the material formed by photooxidation of chromatophores. Its visible spectrum and the spectrum of the material formed from it by acidification suggest that it is a chlorophyll-like substance, possibly derived from bacteriochlorophyll by (two-electron) oxidation of one of the dihydropyrrole rings to a pyrrole ring. Directions are given for separation of this pigment from other colored compounds present in the oxidation mixtures.
Date: October 1, 1964
Creator: Gould, Edwin S.; Kuntz Jr., Irwin D. & Calvin, Melvin
Partner: UNT Libraries Government Documents Department

Magnetic Properties of Copper (II) Complexes of N-(Hydroxyalkyl) Pyrrole-2-Aldimines

Description: In this work magnetic properties of copper(II) complexes on N-(hydroxyalkyl) pyrrole-2-aldimines were investigated by various techniques, one of which was magnetic susceptibility. Magnetic moments are not directly determined experimentally, but magnetic susceptibilities are.
Date: December 1973
Creator: Pauley, Charles Richard
Partner: UNT Libraries

Structure Sensitivity of Carbon-Nitrogen Ring Opening: Impact of Platinum Particle Size from below 1 to 5 nm upon Pyrrole Hydrogenation Product Selectivity over Monodisperse Platinum Nanoparticles Loaded onto Mesoporous Silica

Description: The ability to control fundamental properties (e.g., particle size, surface structure, and metal-oxide interface) in order to design highly selective heterogeneous catalysts would greatly reduce energy intensive separations. Particle size dependence (i.e., structure sensitivity) upon selectivity can now be examined with well defined nanoparticles (NPs) because of advances in synthetic chemistry. Colloidal chemistry has provided means for synthesizing monodisperse Pt NPs as small as {approx}2 nm. Using a dendrimer templated approach, Pt NPs smaller than 1 nm--a new size regime for studying size induced effects in heterogeneous catalysis--can be synthesized (Scheme 1). In this contribution, we report that ring opening for pyrrole hydrogenation is distinctly different for Pt NPs smaller than 2 nm. This insight has not been demonstrated for hydrogenation of cyclic heteroatom bonds to the best of our knowledge. This finding adds fundamental insight into hydrodenitrogenation (HDN) chemistry, which is important for fuel processing and involves removal of N-containing organics. Advances in HDN catalysis are needed to meet new fuel quality regulations because N-containing organics inhibit hydrodesulfurization (HDS) through competitive adsorption and poison acid catalysts, which are used for downstream processing and as supports for HDS catalysts. Pyrrole was selected as the reactant because organics with 5-member N-containing rings are the most common components in fuel.
Date: July 1, 2008
Creator: Kuhn, John N.; Huang, Wenyu; Tsung, Chia-Kuang; Zhang, Yawen & Somorjai, Gabor A.
Partner: UNT Libraries Government Documents Department

Dendrimer Templated Synthesis of One Nanometer Rh and Pt Particles Supported on Mesoporous Silica: Catalytic Activity for Ethylene and Pyrrole Hydrogenation.

Description: Monodisperse rhodium (Rh) and platinum (Pt) nanoparticles as small as {approx}1 nm were synthesized within a fourth generation polyaminoamide (PAMAM) dendrimer, a hyperbranched polymer, in aqueous solution and immobilized by depositing onto a high-surface-area SBA-15 mesoporous support. X-ray photoelectron spectroscopy indicated that the as-synthesized Rh and Pt nanoparticles were mostly oxidized. Catalytic activity of the SBA-15 supported Rh and Pt nanoparticles was studied with ethylene hydrogenation at 273 and 293 K in 10 torr of ethylene and 100 torr of H{sub 2} after reduction (76 torr of H{sub 2} mixed with 690 torr of He) at different temperatures. Catalysts were active without removing the dendrimer capping but reached their highest activity after hydrogen reduction at a moderate temperature (423 K). When treated at a higher temperature (473, 573, and 673 K) in hydrogen, catalytic activity decreased. By using the same treatment that led to maximum ethylene hydrogenation activity, catalytic activity was also evaluated for pyrrole hydrogenation.
Date: May 9, 2008
Creator: Huang, Wenyu; Kuhn, John N.; Tsung, Chia-Kuang; Zhang, Yawen; Habas, Susan E.; Yang, Peidong et al.
Partner: UNT Libraries Government Documents Department

