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Hydrolytic polymerization of chromium (III) hydroxides in the aquatic environment

Description: Products of hydrolytic polymerization of Cr(III) hydroxide were investigated in Milli-Q water and in natural water matrices. Products were first fractionated on Sephadex column using eluents of increasing strength. Ion chromatography (IC) with UV detection at 436 nm was then used to separate the ionic species.
Date: December 1991
Creator: Mbamalu, Godwin E.
Partner: UNT Libraries

The Hydrolysis of α-(Benzenesulfonyl)-Acetophenone

Description: In view of the unexpected behavior of α-(benzenesulfonyl)-acetophenone toward hydrolysis and because of the possible physiological importance of its derivatives it was deemed of interest to make a further study of the hydrolysis of this compound. It was decided to study both the acid and basic hydrolysis of this compound. The problem consisted of finding a satisfactory means of analyzing the hydrolysis products, and carrying out the hydrolysis under the different conditions.
Date: 1950
Creator: Looney, Jesse M.
Partner: UNT Libraries

Near-Monodisperse Ni-Cu Bimetallic Nanocrystals of Variable Composition: Controlled Synthesis and Catalytic Activity for H2 Generation

Description: Near-monodisperse Ni{sub 1-x}Cu{sub x} (x = 0.2-0.8) bimetallic nanocrystals were synthesized by a one-pot thermolysis approach in oleylamine/1-octadecene, using metal acetylacetonates as precursors. The nanocrystals form large-area 2D superlattices, and display a catalytic synergistic effect in the hydrolysis of NaBH{sub 4} to generate H{sub 2} at x = 0.5 in a strongly basic medium. The Ni{sub 0.5}Cu{sub 0.5} nanocrystals show the lowest activation energy, and also exhibit the highest H{sub 2} generation rate at 298 K.
Date: July 22, 2008
Creator: Zhang, Yawen; Huang, Wenyu; Habas, Susan E.; Kuhn, John N.; Grass, Michael E.; Yamada, Yusuke et al.
Partner: UNT Libraries Government Documents Department

The BEI hydrolysis process and reactor system refined engineering proto-type. BEI pilot-plant improvement and operations demonstrations

Description: This BEI project involves BEI-HP and RS's applications toward potential commercial validity demonstrations for dilute-acid corn-fiber cellulose-hydrolysis processing with an aim toward fuel ethanol production.
Date: October 1, 1999
Creator: Brelsford, Donald L.
Partner: UNT Libraries Government Documents Department

Application of Concentration, Adsorption and pH in the Precipitation of the Metal Ions of Groups II and III

Description: In this thesis, the process involved in the precipitations and separations of the metal of Group II and Group III studied. Suggestions have also been offered whereby students can make an analysis without loosing metals in the initial precepitation.
Date: June 1937
Creator: Cockerell, Leone Doris
Partner: UNT Libraries

The Acid Hydrolysis Mechanism of Acetals Catalyzed by a Supramolecular Assembly in Basic Solution

Description: A self-assembled supramolecular host catalyzes the hydrolysis of acetals in basic aqueous solution. The mechanism of hydrolysis is consistent with the Michaelis-Menten kinetic model. Further investigation of the rate limiting step of the reaction revealed a negative entropy of activation ({Delta}S{double_dagger} = -9 cal mol{sup -1}K{sup -1}) and an inverse solvent isotope effect (k(H{sub 2}O)/k(D{sub 2}O) = 0.62). These data suggest that the mechanism of hydrolysis that takes place inside the assembly proceeds through an A-2 mechanism, in contrast to the A-1 mechanism operating in the uncatalyzed reaction. Comparison of the rates of acetal hydrolysis in the assembly with the rate of the reaction of unencapsulated substrates reveals rate accelerations of up to 980 over the background reaction for the substrate diethoxymethane.
Date: September 24, 2008
Creator: Pluth, Michael D.; Bergman, Robert G. & Raymond, Kenneth N.
Partner: UNT Libraries Government Documents Department

Conformational Studies of Myosin and Actin with Calibrated Resonance Energy Transfer

