scholarly journals Laccase Redox Potentials: pH Dependence and Mutants, a QM/MM Study

2016 ◽  
Vol 120 (35) ◽  
pp. 9265-9276 ◽  
Author(s):  
Jan P. Götze ◽  
Michael Bühl
Keyword(s):  
Ph Dependence ◽  
Redox Potentials

Some Physicochemical Peculiarities of Poplar Plastocyanins a and b

2009 ◽  
Vol 64 (5-6) ◽  
pp. 399-404 ◽  
Author(s):  
Petya K. Christova ◽  
Anthony A. Donchev ◽  
Alexandra C. Shosheva ◽  
Vladimir I. Getov ◽  
Mitko I. Dimitrov
Keyword(s):  
Plant Species ◽  
Ph Dependence ◽  
Equilibrium Constants ◽  
The Other ◽  
Redox Potentials ◽  
Extinction Coefficients ◽  
Structural Differences ◽  
Ph Dependent ◽  
Ph Range ◽  
Reduced Forms

The redox potentials of poplar plastocyanins a and b (PCa, PCb) were determined by spectro photometric titrations of their reduced forms with [Fe(CN)6]3-. It was found that the two isoforms have the following millimolar extinction coefficients ε597, equilibrium constants Keq of one-electron exchange with [Fe(CN)6]4-/[Fe(CN)6]3-, and standard electron potentials E0′: PCa: ε597 = (4.72 ± 0.08) mM-1 cm-1, Keq = 0.133 ± 0.009, E0′ = (354 ± 11) mV; PCb: ε597 = (5.23 ± 0.16) mM-1 cm-1, Keq = 0.175 ± 0.010, E0′ = (363 ± 12) mV. The pH dependence of the redox potential of PCb was studied too. It was found, that the value of E0′ for PCb is constant in the pH range 6.5 - 9.5, but decreases in the range 4.8 - 6.5. On the whole, the dependence resembles that of PC from some well-known plant species, including poplar PCa. The changes of E0′ in the pH-dependent region for poplar PCb, however, are smaller and are 13 mV per pH unit, whereas in the other well-known plant species the changes are about 50 - 60 mV per pH unit. It has been assumed that the weaker pH dependence of E0′ of PCb accounts for some structural differences between PCa and PCb

scholarly journals The two cytochromes c in the facultative methylotroph Pseudomonas AM1

1980 ◽  
Vol 192 (2) ◽  
pp. 411-419 ◽  
Author(s):  
David T. O'Keeffe ◽  
Christopher Anthony
Keyword(s):  
Molecular Weight ◽  
Ion Exchange ◽  
Isoelectric Point ◽  
Ph Dependence ◽  
Polyacrylamide Gel Electrophoresis ◽  
Sodium Dodecyl ◽  
Deae Cellulose ◽  
Redox Potentials ◽  
Midpoint Potential ◽  
Cytochromes C

It was previously suggested that there is only one soluble cytochrome c in Pseudomonas AM1, having a molecular weight of 20000, a redox midpoint potential of about +260mV and a low isoelectric pint [Anthony (1975) Biochem. J.146, 289–298; Widdowson & Anthony (1975) Biochem. J.152, 349–356]. A more thorough examination of the soluble fraction of methanol-grown Pseudomonas AM1 has now revealed the presence of two different cytochromes c. These were both purified to homogeneity by acid treatment, ion-exchange chromatography, gel filtration, chromatography on hydroxyapatite and preparative isoelectric focusing. Molecular weights were determined by sodium dodecyl sulphate/polyacrylamide-gel electrophoresis; midpoint redox potentials were determined directly by using platinum and calomel electrodes; isoelectric points were estimated by electrophoresis and by the behaviour of the two cytochromes on ion-exchange celluloses. The more abundant cytochrome cH (λmax. 550.5nm) had a low molecular weight (11000), a midpoint potential of about +294mV and a high isoelectric point, not being adsorbed on DEAE-cellulose in 20mm-Tris/HCl buffer, pH8.0. The less abundant cytochrome cL (λmax. 549nm) was about 30% of the total; it had a high molecular weight (20900), a midpoint potential of about +256mV and a low isoelectric point, binding strongly to DEAE-cellulose in 20mm-Tris/HCl buffer, pH8.0. The pH-dependence of the midpoint redox potentials of the two cytochromes c were very similar. There were four ionizations affecting the redox potentials in the pH range studied (pH4.0–9.5), two in the oxidized form (pK values about 3.5 and 5.5) and two in the reduced form (pK values about 4.5 and 6.5), suggesting that the ionizing groups involved may be the two propionate side chains of the haem. Neither of the cytochromes c was present in mutant PCT76, which was unable to oxidize or grow on C1 compounds, although still able to grow well on multicarbon compounds such as succinate. Whether or not these two cytochromes c have separate physiological functions is not yet certain.