Pyrrole Hydrogenation over Rh(111) and Pt(111) Single-Crystal Surfaces and Hydrogenation Promotion Mediated by 1-Methylpyrrole: A Kinetic and Sum-Frequency Generation Vibrational Spectroscopy Study

Description: Sum-frequency generation (SFG) surface vibrational spectroscopy and kinetic measurements using gas chromatography have been used to study the adsorption and hydrogenation of pyrrole over both Pt(111) and Rh(111) single-crystal surfaces at Torr pressures (3 Torr pyrrole, 30 Torr H{sub 2}) to form pyrrolidine and the minor product butylamine. Over Pt(111) at 298 K it was found that pyrrole adsorbs in an upright geometry cleaving the N-H bond to bind through the nitrogen evidenced by SFG data. Over Rh(111) at 298 K pyrrole adsorbs in a tilted geometry relative to the surface through the p-aromatic system. A pyrroline surface reaction intermediate, which was not detected in the gas phase, was seen by SFG during the hydrogenation over both surfaces. Significant enhancement of the reaction rate was achieved over both metal surfaces by adsorbing 1-methylpyrrole before reaction. SFG vibrational spectroscopic results indicate that reaction promotion is achieved by weakening the bonding between the N-containing products and the metal surface because of lateral interactions on the surface between 1-methylpyrrole and the reaction species, reducing the desorption energy of the products. It was found that the ring-opening product butylamine was a reaction poison over both surfaces, but this effect can be minimized by treating the catalyst surfaces with 1-methylpyrrole before reaction. The reaction rate was not enhanced with elevated temperatures, and SFG suggests desorption of pyrrole at elevated temperatures.
Date: March 4, 2008
Creator: Kliewer, Christopher J.; Bieri, Marco & Somorjai, Gabor A.
Partner: UNT Libraries Government Documents Department

Shale oil value enhancement research. Quarterly report, October 1, 1993--December 31, 1993

Description: A major push was made to identify the hydrocarbon and heteroatom types present in raw shale oil. A comprehensive, qualitative picture of the <400{degrees}C material has been obtained. In addition to the expected types, e.g., pyridines, pyrroles, indoles and phenols, the presence of aliphatic carboxylic acids, ketones and nitrites was confirmed. Most importantly, heteroatom types are able to be concentrated nearly quantitatively by liquid-liquid extraction with polar solvents. Compound types characterization of the >400{degrees}C material, as well as rapid, routine analysis of separations fractions, requires new methodologies founded in the Z-BASIC concept. Advances were made in establishing the interface protocol needed to utilize Z-BASIC methodologies for interpretation of gc-ms output data. It is anticipated that all interface protocols will be completed and a computerized reporting system will be in place by the end of the next quarter. Progress reports were made at the Contractor`s Review Meeting (METC), November 16th and at the Eastern Oil Shale Symposium (Lexington), November 17th. Research results continue to be well-received. The concept of a thermodynamically logical map of potential products from shale oil is a sound approach to value-enhancement research. From a commercial perspective, the concept of establishing a demand for raw shale oil at a reasonable purchase price of, say $30/bbl, is increasingly being recognized as the best means of pulling shale oil into the marketplace.
Date: May 1, 1997
Partner: UNT Libraries Government Documents Department

Ultra-Trace Detection of Fluoride Ion and Hydrofluoric Acid

Description: Describes general synthetic strategies developed under this grant to control interchain electronic communications within conjugated polymers (CPs). Novel chemical architectures built on iptycenes, metallorotaxanes, and canopied pyrroles restrict the dimensionality of electronic structures responsible for excition and charge transport. Structure-property relationships emerging from studies of selected systems are discussed, focusing on their implications for the sensitivity of these materials as sensors.
Date: March 17, 2005
Creator: Swager, Timothy M.
Partner: UNT Libraries Government Documents Department

