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Mechanistic Studies on the Electrochemistry of Glutathione and HomocysteineOyesanya, Olufemi 21 April 2008 (has links)
This research work has investigated the electrochemistry of glutathione (GSH)and homocysteine (HCSH) in order to develop sensors for these biological thiols.Ru(bpy)33+ and IrCl62− have been used as mediators for the electrooxidation of GSH andHCSH because direct oxidation of these thiols is slow at most conventional electrodes.The electrochemical detection of GSH and HCSH has been pursued because of their biological roles.
Concerted proton electron transfer (CPET) and stepwise proton electron transfer(PT/ET) pathways have been observed in the electrooxidation of GSH and HCSH.Oxidation of GSH by Ru(bpy)33+ carried out in deuterated and undeuterated buffered (pH= pD = 5.0) and unbuffered solutions (pH = pD 5.0−9.0) indicates a CPET pathway. AtpH 7.0 buffered solution, the involvement of the buffer was obvious, with rate increasing as the buffer concentration increases − an indication of a general base catalysis. The oxidation of GSH by IrCl62− follows through CPET at pH 7.0 when the optimum concentration of the buffer is established. The plot of the rate vs. buffer concentration gave a curvature at lower buffer concentration and then a plateau at higher concentration,which implies a change in the rate determining step as the buffer concentration increases.At lower buffer concentration, proton transfer was seen to be the rate determining step asthe reduction current increases upon scan rate increase.
In the oxidation of HCSH by IrCl62−, CPET was observed at pH = pD values of7.0 and 8.0, whereas PT/ET was seen at pH = pD values of 9.0 and 10. Increase in the buffer concentration at pH 7.0 revealed the contribution of the buffer, in that, the oxidation proceeds more efficiently, seeing that the catalytic peak current shifts more negatively and the peak broadness diminishes. Increase in the temperature for the electrooxidation of HCSH resulted in increase in the rate.
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Synthese sowie Studien zur Reaktivität eines IridiumperoxidokomplexesBaumgarth, Hanna 10 March 2017 (has links)
Oxygenierungs- und Oxidationsreaktionen sind in unserem Alltag allgegenwärtig und von großer Bedeutung. Sie finden Anwendung von der Natur bis hin zur Industrie. Der Einsatz von O2 als Sauerstoffquelle bzw. Oxidationsmittel ist besonders erstrebenswert. Die Erforschung der Aktivierung von O2 an Übergangsmetallkomplexen und Untersuchung der Reaktivität der resultierenden Verbindung ist von großer Bedeutung für das Verständnis dieser Reaktionen und Mechanismen. In dieser Arbeit wurde zunächst der Komplex trans-[Ir(4-C5F4N)(CNtBu)(PiPr3)2] synthetisiert, welcher mit dem 4-C5F4N- und dem CNtBu-Liganden stabilisierende Komponenten und wertvolle analytische Sonden enthält. Ausgehend von dieser Iridium(I)-Verbindung konnte auf verschiedenen Wegen der Peroxidokomplex trans-[Ir(4-C5F4N)(O2)(CNtBu)(PiPr3)2] erhalten und umfangreich charakterisiert werden. In Gegenwart von [Fe(C5H5)2][PF6] konnten Hinweise auf einen redoxkatalysierten Mechanismus gewonnen werden. Im nächsten Abschnitt konnte gezeigt werden, dass sich der Peroxidokomplex durch Bronstedsäuren aktivieren lässt. So wurde z.B. unter der Verwendung von Säuren wie HCl, CF3COOH oder HF die Bildung von H2O2 erzielt. Dabei entstehen die entsprechenden Iridium(III)-Komplexe mit den koordinierten Säureanionen. In Gegenwart von HCOOH werden ein Carbonatokomplex und H2 als Hauptprodukte gebildet und es konnten Hinweise zum Mechanismus dieser komplexen Reaktion gewonnen werden. Des Weiteren sind Lewissäuren und Elektrophile in der Lage, die metallgebundene Disauerstoffeinheit des Peroxidokomplexes zu