Description: Resonance energy transfer was employed to study the conformational changes of actomyosin during ATP hydrolysis. To calibrate the technique, the parameters for resonance energy transfer were defined. With conformational searching algorithms to predict probe orientation, the distances measured by resonance energy transfer are highly consistent with the atomic models, which verified the accuracy and feasibility of resonance energy transfer for structural studies of proteins and oligonucleotides. To study intramyosin distances, resonance energy transfer probes were attached to skeletal myosin's nucleotide site, subfragment-2, and regulatory light chain to examine nucleotide analog-induced structural transitions. The distances between the three positions were measured in the presence of different nucleotide analogs. No distance change was considered to be statistically significant. The measured distance between the regulatory light chain and nucleotide site was consistent with either the atomic model of skeletal myosin subfragment-1 or an average of the three models claimed for different ATP hydrolysis states, which suggested that the neck region was flexible in solution. To examine the participation of actin in the powerstroke process, resonance energy transfer between different sites on actin and myosin was measured in the presence of nucleotide analogs. The efficiencies of energy transfer between myosin catalytic domain and actin were consistent with the actoS1 docking model. However, the neck region was much closer to the actin filament than predicted by static atomic models. The efficiency of energy transfer between Cys 374 and the regulatory light chain was much greater in the presence of ADP-AlF4, ADP-BeFx, and ADP-vanadate than in the presence of ADP or no nucleotide. These data detect profound differences in the conformations of the weakly and strongly attached crossbridges which appear to result from a conformational selection that occurs during the weak binding of the myosin head to actin. The resonance energy transfer data exclude a number ...
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Date: May 2000
Creator: Xu, Jin
Partner: UNT Libraries

Continuous countercurrent chromatographic separator for the purification of sugars from biomass hydrolyzate. Final project report, July 1, 1996--September 30, 1997

Description: Production of pure sugars is required to enable production of fuels and chemicals from biomass feedstocks. Hydrolysis of cellulose and hemicellulose (principal constituents of biomass) produces sugars that can be utilized in various fermentation process to produce valuable chemicals. Unfortunately, the hydrolysis process also liberates chemicals from the biomass that can be toxic to the fermenting organisms. The two primary toxic components of biomass hydrolyzate are sulfuric acid (catalyst used in the hydrolysis) and acetic acid (a component of the feed biomass). In the standard batch chromatographic separation of these three components, sugar elutes in the middle. Batch chromatographic separations are not practical on a commercial scale, because of excess dilution and high capital costs. Because sugar is the {open_quotes}center product,{close_quotes} a continuous separation would require two costly binary separators. However, a single, slightly larger separator, configured to produce three products, would be more economical. This FIRST project develops a cost-effective method for purifying biomass hydrolyzate into fermentable sugars using a single continuous countercurrent separator to separate this ternary mixture.
Date: December 1, 1997
Creator: Wooley, R. J.
Partner: UNT Libraries Government Documents Department

Lactonization and protonation of gluconic acid: a thermodynamicand kinetic study by potentiometry, nmr and esi-ms

Description: In acidic aqueous solutions, gluconate protonation is coupled with lactonization of gluconic acid. With the decrease of pC{sub H}, two lactones ({delta}/{gamma}) are sequentially formed. The {delta}-lactone forms more readily than the {gamma}-lactone. In 0.1 M gluconate solutions, if pC{sub H} is above 2.5, only the {delta}-lactone is generated. When pC{sub H} is decreased below 2.0, the formation of the {gamma}-lactone is observable although the {delta}-lactone predominates. At I = 0.1 M NaClO{sub 4} and room temperature, the deprotonation constant of the carboxylic group, using the NMR technique, was determined to be log K{sub a} = 3.30 {+-} 0.02; the {delta}-lactonization constant, by the batch potentiometric titrations, was obtained to be log K{sub L} = - (0.54 {+-} 0.04). Using ESI-MS, the rate constants of the {delta}-lactonization and the hydrolysis at pC{sub H} {approx} 5.0 were estimated to be k{sub 1} = 3.2 x 10{sup -5} s{sup -1} and k{sup -1} = 1.1 x 10{sup -4} s{sup -1}, respectively.
Date: January 10, 2007
Creator: Zhang, Z.; Gibson, P.; Clark, S.B.; Tian, G.; Zanonato, P. & Rao, L.
Partner: UNT Libraries Government Documents Department

Time-Dependent Measure of a Nano-Scale Force-Pulse Driven by the Axonemal Dynein Motors in Individual Live Sperm Cells

Description: Nano-scale mechanical forces generated by motor proteins are crucial to normal cellular and organismal functioning. The ability to measure and exploit such forces would be important to developing motile biomimetic nanodevices powered by biological motors for Nanomedicine. Axonemal dynein motors positioned inside the sperm flagellum drive microtubule sliding giving rise to rhythmic beating of the flagellum. This force-generating action makes it possible for the sperm cell to move through viscous media. Here we report new nano-scale information on how the propulsive force is generated by the sperm flagellum and how this force varies over time. Single cell recordings reveal discrete {approx}50 ms pulses oscillating with amplitude 9.8 {+-} 2.6 nN independent of pulse frequency (3.5-19.5 Hz). The average work carried out by each cell is 4.6 x 10{sup -16} J per pulse, equivalent to the hydrolysis of {approx}5,500 ATP molecules. The mechanochemical coupling at each active dynein head is {approx}2.2 pN/ATP, and {approx}3.9 pN per dynein arm, in agreement with previously published values obtained using different methods.
Date: April 23, 2009
Creator: Allen, M J; Rudd, R E; McElfresh, M W & Balhorn, R
Partner: UNT Libraries Government Documents Department