Mixed ionic and electronic conductivity in polymers. Progress report, January 1, 1989--December 31, 1989

Description: The conductivity of iodine-containing polymers was investigated and conductivity along polyiodide chains is implicated by the concentration dependence of the conductivity data and spectroscopic measurements. On the theoretical side, entropy based models were developed to describe ion motion in polymers.
Date: June 1, 1990
Creator: Shriver, D. F.
Partner: UNT Libraries Government Documents Department

Monodisperse metal nanoparticle catalysts on silica mesoporous supports: synthesis, characterizations, and catalytic reactions

Description: The design of high performance catalyst achieving near 100% product selectivity at maximum activity is one of the most important goals in the modern catalytic science research. To this end, the preparation of model catalysts whose catalytic performances can be predicted in a systematic and rational manner is of significant importance, which thereby allows understanding of the molecular ingredients affecting the catalytic performances. We have designed novel 3-dimensional (3D) high surface area model catalysts by the integration of colloidal metal nanoparticles and mesoporous silica supports. Monodisperse colloidal metal NPs with controllable size and shape were synthesized using dendrimers, polymers, or surfactants as the surface stabilizers. The size of Pt, and Rh nanoparticles can be varied from sub 1 nm to 15 nm, while the shape of Pt can be controlled to cube, cuboctahedron, and octahedron. The 3D model catalysts were generated by the incorporation of metal nanoparticles into the pores of mesoporous silica supports via two methods: capillary inclusion (CI) and nanoparticle encapsulation (NE). The former method relies on the sonication-induced inclusion of metal nanoparticles into the pores of mesoporous silica, whereas the latter is performed by the encapsulation of metal nanoparticles during the hydrothermal synthesis of mesoporous silica. The 3D model catalysts were comprehensively characterized by a variety of physical and chemical methods. These catalysts were found to show structure sensitivity in hydrocarbon conversion reactions. The Pt NPs supported on mesoporous SBA-15 silica (Pt/SBA-15) displayed significant particle size sensitivity in ethane hydrogenolysis over the size range of 1-7 nm. The Pt/SBA-15 catalysts also exhibited particle size dependent product selectivity in cyclohexene hydrogenation, crotonaldehyde hydrogenation, and pyrrole hydrogenation. The Rh loaded SBA-15 silica catalyst showed structure sensitivity in CO oxidation reaction. In addition, Pt-mesoporous silica core-shell structured NPs (Pt{at}mSiO{sub 2}) were prepared, where the individual Pt NP is encapsulated by ...
Date: September 14, 2009
Creator: Somorjai, G.A.
Partner: UNT Libraries Government Documents Department

Photoinitiated electron transfer in multichromophoric species: Synthetic tetrads and pentads

Description: This project involves the design, synthesis and study of molecules which mimic some of the important aspects of photosynthetic electron and energy transfer. This research project is leading to a better understanding of the energy conserving steps of photosynthesis via the study of synthetic model systems which abstract features of the natural photosynthetic apparatus. The knowledge gained from these studies will aid in the design of artificial photosynthetic reaction centers which employ the basic chemistry and physics of photosynthesis to help meet mankind`s energy needs. The approach to artificial photosynthesis employed in this project is to use synthetic pigments, electron donors, and electron acceptors similar to those found in biological reaction centers, but to replace the protein component with covalent bonds. These chemical linkages determine the electronic coupling between the various moieties by controlling separation, relative orientation, and overlap of electronic orbitals. The model systems are designed to mimic the following aspects of natural photosynthetic electron transfer: electron donation from a tetrapyrrole excited single state, electron transfer between tetrapyrroles, electron transfer from tetrapyrroles to quinones, and electron transfer between quinones with different redox properties. In addition, they mimic carotenoid antenna function in photosynthesis (singlet-singlet energy transfer from carotenoid polyenes to chlorophyll) and carotenoid photoprotection from singlet oxygen damage (triplet-triplet energy transfer from chlorophyll to carotenoids).
Date: March 1, 1993
Partner: UNT Libraries Government Documents Department