aktivieren. Dazu wurden unter Anderem Silane und Borane eingesetzt. Im Fall von ClSiMe3 und BClCy2 konnten während der Reaktion Intermediate detektiert und analysiert werden. Tragen die Lewissäuren Chloratome wird die entsprechende Dichloridoiridium(III)-Verbindung gebildet. Durch Einsatz von BPh3 konnte eine veränderte Reaktivität erreicht werden und der Ausgangskomplex trans-[Ir(4-C5F4N)(CNtBu)(PiPr3)2] zurückerhalten werden. / Oxygenation- and oxidation reactions are ubiquitous and of great importance to our daily life. They find application from nature to industry. The use of O2 as an oxygen source or oxidation reagent, respectively, is particularly desirable. The research on the activation of O2 at transition metal complexes and the investigations of the reactivity of the resulting compounds is of great significance for the understanding of these reactions and mechanisms. Herein, this work describes the synthesis of the complex trans-[Ir(4-C5F4N)(CNtBu)(PiPr3)2], which incorporates stabilizing and valuable analytical elements provided by the 4-C5F4N and CNtBu ligands. Starting from this iridium(I) compound, the peroxido complex trans-[Ir(4-C5F4N)(O2)(CNtBu)(PiPr3)2] could be synthesized using different methods. In the presence of [Fe(C5H5)2][PF6], indications for a redox catalyzed mechanism could be provided. The next chapter shows that Bronsted acids are capable of activating the peroxido complex. With the help of acids like HCl, CF3COOH or HF, for example, the formation of H2O2 was achieved. Thereby, the corresponding iridium(III) complexes with the coordinating anions are formed. In the presence of HCOOH, a carbonato complex and H2 are formed as main products and ideas for the mechanism of this complex reaction were indicated. Furthermore, Lewis acids and electrophiles have the ability to activate the metal bound dioxygen moiety of the peroxido complex. Silanes and boranes were used for this purpose amongst others. In case of ClSiMe3 and BClCy2, intermediates of the reactions could be detected and analysed. If the Lewis acids carry chloride atoms, the corresponding dichlorido iridium(III) compounds were formed. BPh3 enabled a different reactivity and allowed the isolation of the starting material trans-[Ir(4C5F4N)(CNtBu)(PiPr3)2].
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Studies towards Developing Diastereoselective SN1 Reactions of α-Keto CarbocationsDubland, Joshua 06 April 2010 (has links)
Although α-keto carbocations have been demonstrated to be viable intermediates in solvolysis reactions, their applications in synthesis are scarce. These species can be considered to be equivalent to “reversed polarity” enolates and, as such, could be useful for the asymmetric formation of carbon-carbon and carbon-heteroatom bonds. In principle, facial selectivity in additions to α-keto carbocations may be induced using easily removed ester, amide, or imide chiral auxiliaries. Efforts to achieve such diastereoselective SN1 reactions of α-keto carbocations are described herein.
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Studies towards Developing Diastereoselective SN1 Reactions of α-Keto CarbocationsDubland, Joshua 06 April 2010 (has links)
Although α-keto carbocations have been demonstrated to be viable intermediates in solvolysis reactions, their applications in synthesis are scarce. These species can be considered to be equivalent to “reversed polarity” enolates and, as such, could be useful for the asymmetric formation of carbon-carbon and carbon-heteroatom bonds. In principle, facial selectivity in additions to α-keto carbocations may be induced using easily removed ester, amide, or imide chiral auxiliaries. Efforts to achieve such diastereoselective SN1 reactions of α-keto carbocations are described herein.