scholarly journals Studies on the stabilized ubisemiquinone species in the succinate-cytochrome c reductase segment of the intact mitochondrial membrane system

1980 ◽  
Vol 192 (3) ◽  
pp. 769-781 ◽  
Author(s):  
J C Salerno ◽  
T Ohnishi
Keyword(s):  
Redox State ◽  
Ph Dependence ◽  
Specific Inhibitor ◽  
Membrane System ◽  
Dipolar Interaction ◽  
Energy Transduction ◽  
Redox Potentials ◽  
Succinate Cytochrome C Reductase ◽  
Ph Range ◽  
Reduced State

1. Evidence is presented for the presence of a stable ubisemiquinone pair in the vicinity of iron-sulphur centre S-3, based on its thermodynamic and spin relaxation properties. 2. These semiquinones are coupled by dipolar interaction; quantitative analysis of the signals of the spin-coupled semiquinones (at pH 7.4) gives midpoint redox potentials E1 (oxidized to semiquinone state) and E2 (semiquinone to fully reduced state) of 140 and 80mV, respectively, for individual ubiquinones. 3. Values of pKS (pK of the semiquinone form) below 6.5 and pKR (pK of the fully reduced ubiquinone) of about 8.0 or above were estimated from the pH-dependence of the midpoint potentials of the spin coupled signals. Thus the ubisemiquinone associated with succinate dehydrogenase (designated as SQS) functions mostly in the anionic form of the physiological pH range. 4. Theonyltrifluoroacetone, a specific inhibitor of the succinate-ubiquinone reductase segment of the respiratory chain, destabilized the intermediate redox state; thus it quenches both the g = 2.00 signal and ubisemiquinone (SQS) and split signals from the spin coupled pair. This inhibitor has no significant effect on another bound ubisemiquinone species present in the cytochrome bc1 region (designated as SQC). 5. The possible function and location of these stabilized ubisemiquinone species were discussed in connection with Site-II energy transduction.

Self-association of insulin. Its pH dependence and effect of plasma

Diabetes ◽  
1987 ◽  
Vol 36 (3) ◽  
pp. 261-264 ◽  
Author(s):  
E. Helmerhorst ◽  
G. B. Stokes
Keyword(s):  
Ph Dependence ◽  
Self Association

Using A Segmented Voltage Sweep Mode and A Gaussian Curve Fitting Method to Improve Heavy Metal Measurement System Performance

2012 ◽  
Vol 19 (2) ◽  
pp. 381-394
Author(s):  
José Pereira ◽  
Octavian Postolache ◽  
Pedro Girão
Keyword(s):  
Heavy Metals ◽  
Heavy Metal ◽  
Measurement System ◽  
Curve Fitting ◽  
System Performance ◽  
Redox Potentials ◽  
Voltage Sweep ◽  
Gaussian Curve ◽  
Fitting Method ◽  
Curve Fitting Method

Using A Segmented Voltage Sweep Mode and A Gaussian Curve Fitting Method to Improve Heavy Metal Measurement System PerformanceThis paper presents a voltammetric segmented voltage sweep mode that can be used to identify and measure heavy metals' concentrations. The proposed sweep mode covers a set of voltage ranges that are centered around the redox potentials of the metals that are under analysis. The heavy metal measurement system can take advantage of the historical database of measurements to identify the metals with higher concentrations in a given geographical area, and perform a segmented sweep around predefined voltage ranges or, alternatively, the system can perform a fast linear voltage sweep to identify the voltammetric current peaks and then perform a segmented voltage sweep around the set of voltages that are associated with the voltammetric current peaks. The paper also includes the presentation of two auto-calibration modes that can be used to improve system's reliability and proposes the usage of a Gaussian curve fitting of voltammetric data to identify heavy metals and to evaluate their concentrations. Several simulation and experimental results, that validate the theoretical expectations, are also presented in the paper.