Thin film conductive polymer for microactuator and micromuscle applications

Description: Conductive polymer/polyimide bimorphic microcantilevers have been actuated vertically (out-of-plane) upon the volumetric changes induced by electrochemical doping of the polymer. The microcantilevers that are 200-500 {mu}m in length and 50-100 {mu}m in width can be fully extended from a circularly-curled geometry, and thus generate more than 100 {mu}m displacement. Dynamically the microcantilevers have been driven as fast as 1.2 Hz and the polymer was stable for over a week stored in air and light. Residual stresses in the polymer film is estimated to be as high as 254 MPa, and actuation stresses are as high as 50 MPa.
Date: April 14, 1994
Creator: Lee, A.P.; Hong, K.; Trevino, J. & Northrup, M.A.
Partner: UNT Libraries Government Documents Department

Pyrolysis and Combustion of Acetonitrile (CH{sub 3}CN)

Description: Acetonitrile (CH{sub 3}CN) is formed from the thermal decomposition of a variety of cyclic, noncyclic, and polymeric nitrogen-containing compounds such as pyrrole and polyacrylonitrile. The pyrolysis and combustion of acetonitrile have been studied over the past 30 years to gain a more detailed understanding of the complex mechanisms involved in the release of nitrogen-containing compounds such as hydrogen cyanide (HCN) in fires and nitrogen oxides (NOx) in coal combustion. This report reviews the literature on the formation of HCN and NOx from the pyrolysis and combustion of acetonitrile and discusses the possible products found in an acetonitrile fire.
Date: May 22, 2002
Creator: Britt, P. F.
Partner: UNT Libraries Government Documents Department

Thermodynamic properties for polycyclic systems by non-calorimetric methods. Progress report, August 1, 1992--September 30, 1993

Description: A detailed vibrational spectroscopic study of furan, pyrrole, and thiophene has been completed. These compounds form part of the base of five-membered ring systems on which the rest of the research program will be built Several methyl-substituted derivatives were also studied. The results will be used to confirm the model for alkyl- substitution in the ring systems. Gas-phase spectra and fundamental- frequency assignments were completed for 2,3- and 2,5-dihydrofuran. Those compounds initiate work on ring-puckering within the research program. A paper describing the need for third virial estimation, when using the virial equation of state to derive thermodynamic properties at pressures greater than 1 bar was completed.
Date: March 1, 1993
Creator: Steele, W. V.; Chirico, R. D. & Klots, T. D.
Partner: UNT Libraries Government Documents Department

Mixed ionic and electronic conductivity in polymers. Progress report, January 1, 1990--December 31, 1990

Description: New polymer films were synthesized that are mixed ionic-electronic conductors. Preliminary ion transport measurements have been made on these materials in the reduced state where electronic conductivity is negligible. We also have made preliminary measurements of switching times for these materials. Theoretical studies have been performed ion pairing in insulating and electronically conducting films.
Date: June 1, 1991
Creator: Shriver, D. F.
Partner: UNT Libraries Government Documents Department

Mixed-ionic and electronic conductivity in polymers. Annual technical progress report

Description: The aim in this portion of the research is to prepare new electroactive films with high ion mobility, and to characterize the transport properties of these materials. The classic conducting polymers, polyacetylene, polythiophene, and polypyrrole have dense structures that prevent rapid redox switching because of the low diffusivity of ions. The objective is to modify the last two polymers with pendant polyethers, which should greatly improve ion transport.
Date: December 31, 1991
Creator: Ratner, M. A. & Shriver, D. F.
Partner: UNT Libraries Government Documents Department

Mixed ionic and electronic conductivity in polymers. Progress report, January 1, 1991--December 31, 1991

Description: In the past year, we have made progress in the theory of mixed ionic and electronic conductivity in polymers. On the experimental side, we have prepared polypyrroles with pendant polyethers and studied their conductivity in the reduced state. Theoretical progress was made in the application of Monte Carlo methods to ion motion in polymers.
Date: July 1, 1992
Creator: Ratner, M. A. & Shriver, D. F.
Partner: UNT Libraries Government Documents Department

Sub-10 nm Platinum Nanocrystals with Size and Shape Control: Catalytic Study for Ethylene and Pyrrole Hydrogenation