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Ab Initio Molecular Dynamics Studies of Bronsted Acid-Base Chemistry in Aqueous SolutionsTummanapelli, Anil Kumar January 2015 (has links) (PDF)
Knowledge of the dissociation constants of the ionizable protons of weak acids in aqueous media is of fundamental importance in many areas of chemistry and biochemistry. The pKa value, or equilibrium dissociation constant, of a molecule determines the relative concentration of its protonated and deprotonated forms at a specified pH and is therefore an important descriptor of its chemical reactivity. Considerable efforts have been devoted to the determination of pKa values by deferent experimental techniques. Although in most cases the determination of pKa values from experimental is straightforward, there are situations where interpretation is difficult and the results ambiguous. It is, therefore, not surprising that the capability to provide accurate estimates of the pKa value has been a central goal in theoretical chemistry and there has been a large effort in developing methodologies for predicting pKa values for a variety of chemical systems by differing quantum chemical techniques. A prediction accuracy within 0.5 pKa units of experiment is the desirable level of accuracy. This is a non-trivial exercise, for an error of 1 kcal/mol in estimates of the free energy value would result in an error of 0.74 pKa units.
In this thesis ab initio Car-Parrinello molecular dynamics (CPMD) has been used for investigating the Brϕnsted acid-base chemistry of weak acids in aqueous solution. A key issue in any dissociation event is how the solvating water molecules arrange themselves spatially and dynamically around the neutral and dissociated acid molecule. Ab initio methods have the advantage that all solvent water molecules can, in principle, be con- sidered explicitly. One of the factors that has inhibited the widespread use of ab initio MD methods to study the dissociation reaction is that dissociation of weak acids are rare events that require extremely long simulation times before one is observed. The metady- namics formalism provides a solution to this conundrum by preventing the system from revisiting regions of configuration space where it has been in the past. The formalism allows the system to escape the free-energy minima by biasing the dynamics with a history dependent potential (or force) that acts on select degrees of freedom, referred to as collective variables. The bias potentials, modeled by repulsive inverted Gaussians that are dropped during propagation, drive the system out of any free-energy minima and allow it to explore the configuration space by a relatively quick and efficient sampling. The the- sis deals with a detailed investigation of the Brϕnsted acid-base chemistry of weak acids in aqueous solutions by the CPMD-metadynamics procedure.
In Chapter 1, current approaches for the theoretical estimation of pKa values are summarized while in Chapter 2 the simulation methodology and the metadynamics sampling techniques used in thisstudy are described.
The potential of the CPMD-metadynamics procedure to provide estimates of the acid dissociation constant (pKa) is explored in Chapter 3, using acetic acid as a test sys- tem. Using the bond-distance dependent coordination number of protons bound to the dissociating carboxylic groups as the collective variable, the free-energy profile for the dissociation reaction of acetic acid in water was computed. Convergence of the free-energy profiles and barriers for the simulations parameters is demonstrated. The free-energy profiles exhibit two distinct minima corresponding to the dissociated and neutral states of the acid and the deference in their values provides the estimate for pKa. The estimated value of pKa for acetic acid from the simulations, 4.80, is in good agreement with the experiment at value of 4.76. It is shown that the good agreement with experiment is a consequence of the cancellation of errors, as the pKa values are computed as the difference in the free energy values at the minima corresponding to the neutral and dissociated state. The chapter further explores the critical factors required for obtaining accurate estimates of the pKa values by the CPMD-metadynamics procedure. It is shown that having water molecules sufficient to complete three hydration shells as well as maintaining water density in the simulation cell as close to unity is important.
In Chapter 4, the CPMD-metadynamics procedure described in Chapter-3 has been used to investigate the dissociation of a series of weak organic acids in aqueous solutions. The acids studied were chosen to highlight some of the major factors that influence the dissociation constant. These include the influence of the inductive effect, the stabilization of the dissociated anion by H-bonding as well as the presence of multiple ionizable groups. The acids investigated were aliphatic carboxylic acids, chlorine-substituted carboxylic acids, cid and trans-butenedioic, the isomers of hydroxybenzoic acid and phthalic acids and its isomers. It was found that in each of these examples the CPMD-metadynamics procedure correctly estimates the pKa values, indicating that the formulism is capable of capturing these influences and equally importantly indicating that the cancellation of errors is indeed universal. Further, it is shown that the procedure can provide accurate estimates of the successive pKa values of polypro tic acids as well as the subtle deference in their values for deterrent isomers of the acid molecule.
