L. A. Shaposhnikov, S. S. Savin, D. L. Atroshenko, T. A. Chubar, E. V. Pometun, V. I. Tishkov, A. A. Pometun
{"title":"Engineering the N-Terminal Sequence of Glycine max Soybean Formate Dehydrogenase","authors":"L. A. Shaposhnikov, S. S. Savin, D. L. Atroshenko, T. A. Chubar, E. V. Pometun, V. I. Tishkov, A. A. Pometun","doi":"10.3103/S0027131423040053","DOIUrl":"10.3103/S0027131423040053","url":null,"abstract":"<p>NAD(P)<sup>+</sup>-dependent formate dehydrogenase (FDH, EC 1.2.1.2.) catalyzes the oxidation of formate ion with the coupled reduction of NAD(P)<sup>+</sup> to NAD(P)H. Previously, in our laboratory, a genetic construct was obtained with the <i>soyfdh2</i> gene encoding isoenzyme 2 of formate dehydrogenase from soybean <i>Glycine max</i> (SoyFDH). In this construct the nucleotide sequence encoding the signal peptide responsible for the transport of the pro-enzyme into the mitochondria of plant cells (the SoyFDH_L enzyme) was deleted. In this work, a second variant of SoyFDH_S was obtained, in which, compared to SoyFDH_L, the sequence at the N-terminus was reduced and changed to mimic the N-terminus sequence in FDH from <i>Pseudomonas</i> sp.101 bacterium. Next, a sequence of six histidine residues (His-tag) was added to the N-terminus of the long and short forms of SoyFDH. All four SoyFDH variants were expressed in <i>E. coli</i> BL21(DE3)CodonPlus cells. These enzymes were purified, their kinetic parameters were determined, and thermal stability was studied. In the case of SoyFDH_L, which is similar to the natural form of the enzyme, both variants, with and without His-tag, the expression level is two times higher compared to the truncated variant. The addition of His-tag to the N-terminus of enzymes reduces the level of expression. Changing the sequence of the N-terminus, as well as introducing the His-tag sequence to the N-terminus, does not significantly affect thermal stability of the enzymes at temperatures of 50–56°C. However, due to the higher values of the activation enthalpy Δ<i>H</i><sup>≠</sup> of the thermal inactivation process, the shortened form at normal temperatures is 3 times more stable than the natural one. A comparison of the kinetic parameters of the two SoyFDH variants shows that the catalytic constants are the same, but the long version SoyFDH_L has lower values <span>(K_{{text{M}}}^{{{text{HCOO}} - }})</span>, and the short version SoyFDH_S has lower <span>(K_{{text{M}}}^{{{text{NAD + }}}})</span> values. The introduction of His-tag into the N-terminus of enzymes does not affect their kinetic parameters.</p>","PeriodicalId":709,"journal":{"name":"Moscow University Chemistry Bulletin","volume":"78 4","pages":"220 - 229"},"PeriodicalIF":0.7,"publicationDate":"2023-08-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"4671230","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
N. V. Panin, D. T. Guranda, I. V. Shapovalova, V. K. Švedas
{"title":"Penicillin Acylase: A Retrospective Study of the Kinetics and Thermodynamics of Practically Significant Reactions","authors":"N. V. Panin, D. T. Guranda, I. V. Shapovalova, V. K. Švedas","doi":"10.3103/S0027131423040041","DOIUrl":"10.3103/S0027131423040041","url":null,"abstract":"<p>This review considers the contribution of works carried out at the scientific school of Ilya Vasilievich Berezin to research on the kinetics and thermodynamics of penicillin acylase-catalyzed reactions. Methods for determining the activity of penicillin acylases, the reversibility of the enzymatic hydrolysis of a number of penicillins, cephalosporins, and related compounds, the influence of the β-lactam ring on the thermodynamics of the synthesis of new penicillins and cephalosporins by direct condensation as well as by acyl transfer, the issues of optimizing the conditions for enzymatic acyl transfer, and the use of supersaturated reagent solutions are discussed. The role of chromogenic substrates in the study of penicillin acylase, the possibility of using the methods of titration of active sites of the enzyme and the creation of “smart” biocatalysts based on penicillin acylase due to the formation of conjugates with stimulus-sensitive polymers are considered.</p>","PeriodicalId":709,"journal":{"name":"Moscow University Chemistry Bulletin","volume":"78 4","pages":"187 - 200"},"PeriodicalIF":0.7,"publicationDate":"2023-08-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"4673263","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
