"3-in-1" Hybrid Biocatalysts: Association of Yeast Cells Immobilized in a Sol-Gel Matrix for Determining Sewage Pollution.

This study presents a novel ″3-in-1″ hybrid biocatalyst design that combines the individual efficiency of microorganisms while avoiding negative interactions between them. Yeast cells of Ogataea polymorpha VKM Y-2559, Blastobotrys adeninivorans VKM Y-2677, and Debaryomyces hansenii VKM Y-2482 were immobilized in an organosilicon material by using the sol-gel method, resulting in a hybrid biocatalyst. The catalytic activity of the immobilized microorganism mixture was evaluated by employing it as the bioreceptor element of a biosensor. Optical and scanning electron microscopies were used to examine the morphology of the biohybrid material. Elemental distribution analysis confirmed the encapsulation of yeast cells in a matrix composed of methyltriethoxysilane (MTES) and tetraethoxysilane (TEOS) (85 and 15 vol %, respectively). The resulting heterogeneous biocatalyst exhibited excellent performance in determining the biochemical oxygen demand (BOD) index in real surface water samples, with a sensitivity coefficient of 50 ± 3 × 10-3·min-1, a concentration range of 0.3-31 mg/L, long-term stability for 25 days, and a relative standard deviation of 3.8%. These findings demonstrate the potential of the developed hybrid biocatalyst for effective pollution monitoring and wastewater treatment applications.

Conductive Polymers and Their Nanocomposites: Application Features in Biosensors and Biofuel Cells.

Conductive polymers and their composites are excellent materials for coupling biological materials and electrodes in bioelectrochemical systems. It is assumed that their relevance and introduction to the field of bioelectrochemical devices will only grow due to their tunable conductivity, easy modification, and biocompatibility. This review analyzes the main trends and trends in the development of the methodology for the application of conductive polymers and their use in biosensors and biofuel elements, as well as describes their future prospects. Approaches to the synthesis of such materials and the peculiarities of obtaining their nanocomposites are presented. Special emphasis is placed on the features of the interfaces of such materials with biological objects.

The Antimicrobial and Antibiofilm Potential of New Water-Soluble Tris-Quaternary Ammonium Compounds.

The invention and innovation of highly effective antimicrobials are always crucial tasks for medical and organic chemistry, especially at the current time, when there is a serious threat of shortages of effective antimicrobials following the pandemic. In the study presented in this article, we established a new approach to synthesizing three novel series of bioactive water-soluble tris-quaternary ammonium compounds using an optimized one-pot method, and we assessed their antimicrobial and antibiofilm potential. Five pathogenic microorganisms of the ESKAPE group, including highly resistant clinical isolates, were used as the test samples. Moreover, we highlighted the dependence of antibacterial activity from the hydrophilic-hydrophobic balance of the QACs and noted the significant performance of the desired products on biofilms with MBEC as low as 16 mg/L against bacteria and 8 mg/L against fungi. Particularly notable was the high activity against Pseudomonas aeruginosa and Acinetobacter baumannii, which are among the most resilient bacteria known. The presented work will provide useful insights for future research on the topic.

Multicationic Quaternary Ammonium Compounds: A Framework for Combating Bacterial Resistance.

During previous stages of research, high biocidal activity toward microorganism archival strains has been used as the main indicator in the development of new antiseptic formulations. Although this factor remains one of the most important characteristics of biocide efficiency, the scale of antimicrobial resistance spread causes serious concern. Therefore, focus shifts toward the development of formulations with a stable effect even in the case of prolonged contact with pathogens. Here, we introduce an original isocyanuric acid alkylation method with the use of available alkyl dichlorides, which opened access to a wide panel of multi-QACs with alkyl chains of various lengths between the nitrogen atoms of triazine and pyridine cycles. We used a complex approach for the resulting series of 17 compounds, including their antibiofilm properties, bacterial tolerance development, and antimicrobial activity toward multiresistant pathogenic strains. As a result of these efforts, available compounds have shown higher levels of antibacterial activity against ESKAPE pathogens than widely used commercial QACs. Hit compounds possessed high activity toward clinical bacterial strains and have also demonstrated a long-term biocidal effect without significant development of microorganism tolerance. The overall results indicated a high level of antibacterial activity and the broad application prospects of multi-QACs based on isocyanuric acid against multiresistant bacterial strains.

From Antibacterial to Antibiofilm Targeting: An Emerging Paradigm Shift in the Development of Quaternary Ammonium Compounds (QACs).

In a previous development stage, mostly individual antibacterial activity was a target in the optimization of biologically active compounds and antiseptic agents. Although this targeting is still valuable, a new trend has appeared since the discovery of superhigh resistance of bacterial cells upon their aggregation into groups. Indeed, it is now well established that the great majority of pathogenic germs are found in the environment as surface-associated microbial communities called biofilms. The protective properties of biofilms and microbial resistance, even to high concentrations of biocides, cause many chronic infections in medical settings and lead to serious economic losses in various areas. A paradigm shift from individual bacterial targeting to also affecting more complex cellular frameworks is taking place and involves multiple strategies for combating biofilms with compounds that are effective at different stages of microbiome formation. Quaternary ammonium compounds (QACs) play a key role in many of these treatments and prophylactic techniques on the basis of both the use of individual antibacterial agents and combination technologies. In this review, we summarize the literature data on the effectiveness of using commercially available and newly synthesized QACs, as well as synergistic treatment techniques based on them. As an important focus, techniques for developing and applying antimicrobial coatings that prevent the formation of biofilms on various surfaces over time are discussed. The information analyzed in this review will be useful to researchers and engineers working in many fields, including the development of a new generation of applied materials; understanding biofilm surface growth; and conducting research in medical, pharmaceutical, and materials sciences. Although regular studies of antibacterial activity are still widely conducted, a promising new trend is also to evaluate antibiofilm activity in a comprehensive study in order to meet the current requirements for the development of highly needed practical applications.