Changes in protonation-deprotonation of amino acid residues in proteins play a key role in many biological processes and pathways. It is shown that CPMD simulations in conjunction with metadynamics calculations of the free energy profile of the protonation- deprotonation reaction can provide estimates of the multiple pKa values of the 20 canonical α-amino acids in aqueous solutions in good agreement with experiment (Chapter 5). The distance-dependent coordination number of the protons bound to the hydroxyl oxygen of the carboxylic and the amine groups is used as the collective variable to explore the free energy profiles of the Brϕnsted acid-base chemistry of amino acids in aqueous solutions. Water molecules, sufficient to complete three hydration shells surrounding the acid molecule were included explicitly in the computation procedure. The method works equally well for amino acids with neutral, acidic and basic side chains and provides estimates of the multiple pKa values with a mean relative error with respect to experimental results, of 0.2 pKa units.
The tripeptide Glutathione (GSH) is one of the most abundant peptides and the major repository for non-protein sulfur in both animal and plant cells. It plays a critical role in intracellular oxidative stress management by the reversible formation of glutathione disulfide with the thioldisulfide pair acting as a redox buffer. The state of charge of the ionizable groups of GSH can influences the redox couple and hence the pKa value of the cysteine residue of GSH is critical to its functioning. In Chapter 6, it has been reported that ab initio Car-Parrinello Molecular Dynamics simulations of glutathione solvated by 200 water molecules, all of which are considered in the simulation. It is shown that the free-energy landscape for the protonation - deprotonation reaction of the cysteine residue of GSH computed using metadynamics sampling provides accurate estimates of the pKa and correctly predicts the shift in the dissociation constant values as compared to the isolated cysteine amino acid.
The dissociation constants of weak acids are commonly determined from pH-titration
curves. For simple acids the determination of the pKa from the titration curves using the Henderson-Hasselbalch equation is relatively straightforward. There are situations, however, especially in polypro tic acids with closely spaced dissociation constants, where titration curves do not exhibit clear inflexion and equivalence stages and consequently the estimation of multiple pKa values from a single titration curve is no longer straightfor-
ward resulting in uncertainties in the determined pKa values. In Chapter 7, the multiple
dissociation constant of the hexapeptide glutathione disulfide (GSSG) with six ionizable groups and six associated dissociation constants has been investigated. The six pKa values of GSSG were estimated using the CPMD-metadynamics procedure from the free-energy profiles for each dissociation reaction computed using the appropriate collective variable. The six pKa values of GSSG were estimated and the theoretical pH-titration curve was then compared with the experimentally measured pH-titration curve and found to be in excellent agreement. The object of the exercise was to establish whether interpretation of pH-titration curves of complex molecules with multiple ionizable groups could be facilitated using results of ab initio molecular dynamics simulations.