{"title":"Formate Dehydrogenase: From NAD(P)H Regeneration to Targeting Pathogen Biofilms, Composing Highly Efficient Hybrid Biocatalysts and Atmospheric CO2 Fixation","authors":"V. I. Tishkov, A. A. Pometun, S. S. Savin","doi":"10.3103/S0027131423040077","DOIUrl":"10.3103/S0027131423040077","url":null,"abstract":"<p>NAD(P)<sup>+</sup>-dependent formate dehydrogenase (EC 1.2.1.2, FDH) catalyzes the simplest reaction from chemical and biological points of view, oxidation of formate-ion to carbon dioxide coupled to NAD(P)<sup>+</sup> reduction to yield NAD(P)H. Advances in the life sciences have shown that this reaction plays an extremely important role in a wide variety of organisms. The areas and types of practical applications of FDH are also permanently expanding. The review analyzes the key steps in the development of our knowledge on the role of formate dehydrogenase in living systems. Achievements in creation of highly efficient catalysts based on FDH for classic biotechnology as well as for new areas are also considered. The importance of a correct selection of the starting FDH form for the purpose of a biocatalyst design with required properties with minimal costs is demonstrated. The prospects for the use of FDH for CO<sub>2</sub> fixation of CO<sub>2</sub> are discussed.</p>","PeriodicalId":709,"journal":{"name":"Moscow University Chemistry Bulletin","volume":"78 4","pages":"151 - 169"},"PeriodicalIF":0.7,"publicationDate":"2023-08-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"4671281","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
{"title":"Solubility of Ketoconazole in Ethylene Glycol + Water Mixtures at Different Temperatures","authors":"Homa Rezaei, Abolghasem Jouyban, Fleming Martinez, Elaheh Rahimpour","doi":"10.3103/S0027131423030094","DOIUrl":"10.3103/S0027131423030094","url":null,"abstract":"<p>Solubility profile of ketoconazole in the aqueous binary mixtures of ethylene glycol is measured by a shake-flask method at 293.2–313.2 K and mathematically represented by some cosolvency models (e.g. van’t Hoff, the λ<i>h</i> equation, the Yalkowsky, the Jouyban–Acree, and the Jouyban–Acree–van’t Hoff models) and the models’ performances are illustrated by mean relative deviations. The density values of ketoconazole saturated solutions are also determined and represented by Jouyban–Acree model.</p>","PeriodicalId":709,"journal":{"name":"Moscow University Chemistry Bulletin","volume":"78 3","pages":"145 - 149"},"PeriodicalIF":0.7,"publicationDate":"2023-06-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"4308913","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
D. A. Pomogailo, O. I. Gromov, V. I. Pergushov, I. D. Sorokin, M. Ya. Melnikov
{"title":"Phototransformations of 1,3-Butadiene Diepoxide Radical Cations in CF3CCl3 at 77 K","authors":"D. A. Pomogailo, O. I. Gromov, V. I. Pergushov, I. D. Sorokin, M. Ya. Melnikov","doi":"10.3103/S0027131423030082","DOIUrl":"10.3103/S0027131423030082","url":null,"abstract":"<p>The nature of radical cations stabilized in irradiated frozen 1,3-butadiene diepoxide/CF<sub>3</sub>CCl<sub>3</sub> solutions was determined <i>via</i> low-temperature UV/Vis spectroscopy, electron paramagnetic resonance spectroscopy, and quantum chemistry. It was found that the cyclic radical cations yielded as radiolysis products undergo C–C bond cleavage in both oxirane cycles under the action of light with further elimination of molecular formaldehyde resulting in distonic <sup>•</sup>CH<sub>2</sub>OC<sup>+</sup>CH<sub>2</sub> radical cations.</p>","PeriodicalId":709,"journal":{"name":"Moscow University Chemistry Bulletin","volume":"78 3","pages":"114 - 117"},"PeriodicalIF":0.7,"publicationDate":"2023-06-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"4305043","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
{"title":"Atomic Force Microscopy of Antibacterial Coatings Produced from Polycation and Its Water-Soluble Complex with Polyanion","authors":"V. A. Pigareva, A. V. Bolshakova, A. V. Sybachin","doi":"10.3103/S0027131423030070","DOIUrl":"10.3103/S0027131423030070","url":null,"abstract":"<div><div><h3>\u0000 <b>Abstract</b>—</h3><p>In this work, the morphology and stability of coatings formed from polydimethyldiallylammonium chloride, as well as its complex with sodium polystyrenesulfonate, on the surface of glass and polycarbonate were studied. It has been established that the modification of a polycation with a polyanion makes it possible to increase the resistance of the formed coatings to wash-off with water, ensuring the creation of effective antibacterial coatings on various surfaces.</p></div></div>","PeriodicalId":709,"journal":{"name":"Moscow University Chemistry Bulletin","volume":"78 3","pages":"132 - 135"},"PeriodicalIF":0.7,"publicationDate":"2023-06-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"4308898","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
N. Yu. Chikurova, A. O. Shemiakina, D. S. Kryzhanovskaya, O. A. Shpigun, A. V. Chernobrovkina
