scholarly journals Synthesis, Spectroscopic Properties and Redox Behavior Kinetics of Rare-Earth Bistetrakis-4-[3-(3,4-dicyanophenoxy)phenoxy]phthalocyaninato Metal Complexes with Er, Lu and Yb

Molecules ◽  
2021 ◽  
Vol 26 (8) ◽  
pp. 2181
Author(s):  
Dmitry A. Erzunov ◽  
Anna A. Botnar ◽  
Natalia P. Domareva ◽  
Tatiana V. Tikhomirova ◽  
Arthur S. Vashurin
Keyword(s):  
Bathochromic Shift ◽  
Spectroscopic Properties ◽  
Polymerization Process ◽  
Reduced Form ◽  
Electron Absorption Spectroscopy ◽  
Neutral Radical ◽  
Extinction Coefficients ◽  
Kinetics Of ◽  
Reduced Forms ◽  
Reducing Properties

Novel bistetrakis-4-[3-(3,4-dicyanophenoxy)phenoxy]phthalocyaninato of complexes erbium, lutetium and ytterbium were synthesized using a template fusion method to prevent any polymerization process. The complexes were separated from the reaction mixtures and characterized by NMR, IR and electron absorption spectroscopy. The spectroscopic properties of the metal phthalocyaninates in chloroform, acetone and tetrahydrofuran were studied. The regular bathochromic shift in the Er–Yb–Lu series was determined. In acetone medium all the complexes obtained were found to exist in an equilibrium state between neutral and reduced forms. The linearity of Lambert-Bouger-Beer curves makes it possible to study the kinetics of redox processes in the presence of phenylhydrazine and bromine. The lutetium complex showed better reducing properties and turned fully into the reduced form, while the erbium and ytterbium ones changed only partially. Upon oxidizing all the phthalocyaninates transformed into a mixture of oxidized and neutral-radical forms. The extinction coefficients and effective redox constants were calculated.

Type 2 diabetes mellitus in patients with acute ischemiс stroke is associated with a decrease in plasma glutathione levels

2020 ◽  
Vol 25 (5) ◽  
pp. 29-35
Author(s):  
M. Yu. Maksimova ◽  
A. V. Ivanov ◽  
K. A. Nikiforova ◽  
F. R. Ochtova ◽  
E. T. Suanova ◽  
...  
Keyword(s):  
Diabetes Mellitus ◽  
Type 2 Diabetes ◽  
Type 2 Diabetes Mellitus ◽  
Redox Status ◽  
Reduced Form ◽  
Glutathione Level ◽  
Total Glutathione ◽  
Diabetes Mellitus Group ◽  
Reduced Forms

Ischemic stroke (IS) and type 2 diabetes mellitus are factors that affect the homeostasis of low-molecularweight aminothiols (cysteine, homocysteine, glutathione etc.). It has already been shown that IS in the acute period led to a decrease a level of reduced forms of aminothiols, but it is not clear whether type 2 diabetes mellitus has a noticeable effect there. Objective: to reveal the features of homeostasis of aminothiols in patients with type 2 diabetes mellitus in acute IS. Material and methods. The study involved 76 patients with primary middle cerebral artery IS in the first 10–24 hours after development of neurological symptoms. Group 1 included 15 patients with IS and type 2 diabetes mellitus, group 2 — 61 patients with IS and stress hyperglycemia. Their total plasma levels of cysteine, homocysteine, and glutathione, their reduced forms, and redox status were determined at admission (in the first 24 hours after IS). Results. There was a decrease in the level of total glutathione level (1.27 vs. 1.65 μM, p = 0.021), as well as its reduced form (0.03 vs. 0.04 μM, p = 0.007) in patients with IS and type 2 diabetes mellitus. Patients with type 2 diabetes mellitus who had a low redox status of homocysteine (0.65–1.2%) and glutathione (0.7–2.0%) were also characterized by a decrease in total glutathione level (p = 0.02; p = 0.03). Conclusion. Thus, type 2 diabetes mellitus is associated with a decrease in the level of total glutathione in acute IS. Probably, type 2 diabetes mellitus is characterized by a particular relationship between the metabolism of homocysteine, glutathione and glucose. Therefore, the search for homocysteine-dependent approaches to correct glutathione metabolism in type 2 diabetes mellitus may be of interest as an adjuvant therapy for IS.