EM 14 - Bubbleless Gas Transfer Technology for the In Situ Remediation of Chlorinated Hydrocarbons

Description: The primary objective of this project is to demonstrate the ability of hydrogen to supply reducing equivalents for the reductive dehalogenation of PCE. This objective will be accomplished by two types of activities. First, laboratory experiments will compare the kinetics of hydrogen-mediated dehalogenation with natural routes of loss (hydrolysis and natural attenuation). Secondly, bench-scale column experiments will be performed to demonstrate hydrogen-mediated reductive dehalogenation in aquifer sediments.
Date: November 1, 1998
Creator: Gallaher, John R. & Kurz, Marc D.
Partner: UNT Libraries Government Documents Department

Batch Microreactor Studies of Base Catalyzed Ligin Depolymerization in Alcohol Solvents

Description: The depolymerization of organosolv-derived lignins by bases in methanol or ethanol solvent was studied in rapidly heated batch microreactors. The conversion of lignin to ether solubles by KOH in methanol or ethanol was rapid at 290 "C, reaching the maximum value within 10-15 minutes. An excess of base relative to Lignin monomer units was required for maximum conversion. Strong bases (KOH, NaOH, CSOH) convert more of the lignin to ether soluble material than do weaker bases LiOH, Ca(OH)2, and NacCO2). Ethanol and methanol are converted to acetic and formic acid respectively under the reaction conditions with an activation energy of approximately 50 kcal/mol. This results in a loss of solvent, but more importantly neutralizes the base catalyst, halting forward progress of the reaction.
Date: February 3, 1999
Creator: Evans, L.; Littlewolf, A.; Lopez, M. & Miller, J.E.
Partner: UNT Libraries Government Documents Department

Polymethylsilsesquioxanes through base-catalyzed redistribution of oligomethylhydridosiloxanes

Description: There has been an increasing amount of interest in silsesquioxanes and polysilsesquioxanes. They have been used as models for silica surfaces and have been shown to have great potential for several industrial applications. Typical synthesis of polysilsesquioxanes involves the hydrolysis of organotricholorosilanes and/or organotrialkoxysilanes in the presence of acid or base catalysts, usually in the presence of organic solvents.
Date: April 4, 2000
Partner: UNT Libraries Government Documents Department

In Situ Template Generation for Zincophosphate Synthesis Leading to C2H7N4O-ZnPO4 Containing Template-to-Template N--H...O Hydrogen Bonds

Description: The synthesis, structure and some properties of C{sub 2}H{sub 7}N{sub 4}O {center_dot} ZnPO{sub 4} (guanylurea zinc phosphate) are reported. The cationic template was prepared in situ by partial hydrolysis of the neutral 2-cyanoguanidine starting material. The resulting structure contains a new, unprotonated, zincophosphate layer topology as well as unusual N-H-O template-to-template hydrogen bonds which help to stabilize a ''double sandwich'' of templating cations between the inorganic sheets. Crystal data: C{sub 2}H{sub 7}N{sub 4}O {center_dot} ZnPO{sub 4}, M{sub r} = 229.44, monoclinic, P2{sub 1}/c, a = 13.6453 (9) {angstrom}, b = 5.0716 (3) {angstrom}, c = 10.6005 (7) {angstrom}, {beta} = 95.918 (2){sup 0}, V = 729.7 (1) {angstrom}{sup 3}, R(F) = 0.034, wR(F) = 0.034.
Date: December 20, 2000
Partner: UNT Libraries Government Documents Department

Measurement of the Hydrogen Yield in the Radiolysis of Water by Dissolved Fission Products

Description: Hydrogen from the radiolysis of water by dissolved fission products is stripped from the solution and collected by bubbling carbon dioxide through the solution. Quantitative measurements of the G value for hydrogen show that the yield is essentially the same as would be obtained by external gamma radiolysis of nonradioactive solutions of the same chemical composition. The hydrogen yield can be enhanced by addition of a hydrogen-atom donor, such as formic acid, to the solution. The yield of hydrogen from fission-waste solutions is discussed with respect to the question of whether it represents a significant energy source.
Date: April 1976
Creator: Sauer, M. C.; Hart, E. J.; Flynn, K. F. & Gindler, J. E.
Partner: UNT Libraries Government Documents Department