{"title":"Comparison of the Properties of 3-Aminopropyl Silica with Different Nitrogen Content in HILIC Mode","authors":"N. Yu. Chikurova, A. O. Shemiakina, D. S. Kryzhanovskaya, O. A. Shpigun, A. V. Chernobrovkina","doi":"10.3103/S0027131423030057","DOIUrl":"10.3103/S0027131423030057","url":null,"abstract":"<p>Four amino phases representing 3-aminopropyl silica gel batches with different numbers of grafted functional groups are compared. To evaluate the chromatographic properties of the adsorbents, the Tanaka test for hydrophilic stationary phases is used and the retention of polar substances of various classes in the HILIC (hydrophilic) mode is studied. It is shown that even small changes in the nitrogen content between different batches of 3-aminopropyl silica gel have a significant effect on the retention of polar analytes. The hydrophilicity of a substrate is shown to have the greatest effect on its chromatographic behavior, and its evaluation using the Tanaka test is the basis for selecting a batch to separate specific classes of polar substances or for further modification to obtain new phases.</p>","PeriodicalId":709,"journal":{"name":"Moscow University Chemistry Bulletin","volume":"78 3","pages":"118 - 125"},"PeriodicalIF":0.7,"publicationDate":"2023-06-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"4306582","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
A. S. Samadov, A. F. Stepnova, E. F. Faizullozoda, A. N. Kuzmenko, O. N. Plakhotnaya, A. V. Kuzin, K. J. Suyarov, K. Ya. Khuseinov
{"title":"Complex Formation of Silver(I) with 1,2,3-Benzotriazole: Protonization Constants of 1,2,3-Benzotriazole","authors":"A. S. Samadov, A. F. Stepnova, E. F. Faizullozoda, A. N. Kuzmenko, O. N. Plakhotnaya, A. V. Kuzin, K. J. Suyarov, K. Ya. Khuseinov","doi":"10.3103/S0027131423030100","DOIUrl":"10.3103/S0027131423030100","url":null,"abstract":"<p>The acid–base properties of 1,2,3-benzotriazole (Bta) at 25°C and <i>I</i> = 0.1 mol/L KCl are studied in an aqueous solution by the pH-metric method. It is found that in the strongly acidic region of the solution, one of the two nitrogen atoms of the pyridine type of the Bta triazole rings undergoes protonation, and at high pH values, hydrogen abstraction occurs from the NH fragment of the molecule. The obtained values of the protonization constants of 1,2,3-benzotriazole log <i>K</i><sub>1</sub> and log <i>K</i><sub>2</sub> are 8.27 and 0.65, respectively. Using the potential of a silver electrode, the equilibria of silver(I) complex formation with 1,2,3-benzotriazole are studied. The data obtained indicate that Ag<sup>+</sup> replaces the hydrogen ions of the ligand molecule and forms AgBta and <span>({text{AgBta}}_{2}^{ - })</span> complexes with the stability constants log β<sub>1</sub> = 8.50 (AgBta) and log β<sub>2</sub> = 12.65 (<span>({text{AgBta}}_{2}^{ - })</span>).</p>","PeriodicalId":709,"journal":{"name":"Moscow University Chemistry Bulletin","volume":"78 3","pages":"136 - 140"},"PeriodicalIF":0.7,"publicationDate":"2023-06-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"4309168","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
{"title":"Groupoid of Intermolecular Contacts and its Fuzzy Cayley Graph","authors":"A. M. Banaru, D. A. Banaru, S. M. Aksenov","doi":"10.3103/S0027131423030033","DOIUrl":"10.3103/S0027131423030033","url":null,"abstract":"<p>This article defines a group of intermolecular contacts for a monosystemic molecular structure described by one of the crystallographic symmetry groups (space, subperiodic, point) in <i>n</i>-dimensional Euclidean space with unoccupied special positions. The definition of a monoid of contacts for a polysystemic molecular structure is given. Crisp and fuzzy Cayley graphs of groups and monoids of contacts are constructed. Some examples of crystal structures are considered.</p>","PeriodicalId":709,"journal":{"name":"Moscow University Chemistry Bulletin","volume":"78 3","pages":"103 - 113"},"PeriodicalIF":0.7,"publicationDate":"2023-06-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"4309173","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
{"title":"Crucible Atomizer with the Function of Separating Matrix Components for Determination of Atomic Absorption of Elements in Solid Samples","authors":"V. N. Oreshkin, G. I. Tsysin","doi":"10.3103/S0027131423030069","DOIUrl":"10.3103/S0027131423030069","url":null,"abstract":"<p>A design is proposed for a crucible electrothermal atomizer with a vertical arrangement of evaporation, condensation, and atomization zones in graphite cylindrical blocks with transverse heating. The heat treatment is carried out in such a cylindrical column: the evaporation of a solid sample evaporation and the condensation of vapors, and then the evaporation of the condensate into the atomization zone, in which vapors were filtered through the porous medium of the graphite filter into the analytical zone. The metrological characteristics of the determination of elements in solid organomineral samples are improved due to the separation of matrix components and the reduction of interference.</p>","PeriodicalId":709,"journal":{"name":"Moscow University Chemistry Bulletin","volume":"78 3","pages":"126 - 131"},"PeriodicalIF":0.7,"publicationDate":"2023-06-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"4310288","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}