Effect of thiol oxidation and thiol export from erythrocytes on determination of redox status of homocysteine and other thiols in plasma from healthy subjects and patients with cerebral infarction

1995 ◽  
Vol 41 (3) ◽  
pp. 361-366 ◽  
Author(s):  
A Andersson ◽  
A Lindgren ◽  
B Hultberg
Keyword(s):  
Cerebral Infarction ◽  
Healthy Subjects ◽  
Redox Status ◽  
Reduced Form ◽  
Temperature Dependent ◽  
First Order ◽  
First Order Kinetics ◽  
Before And After ◽  
Reduced Forms

Abstract Changes in concentration of reduced and oxidized low-M(r) thiols were measured in blood and plasma before and after the separation of blood cells. If centrifugation of blood was postponed, the reduced form of homocysteine in plasma increased with time at 22 degrees C; in contrast, the concentrations of other reduced thiols (cysteine, glutathione, and cysteinylglycine) decreased. In plasma the reduced forms of all thiols disappeared at a rate that followed first-order kinetics. The rates of disappearance ("half-lives") were temperature-dependent; they were about the same for glutathione and homocysteine (11.7 and 14.3 min, respectively, at 22 degrees C) and somewhat higher for cysteinylglycine and cysteine. After establishing proper sampling conditions for reduced thiols, we measured this thiol fraction as well as free (non-protein-bound) and total thiols in 10 reference subjects and 19 patients with cerebral infarction. Mild but significant hyperhomocysteinemia involving total and free homocysteine (but not reduced homocysteine) was found in the patients.

The mercury (63P1) photosensitized hydrogenation of ethylene. Kinetics of the reaction C2H5 + H2 = C2H6 + H

1968 ◽  
Vol 46 (20) ◽  
pp. 3275-3281 ◽  
Author(s):  
L. E. Reid ◽  
D. J. Le Roy
Keyword(s):  
Gas Phase ◽  
Molecular Hydrogen ◽  
Mercury Vapor ◽  
Experimental Conditions ◽  
Working Pressure ◽  
Extinction Coefficients ◽  
Secondary Reactions ◽  
Ethyl Radicals ◽  
Kinetics Of ◽  
Hydrogenation Of Ethylene

A quantitative study has been made of the reaction of ethyl radicals with molecular hydrogen in the gas phase in the temperature range 240 to 320 °C. The mercury (63Pi) photosensitized decomposition of hydrogen in the presence of ethylene was used to generate ethyl radicals. Extinction coefficients for the absorption of 2537 Å by mercury vapor were measured and Beer's law was shown to be obeyed under the experimental conditions used. The corrections required to allow for the nonuniformity of radical concentrations in the cell were small. After delineating the experimental conditions necessary to minimize secondary reactions, the rate constant (cm3 mole−1 s−1) for the reaction C2H5 + H2 = C2H6 + H was found to be given by log10k = 12.57 − 13.7/θ. Experiments in the presence of added carbon dioxide showed the absence of hot radical effects at the working pressure of 92 Torr of hydrogen.

scholarly journals Substitution Effect on the Charge Transfer Processes in Organo-Imido Lindqvist-Polyoxomolybdate