[Energies of organic compounds]

Description: The enthalpy of reduction of lactones to the corresponding diols has been determined, allowing the enthaipies of formation of the lactones to be determined. Results of this study agree well with data obtained for enthalpies of hydrolysis of the lactones. We have begun the measurement of the enthalpies of reduction of norbornanones, and we have shown that it is possible to determine the difference in energy between the exo and endo forms of the product alcohols by measuring the equilibrium constant as a function of temperature. The study of the enthalpies of hydration of carbonyl compounds has continued, and the enthalpies of hydrolysis of the corresponding ketals is being determined. The study of the enthalpies of hydration of alkenes is nearly completed, and the rearrangement reactions which were uncovered are being investigated.
Date: December 31, 1991
Creator: Wiberg, K.B.
Partner: UNT Libraries Government Documents Department

Final report for DOE Grant No. DE-FG02-07ER64404 - Field Investigations of Microbially Facilitated Calcite Precipitation for Immobilization of Strontium-90 and Other Trace Metals in the Subsurface

Description: Subsurface radionuclide and metal contaminants throughout the U.S. Department of Energy (DOE) complex pose one of DOE’s greatest challenges for long-term stewardship. One promising stabilization mechanism for divalent ions, such as the short-lived radionuclide 90Sr, is co-precipitation in calcite. We have previously found that that nutrient addition can stimulate microbial ureolytic activity that this activity accelerates calcite precipitation and co-precipitation of Sr, and that higher calcite precipitation rates can result in increased Sr partitioning. We have conducted integrated field, laboratory, and computational research to evaluate the relationships between ureolysis and calcite precipitation rates and trace metal partitioning under environmentally relevant conditions, and investigated the coupling between flow/flux manipulations and precipitate distribution. A field experimental campaign conducted at the Integrated Field Research Challenge (IFRC) site located at Rifle, CO was based on a continuous recirculation design; water extracted from a down-gradient well was amended with urea and molasses (a carbon and electron donor) and re-injected into an up-gradient well. The goal of the recirculation design and simultaneous injection of urea and molasses was to uniformly accelerate the hydrolysis of urea and calcite precipitation over the entire inter-wellbore zone. The urea-molasses recirculation phase lasted, with brief interruptions for geophysical surveys, for 12 days followed by long-term monitoring which continued for 13 months. Following the recirculation phase we found persistent increases in urease activity (as determined from 14C labeled laboratory urea hydrolysis rates) in the upper portion of the inter-wellbore zone. We also observed an initial increase (approximately 2 weeks) in urea concentration associated with injection activities followed by decreasing urea concentration and associated increases in ammonium and dissolved inorganic carbon (DIC) following the termination of injection. Based on the loss of urea and the appearance of ammonium, a first order rate constant for urea hydrolysis of 0.18 day-1 rate with an associate ...
Date: October 12, 2012
Creator: Smith, Robert W.; Fujita, Yoshiko; Ginn, Timothy R. & Hubbard, Susan S.
Partner: UNT Libraries Government Documents Department

Are mixed explicit/implicit solvation models reliable for studying phosphate hydrolysis? A comparative study of continuum, explicit and mixed solvation models.

Description: Phosphate hydrolysis is ubiquitous in biology. However, despite intensive research on this class of reactions, the precise nature of the reaction mechanism remains controversial. In this work, we have examined the hydrolysis of three homologous phosphate diesters. The solvation free energy was simulated by means of either an implicit solvation model (COSMO), hybrid quantum mechanical / molecular mechanical free energy perturbation (QM/MM-FEP) or a mixed solvation model in which N water molecules were explicitly included in the ab initio description of the reacting system (where N=1-3), with the remainder of the solvent being implicitly modelled as a continuum. Here, both COSMO and QM/MM-FEP reproduce Delta Gobs within an error of about 2kcal/mol. However, we demonstrate that in order to obtain any form of reliable results from a mixed model, it is essential to carefully select the explicit water molecules from short QM/MM runs that act as a model for the true infinite system. Additionally, the mixed models tend to be increasingly inaccurate the more explicit water molecules are placed into the system. Thus, our analysis indicates that this approach provides an unreliable way for modelling phosphate hydrolysis in solution.
Date: May 1, 2009
Creator: Kamerlin, Shina C. L.; Haranczyk, Maciej & Warshel, Arieh
Partner: UNT Libraries Government Documents Department