Description: Platinum nanocubes and nanopolyhedra with tunable size from 5 to 9 nm were synthesized by controlling the reducing rate of metal precursor ions in a one-pot polyol synthesis. A two-stage process is proposed for the simultaneous control of size and shape. In the first stage, the oxidation state of the metal ion precursors determined the nucleation rate and consequently the number of nuclei. The reaction temperature controlled the shape in the second stage by regulation of the growth kinetics. These well-defined nanocrystals were loaded into MCF-17 mesoporous silica for examination of catalytic properties. Pt loadings and dispersions of the supported catalysts were determined by elemental analysis (ICP-MS) and H2 chemisorption isotherms, respectively. Ethylene hydrogenation rates over the Pt nanocrystals were independent of both size and shape and comparable to Pt single crystals. For pyrrole hydrogenation, the nanocubes enhanced ring-opening ability and thus showed a higher selectivity to n-butylamine as compared to nanopolyhedra.
Date: March 2, 2009
Creator: Tsung, Chia-Kuang; Kuhn, John N.; Huang, Wenyu; Aliaga, Cesar; Hung, Ling-I; Somorjai, Gabor A. et al.
Partner: UNT Libraries Government Documents Department

Hydrodenitrogenation: An increasingly important part of catalytic hydroprocessing interlocking of thermodynamics and kinetics

Description: This report outlines a new use of thermodynamic property data. The Gibbs energies of reaction obtained from thermodynamic property measurements are used to estimate, with some success, relative reactivities for aromatic organonitrogen compounds. Calculated relative rates of reaction reproduce literature values within one power of ten. The relative rates of reaction are shown to be directly proportional to the concentration of hydrogenated species formed during hydrodenitrogenation (HDN). The production of completely saturated ring systems (overhydrogenation) in HDN reactions using conventional hydroprocessing is explained solely in terms of the thermodynamics in operation in the system. The results obtained show that the order of relative reactivity obtained is strongly dependence can account for some apparent contradictions when kinetic studies reported in the literature are compared. The results for a study of the hydroprocessing of a straight-run gas oil are reproduced in this report. The formation of anilines and the increase in indole concentration above that in the original gas oil sample are explained via the thermodynamics operating in the system.
Date: April 1, 1992
Creator: Steele, W.V. & Chirico, R.D.
Partner: UNT Libraries Government Documents Department

Transition metal activation and functionalization of carbon-hydrogen bonds. Progress report, December 1, 1989--November 30, 1992

Description: We are investigating the fundamental thermodynamic and kinetic factors that influence carbon-hydrogen bond activation at homogeneous transition metal centers and the conversion of hydrocarbons into functionalized products of potential use to the chemical industry. Advances have been made in both understanding the interactions of hydrocarbons with metals and in the functionalization of hydrocarbons. We have found that RhCl(PR{sub 3}){sub 2}(CNR) complexes can catalyze the insertion of isonitriles into the C-H bonds or arenes upon photolysis. The mechanism of these reactions was found to proceed by way of initial phosphine dissociation, followed by C-H activation and isonitrile insertion. We have also examined reactions of a series of arenes with (C{sub 5}Me{sub 5})Rh(PMe{sub 3})PhH and begun to map out the kinetic and thermodynamic preferences for arene coordination. The effects of resonance, specifically the differences in the Hueckel energies of the bound vs free ligand, are now believed to fully control the C-H activation/{eta}{sup 2}-coordination equilibria. We have begun to examine the reactions of rhodium isonitrile pyrazolylborates for alkane and arene C-H bond activation. A new, labile, carbodiimide precursor has been developed for these studies. We have completed studies of the reactions of (C{sub 5}Me{sub 5})Rh(PMe{sub 3})H{sub 2} with D{sub 2} and PMe{sub 3} that indicate that both {eta}{sup 5} {yields} {eta}{sup 3} ring slippage and metal to ring hydride migration occur more facilely than thermal reductive elimination of H{sub 2}. We have examined the reactions of heterocycles with (C{sub 5}Me{sub 5})Rh(PMe{sub 3})PhH and found that pyrrole and furan undergo C-H or N-H activation. Thiophene, however, undergoes C-S bond oxidative addition, and the mechanism of activation has been shown to proceed through sulfur coordination prior to C-S insertion.
Date: June 1, 1992
Creator: Jones, W. D.
Partner: UNT Libraries Government Documents Department