Rationalizing the pH-Activity Response for Escherichia Coli’s Glycinamide Ribonucleotidetransformylase Through Computational Methods

2019 ◽  
Author(s):  
Adrian Roitberg ◽  
Pancham Lal Gupta
Keyword(s):  
Transfer Reaction ◽  
Catalytic Mechanism ◽  
Ph Dependence ◽  
Ph Effects ◽  
Dependent Manner ◽  
E Coli ◽  
Gar Tfase ◽  
Activity Curve ◽  
Ph Dependent ◽  
Formyl Transfer

<div>Human Glycinamide ribonucleotide transformylase (GAR Tfase), a regulatory enzyme in the de novo purine biosynthesis pathway, has been established as an anti-cancer target. GAR Tfase catalyzes the formyl transfer reaction from the folate cofactor to the GAR ligand. In the present work, we study E. coli GAR Tfase, which has high sequence similarity with the human GAR Tfase with most functional residues conserved. E. coli GAR Tfase exhibits structural changes and the binding of ligands that varies with pH which leads to change the rate of the formyl transfer reaction in a pH-dependent manner. Thus, the inclusion of pH becomes essential for the study of its catalytic mechanism. Experimentally, the pH-dependence of the kinetic parameter kcat is measured to evaluate the pH-range of enzymatic activity. However, insufficient information about residues governing the pH-effects on the catalytic activity leads to ambiguous assignments of the general acid and base catalysts and consequently its catalytic mechanism. In the present work, we use pH-replica exchange molecular dynamics (pH-REMD) simulations to study the effects of pH on E. coli GAR Tfase enzyme. We identify the titratable residues governing the pH-dependent conformational changes in the system. Furthermore, we filter out the protonation states which are essential in maintaining the structural integrity, keeping the ligands bound and assisting the catalysis. We reproduce the experimental pH-activity curve by computing the population of key protonation states. Moreover, we provide a detailed description of residues governing the acidic and basic limbs of the pH-activity curve.</div>

1,1’-Biaceanthrylene and 2,2'-Biaceanthrylene: Models for Linking Larger Polycyclic Aromatic Hydrocarbons via Five-Membered Rings

2019 ◽  
Author(s):  
Yachu Du ◽  
Kyle Plunkett
Keyword(s):  
Polycyclic Aromatic Hydrocarbons ◽  
Polycyclic Aromatic Hydrocarbon ◽  
Aromatic Hydrocarbon ◽  
Electronic Properties ◽  
Aromatic Hydrocarbons ◽  
Model Systems ◽  
Redox Potentials ◽  
Dimer Model ◽  
Optical And Electronic Properties ◽  
Polycyclic Aromatic

We show that polycyclic aromatic hydrocarbon (PAH) chromophores that are linked between two five-membered rings can access planarized structures with reduced optical gaps and redox potentials. Two aceanthrylene chromophores were connected into dimer model systems with the chromophores either projected outward (2,2’-biaceanthrylene) or inward (1,1’-biaceanthrylene) and the optical and electronic properties were compared. Only the planar 2,2’-biaceanthrylene system showed significant reductions of the optical gaps (1 eV) and redox potentials in relation to the aceanthrylene monomer.<br>

1,1’-Biaceanthrylene and 2,2'-Biaceanthrylene: Models for Linking Larger Polycyclic Aromatic Hydrocarbons via Five-Membered Rings

2019 ◽  
Author(s):  
Yachu Du ◽  
Kyle Plunkett
Keyword(s):  
Polycyclic Aromatic Hydrocarbons ◽  
Polycyclic Aromatic Hydrocarbon ◽  
Aromatic Hydrocarbon ◽  
Electronic Properties ◽  
Aromatic Hydrocarbons ◽  
Model Systems ◽  
Redox Potentials ◽  
Dimer Model ◽  
Optical And Electronic Properties ◽  
Polycyclic Aromatic

We show that polycyclic aromatic hydrocarbon (PAH) chromophores that are linked between two five-membered rings can access planarized structures with reduced optical gaps and redox potentials. Two aceanthrylene chromophores were connected into dimer model systems with the chromophores either projected outward (2,2’-biaceanthrylene) or inward (1,1’-biaceanthrylene) and the optical and electronic properties were compared. Only the planar 2,2’-biaceanthrylene system showed significant reductions of the optical gaps (1 eV) and redox potentials in relation to the aceanthrylene monomer.<br>

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