Molecules ◽  
2018 ◽  
Vol 24 (1) ◽  
pp. 44 ◽  
Author(s):  
Patricio Hermosilla-Ibáñez ◽  
Kerry Wrighton-Araneda ◽  
Walter Cañón-Mancisidor ◽  
Marlen Gutiérrez-Cutiño ◽  
Verónica Paredes-García ◽  
...  
Keyword(s):  
Charge Transfer ◽  
Theoretical Study ◽  
Bathochromic Shift ◽  
Substitution Effect ◽  
Spectroscopic Properties ◽  
Electrochemical Studies ◽  
Redox Potentials ◽  
Metal Centre ◽  
Transfer Processes ◽  
Organic Fragment

Two new aromatic organo-imido polyoxometalates with an electron donor triazole group ([n-Bu4N]2[Mo6O18NC6H4N3C2H2]) (1) and a highly conjugated fluorene ([n-Bu4N]2[Mo6O18NC13H9]) (2) have been obtained. The electrochemical and spectroscopic properties of several organo-imido systems were studied. These properties were analysed by the theoretical study of the redox potentials and by means of the excitation analysis, in order to understand the effect on the substitution of the organo-imido fragment and the effect of the interaction to a metal centre. Our results show a bathochromic shift related to the charge transfer processes induced by the increase of the conjugated character of the organic fragment. The cathodic shift obtained from the electrochemical studies reflects that the electronic communication and conjugation between the organic and inorganic fragments is the main reason of this phenomenon.

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 Can hearing puter activate pupil? Phonological competition and the processing of reduced spoken words in spontaneous conversations

2012 ◽  
Vol 65 (11) ◽  
pp. 2193-2220 ◽  
Author(s):  
Susanne Brouwer ◽  
Holger Mitterer ◽  
Falk Huettig
Keyword(s):  
Target Word ◽  
Time Window ◽  
Eye Gaze ◽  
Reduced Form ◽  
Late Time ◽  
Word Form ◽  
Surface Form ◽  
Visual World Paradigm ◽  
Casual Speech ◽  
Reduced Forms

In listeners' daily communicative exchanges, they most often hear casual speech, in which words are often produced with fewer segments, rather than the careful speech used in most psycholinguistic experiments. Three experiments examined phonological competition during the recognition of reduced forms such as [pjutər] for computer using a target-absent variant of the visual world paradigm. Listeners' eye movements were tracked upon hearing canonical and reduced forms as they looked at displays of four printed words. One of the words was phonologically similar to the canonical pronunciation of the target word, one word was similar to the reduced pronunciation, and two words served as unrelated distractors. When spoken targets were presented in isolation (Experiment 1) and in sentential contexts (Experiment 2), competition was modulated as a function of the target word form. When reduced targets were presented in sentential contexts, listeners were probabilistically more likely to first fixate reduced-form competitors before shifting their eye gaze to canonical-form competitors. Experiment 3, in which the original /p/ from [pjutər] was replaced with a “real” onset /p/, showed an effect of cross-splicing in the late time window. We conjecture that these results fit best with the notion that speech reductions initially activate competitors that are similar to the phonological surface form of the reduction, but that listeners nevertheless can exploit fine phonetic detail to reconstruct strongly reduced forms to their canonical counterparts.

scholarly journals Spectroscopic Insights into the Oxygen-tolerant Membrane-associated [NiFe] Hydrogenase of Ralstonia eutropha H16

2009 ◽  
Vol 284 (24) ◽  
pp. 16264-16276 ◽  
Author(s):  
Miguel Saggu ◽  
Ingo Zebger ◽  
Marcus Ludwig ◽  
Oliver Lenz ◽  
Bärbel Friedrich ◽  
...  
Keyword(s):  
Active Site ◽  
Ralstonia Eutropha ◽  
Large Subunit ◽  
Magnetic Coupling ◽  
Spectroscopic Characterization ◽  
Spectroscopic Properties ◽  
Small Subunit ◽  
Reduced Form ◽  
Strictly Anaerobic ◽  
Redox States