Activated sludge studies of selected contaminants of PFH wastewater

Description: Acetone, propionitrile, pyrrole, and thiocyanate were selected as representative compounds of wastewater expected from pressurized, fluidized-bed hydroretorting (PFH) of Eastern oil shales. The PFH process has been the subject of investigation by the Institute of Gas Technology, under contract with the United States Department of Energy, for the purpose of obtaining higher oil yields from Eastern shales than has been possible using conventional retorting methods. Preliminary batch experiments illustrated that acetone, propionitrile, pyrrole, and thiocyanate are aerobically biodegradable by heterogeneous microbiological cultures. Three continuous flow activated sludge reactors were used to further evaluate the biological treatability of the synthetic waste. The studies revealed that the compounds could be removed at hydraulic residence times of as low as one day. Three one-day experiments demonstrated that biological system`s capability to accept organic shock loadings without a change in effluent quality. A no-recycle reactor illustrated that the flocculent microbiological population had a high resistance to solids washout. Because a supplementary nitrogen source was not included in synthetic waste treated by the no-recycle unit, it was shown that propionitrile, pyrrole, and/or thiocyanate supplied the nitrogen necessary for biological activity.
Date: December 31, 1991
Creator: Dudley, S. K.; Bustamante, R. B. & Bonner, W. P.
Partner: UNT Libraries Government Documents Department

Application of conducting polymers to electroanalysis

Description: Conducting polymers can be used as sensitive layers in chemical microsensors leading to new applications of theses devices. They offer the potential for developing material properties that are critical to the sensor sensitivity, selectivity and fabrication. The advantages and limitations of the use of thin polymer layers in electrochemical sensors are discussed.
Date: April 1, 1994
Creator: Josowicz, M. A.
Partner: UNT Libraries Government Documents Department

Feasibility Study of Using Short Wave Infrared Cavity Ringdown Spectroscopy (SWIR-CRDS) for Biological Agent Detection

Description: This project focused on determining the feasibility of using short wave infrared (SWIR) cavity ring down spectroscopy (CRDS) as a means for real-time detection of biological aerosols. The first part of the project involved identifying biological agent signatures that could be detected with SWIR CRDS. After an exhaustive search of the open literature it was determined that whole biological spores and/or cells would not be good candidates for direct SWIR CRDS probing because they have no unique SWIR signatures. It was postulated that while whole cells or spores are not good candidates for SWIR CRDS detection, their pyrolysis break-down products might be. A literature search was then conducted to find biological pyrolysis products with low molecular weights and high symmetry since these species most likely would have overtone and combination vibrational bands that can be detected in the SWIR. It was determined that pyrrole, pyridine and picolinamide were good candidates for evaluation. These molecules are formed when proteins and porphyrins, proteins and dipicolinic acid, and dipicolinic acid are pyrolyzed, respectively. The second part of the project involved measuring quantitative SWIR spectra of pyrrole, pyridine and picolinamide in PNNL’s FTIR Spectroscopy Laboratory. Spectral information about these molecules, in the vapor phase is sparse – there were only a few prior studies that measured line positions and no information on absorption cross sections. Absorption cross sections are needed in order to estimate the SWIR CRDS detection sensitivity, and line position determines what type of laser will be needed for the sensor. The results of the spectroscopy studies allowed us to estimate the SWIR CRDS detection sensitivity for pyrrole to be 3 x 1012 molec cm-3 or 0.1 ppmv, and for pyridine it was 1.5 x 1015 molec cm-3 or 0.6 ppmv. These detection sensitivity limits are close what we have measured for ...
Date: October 1, 2007
Creator: Aker, Pam M.; Johnson, Timothy J.; Williams, Richard M. & Valentine, Nancy B.
Partner: UNT Libraries Government Documents Department