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The Direct Detection and Kinetic Studies of Dimethylgermylene and Tetramethyldigermene In Solution By Nanosecond Laser Flash Photolysis / Dimethylgermylene and Tetramethyldigermene In SolutionLollmahomed, Farahnaz Begum 10 1900 (has links)
<p> Dimethylgermylene (GeMe2) has been generated by laser flash photolysis of 1,1dimethyl-3-phenylgermacyclopent-3-ene (23) and 1,1,3-trimethyl-4phenylgermacyclopent-3-ene (24) in hexanes at 25°C and its absorption maximum (λmax) has been unambiguously established to be 470 nm. GeMe2 decays with second-order kinetics under these conditions (2k/ε. = (10 ± 2) x 10^7 cm s^(-1)) to give Ge2Me4 (λmax = 370 nm). Kinetic studies of the reactions of GeMe2 and Ge2Me4 with typical germylene/digermene scavengers such as 1,3-dienes, olefins, alkynes, alkyl halides, group 14 metal hydrides, carboxylic acids, and amines have been carried out. </p>
<p> GeMe2 reacts reversibly with MeOH, t-BuOH and THF to form Lewis acid-base complexes which exhibit relatively strong absorption bands that are blue-shifted with respect to GeMe2 (λmax ~ 295-310 nm). The decay of the Me2Ge-MeOH complex is accelerated in the presence of a Brnnsted acid (acetic acid or methanesulfonic acid) or base (MeONa). The reactions of the Me2Ge-THF complex with sodium methoxide, methanesulfonic acid, 4,4-dimethyl-1-pentene, 2,3-dimethyl-1-butadiene, acetic acid and CC4 have also been studied in THF. </p>
<p> The photochemistry of two well-known precursors to GeMe2, namely dodecamethylcyclohexagermane (14) and dimethylphenyl(trimethylsilyl)germane (18) was reinvestigated. Laser flash photolysis of 14 in hexanes led to the formation of two transients, one with λmax= 490 nm (τ < & = 10 ns) and the second with λmax= 470 nm. The latter decays with second-order kinetics with concomitant formation of a new transient with λmax= 370 nm. The transient at 470 nm is assigned to GeMe2 and that at 370 nm to Ge2Me4, based on comparisons to the results obtained from laser flash photolysis of 23 and 24. Laser flash photolysis of 18-in hexane gives rise to two absorption bands centered at λmax = 300 nm and λmax = 430 nm, which are assigned to the dimethylphenylgerrnyl radical and the conjugated gerrnene derivative 38, respectively. GeMe2 cannot be detected in laser flash photolysis experiments with this compound. </p> / Thesis / Doctor of Philosophy (PhD)
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Estudio de catalizadores microporosos Mo/zeolita en la reacción de deshidroaromatización de metanoPeris Chanzá, Ernesto José 07 January 2016 (has links)
[EN] This doctoral thesis shows the study carried out on Mo/zeolite
catalysts in the dehydroaromatization reaction of methane (MDA) with
the intention to contribute to this technical approximation regarding the
valorisation of said reactant. As it is observed from the information
contributed in the introductory chapter, methane (main component in
natural gas deposits, but also present in those of oil and coal) may be
considered, in a near future, as an alternative source to oil in obtaining
primary hydrocarbons for the petrochemical industry. Taking into
account the state-of-art previous to the start this thesis, it was
proposed to develop a series of studies adressed to surpass and
improve some of the difficulties referenced in the consulted literature.
In this sense, the work was oriented to mitigate the processes
involved in the accumulation of coke on the zeolitic acid sites and, this
way, reduce the high deactivation rates registered on the catalysts
usually employed in this reaction. In brief, the control of the density of
zeolitic acid sites (mainly, the excess of Brønsted ones) was designed
from distinct approaches: the reduction/elimination of this possible
excess by dealumination methods (chapter 5), their reduction by
means of selective exchange of the zeolite with mono- and divalent
cations (chapter 6) and their reduction by means of the use of a ZSM-
5 mesoporous sample (chapter 7). In view of the results obtained in
chapter 7, it was considered relevant to analyse the effect that zeolites
with large cavities or intersections could have in the tendency to
accumulate coke, the obtained data being supported by molecular
dynamic modelling (chapter 8). Finally, this thesis incorporates some
general conclusions regarding the shown work and, also, the future of
the MDA process. / [ES] En esta tesis doctoral se presenta el estudio llevado a cabo sobre
catalizadores Mo/zeolita en la reacción de deshidroaromatización de
metano (MDA) con la intención de contribuir a esta aproximación
técnica hacia la valorización de dicho reactante. Como se observa de
la información aportada en el capítulo de introducción, el metano
(componente principal de los yacimientos de gas natural, pero
también presente en aquellos de petróleo y carbón) se postula, en un
futuro próximo, como fuente alternativa al petróleo en la obtención de
hidrocarburos primarios para la industria petroquímica. Teniendo en
cuenta el estado del arte previo al inicio de esta tesis, se planteó el
desarrollo de un conjunto de estudios dirigidos a superar y mejorar
algunas de las dificultades a las que la literatura hacía referencia. En
este sentido, se orientó el trabajo a paliar los procesos causantes de
la acumulación de coque sobre los centros ácidos zeolíticos y, así,
poder reducir las elevadas tasas de desactivación registradas sobre
los catalizadores habitualmente empleados en esta reacción.