This study provides the first spectroscopic characterization of the membrane-bound oxygen-tolerant [NiFe] hydrogenase (MBH) from Ralstonia eutropha H16 in its natural environment, the cytoplasmic membrane. The H2-converting MBH is composed of a large subunit, harboring the [NiFe] active site, and a small subunit, capable in coordinating one [3Fe4S] and two [4Fe4S] clusters. The hydrogenase dimer is electronically connected to a membrane-integral cytochrome b. EPR and Fourier transform infrared spectroscopy revealed a strong similarity of the MBH active site with known [NiFe] centers from strictly anaerobic hydrogenases. Most redox states characteristic for anaerobic [NiFe] hydrogenases were identified except for one remarkable difference. The formation of the oxygen-inhibited Niu-A state was never observed. Furthermore, EPR data showed the presence of an additional paramagnetic center at high redox potential (+290 mV), which couples magnetically to the [3Fe4S] center and indicates a structural and/or redox modification at or near the proximal [4Fe4S] cluster. Additionally, significant differences regarding the magnetic coupling between the Nia-C state and [4Fe4S] clusters were observed in the reduced form of the MBH. The spectroscopic properties are discussed with regard to the unusual oxygen tolerance of this hydrogenase and in comparison with those of the solubilized, dimeric form of the MBH.

scholarly journals Triangulations of root polytopes and reduced forms (Extended abstract)

2009 ◽  
Vol DMTCS Proceedings vol. AK,... (Proceedings) ◽  
Author(s):  
Karola Mészáros
Keyword(s):  
Convex Hull ◽  
Reduced Form ◽  
Vertex Set ◽  
International Audience ◽  
Reduced Forms ◽  
Root Polytope

International audience The type $A_n$ root polytope $\mathcal{P}(A_n^+)$ is the convex hull in $\mathbb{R}^{n+1}$ of the origin and the points $e_i-e_j$ for $1 \leq i < j \leq n+1$. Given a tree $T$ on vertex set $[n+1]$, the associated root polytope $\mathcal{P}(T)$ is the intersection of $\mathcal{P}(A_n^+)$ with the cone generated by the vectors $e_i-e_j$, where $(i, j) \in E(T)$, $i < j$. The reduced forms of a certain monomial $m[T]$ in commuting variables $x_{ij}$ under the reduction $x_{ij} x_{jk} \to x_{ik} x_{ij} + x_{jk} x_{ik} + \beta x_{ik}$, can be interpreted as triangulations of $\mathcal{P}(T)$. If we allow variables $x_{ij}$ and$x_{kl}$ to commute only when $i, j, k, l$ are distinct, then the reduced form of $m[T]$ is unique and yields a canonical triangulation of $\mathcal{P}(T)$ in which each simplex corresponds to a noncrossing alternating forest. Le polytope des racines $\mathcal{P}(A_n^+)$ de type $A_n$ est l'enveloppe convexe dans $\mathbb{R}^{n+1}$ de l'origine et des points $e_i-e_j$ pour $1 \leq i < j \leq n+1$. Étant donné un arbre $T$ sur l'ensemble des sommets $[n+1]$, le polytope des racines associé, $\mathcal{P}(T)$, est l'intersection de $\mathcal{P}(A_n^+)$ avec le cône engendré par les vecteurs $e_i-e_j$, où $(i, j) \in E(T)$, $i < j$. Les formes réduites d'un certain monôme $m[T]$ en les variables commutatives $x_{ij}$ sous la reduction $x_{ij} x_{jk} \to x_{ik} x_{ij} + x_{jk} x_{ik} + \beta x_{ik}$ peuvent être interprétées comme des triangulations de $\mathcal{P}(T)$. Si on impose la restriction que les variables $x_{ij}$ et $x_{kl}$ commutent seulement lorsque les indices $i, j, k, l$ sont distincts, alors la forme réduite de $m[T]$ est unique et produit une triangulation canonique de $\mathcal{P}(T)$ dans laquelle chaque simplexe correspond à une forêt alternée non croisée.

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