Brevemente, se diseñó el control de la densidad de centros ácidos
zeolíticos (concretamente, el exceso de aquellos de tipo Brønsted)
desde distintos enfoques: la reducción/eliminación de un posible
exceso por métodos de desaluminización (capítulo 5), su reducción
mediante intercambio selectivo de la zeolita con cationes mono y
divalentes (capítulo 6) y su reducción mediante el uso de una zeolita
ZSM-5 con mesoporos (capítulo 7). Por último, en vista de los
resultados obtenidos en el capítulo 7, se consideró relevante analizar
el efecto que zeolitas con cavidades o intersecciones de grandes
dimensiones podrían tener en la tendencia a acumular coque,
apoyando los datos obtenidos a este respecto con estudios de
modelización molecular (capítulo 8). Finalmente, esta tesis incorpora
unas conclusiones generales referidas al propio trabajo presentado y,
también, orientadas al futuro del proceso de MDA. / [CAT] En aquesta tesi doctoral es presenta l'estudi dut a terme sobre
catalitzadors Mo/zeolita en la reacció de deshidroaromatització de
metà (MDA) amb la intenció de contribuir a aquesta aproximació
tècnica cap a la valorització d'aquest reactant. Com s'observa de la
informació aportada en el capítol d'introducció, el metà (component
principal dels jaciments de gas natural, però també present en aquells
de petroli i carbó) es postula, en un futur pròxim, com font alternativa
al petroli en l'obtenció d'hidrocarburs primaris per a la indústria
petroquímica. Tenint en compte l'estat de l'art previ a l'inici d'aquesta
tesi, es va plantejar el desenvolupament d'un conjunt d'estudis dirigits
a superar i millorar algunes de les dificultats a les quals la literatura
feia referència. En aquest sentit, es va orientar el treball a pal·liar els
processos causants de l'acumulació de coc sobre el centres ácids
zeolítics i, així, poder reduir les elevades taxes de desactivació
registrades sobre els catalitzadors habitualmente emprats en aquesta
reacció. Breument, es va dissenyar el control de la densitat de centres
àcids zeolítics (concretament, l'excés d'aquells de tipus Brønsted) des
de distints enfocaments: la reducció/eliminació d'aquest possible
excés per métodes de desaluminització (capítol 5), la seua reducció
mitjançant intercanvi selectiu de la zeolita amb cations mono- i
divalents (capítol 6) i la seua reducció mitjançant l'ús d'una zeolita
ZSM-5 amb mesoporus (capítol 7). A partir dels resultats obtinguts en
el capítol 7, es va considerar rellevant analitzar l'efecte que zeolites
amb cavitats o interseccions de grans dimensions podrien tenir en la
tendència a acumular coc, recolzant les dades obtingudes a este
respecte amb estudis de modelització molecular (capítol 8).
Finalment, aquesta tesi incorpora unes conclusions generals referides
al propi treball presentat i, també, orientades al futur del procés de
MDA. / Peris Chanzá, EJ. (2015). Estudio de catalizadores microporosos Mo/zeolita en la reacción de deshidroaromatización de metano [Tesis doctoral no publicada]. Universitat Politècnica de València. https://doi.org/10.4995/Thesis/10251/59441 / TESIS
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