Preparation of Hybrid Sol-Gel Materials Based on Living Cells of Microorganisms and Their Application in Nanotechnology.

Microorganism-cell-based biohybrid materials have attracted considerable attention over the last several decades. They are applied in a broad spectrum of areas, such as nanotechnologies, environmental biotechnology, biomedicine, synthetic chemistry, and bioelectronics. Sol-gel technology allows us to obtain a wide range of high-purity materials from nanopowders to thin-film coatings with high efficiency and low cost, which makes it one of the preferred techniques for creating organic-inorganic matrices for biocomponent immobilization. This review focuses on the synthesis and application of hybrid sol-gel materials obtained by encapsulation of microorganism cells in an inorganic matrix based on silicon, aluminum, and transition metals. The type of immobilized cells, precursors used, types of nanomaterials obtained, and their practical applications were analyzed in detail. In addition, techniques for increasing the microorganism effective time of functioning and the possibility of using sol-gel hybrid materials in catalysis are discussed.

Remote Stereoelectronic Effects in Pyrrolidone- and Caprolactam-Substituted Phenols: Discrepancies in Antioxidant Properties Evaluated by Electrochemical Oxidation and H-Atom Transfer Reactivity.

New antioxidants are commonly evaluated via two main approaches, i.e., the ability to donate an electron and the ability to intercept free radicals. We compared these approaches by evaluating the properties of 11 compounds containing both antioxidant moieties (mono- and polyphenols) and auxiliary pharmacophores (pyrrolidone and caprolactam). Several common antioxidants, such as butylated hydroxytoluene (BHT), 2,3,5-trimethylphenol (TMP), quercetin, and dihydroquercetin, were added for comparison. The antioxidant properties of these compounds were determined by their rates of reaction with 2,2-diphenyl-1-picrylhydrazyl (DPPH) radical and their oxidation potentials from cyclic voltammetry. Although these methods test different chemical properties, their results correlate reasonably well. However, several exceptions exist where the two methods give opposite predictions! One of them is the different behavior of mono- and polyphenols: polyphenols can react with DPPH more than an order of magnitude faster than monophenols of a similar oxidation potential. The second exception stems from the size of a "bystander" lactam ring at the benzylic position. Although the phenols with a seven-membered lactam ring are harder to oxidize, the sterically nonhindered compounds react with DPPH about 2× faster than the analogous five-membered lactams. The limitations of computational methods, especially those based on a single parameter, are also evaluated and discussed.

Supramolecular D⋯A-layered structures based on germanium complexes with 2,3-dihydroxynaphthalene and N,N'-bidentate ligands.

The concept of using redox-active ligands, which has become extremely widespread in organometallic chemistry, is often considered from 'their effect on the metal center properties' point of view and 'how to modify the ligands'. In this paper, we present the reverse side of this effective approach - a dramatic change of redox properties of ligands under the influence of a redox-inert metal. Germanium derivatives based on 2,3-dihydroxynaphthalene (1) and N,N'-bidentate ligands, namely 2,2'-bipyridine (2) and 1,10-phenanthroline (3), were obtained and characterized by CV, UV-vis spectroscopy, DFT calculations and in the case of 3 X-ray diffraction. It was shown that the HOMO of the complexes is almost completely located on the naphthalene fragment while the LUMO is on the N,N-ligands. At the same time, there are no boundary molecular orbitals on the germanium atom, but it forms the axial part of the molecule holding two opposite motifs together. Moreover, it sharply affects the level of HOMO and LUMO. Derivatives 2 and 3 are more easily oxidized compared to 2,3-dihydroxynaphthalene by 0.31-0.34 V (7-8 kcal mol-1) and are more easily reduced compared to N,N-donors by 1.08-1.15 V (25-26.5 kcal mol-1). All this together makes it possible to form a system with a narrow HOMO/LUMO gap (∼2 eV). The crystal structure of 3 consists of alternating monomolecular easily oxidizing and easily reducing layers formed due to intermolecular interactions, in particular π-stacking. In addition, in contrast to 1 that starts to decompose noticeably at the temperatures from 200 °C, 2 and 3 have an extremely high thermal stability. They remain stable with no signs of decomposition and melting up to 400 °Ð¡. We believe that this approach to the formation of the supramolecular structure may present prospects for obtaining new functional materials.

2-Carboxyethylgermanium Sesquioxide as A Promising Anode Material for Li-Ion Batteries.

Various forms of germanium and germanium-containing compounds and materials are actively investigated as energy-intensive alternatives to graphite as the anode of lithium-ion batteries. The most accessible form-germanium dioxide-has the structure of a 3D polymer, which accounts for its rapid destruction during cycling, and requires the development of further approaches to the production of nanomaterials and various composites based on it. For the first time, we propose here the strategy of using 2-carboxyethylgermanium sesquioxide ([O1.5 GeCH2 CH2 CO2 H]n , 2-CEGS), in lieu of GeO2 , as a promising, energy-intensive, and stable new source system for building lithium-ion anodes. Due to the presence of the organic substituent, the formed polymer has a 1D or a 2D space organization, which facilitates the reversible penetration of lithium into its structure. 2-CEGS is common and commercially available, completely safe and non-toxic, insoluble in organic solvents (which is important for battery use) but soluble in water (which is convenient for manufacturing diverse materials from it). This paper reports the preparation of micro- (flower-shaped agglomerates of ≈1 µm thick plates) and nanoformed (needle-shaped nanoparticles of ≈500×(50-80) nm) 2-CEGS using methods commonly available in laboratories and industry such as vacuum and freeze-drying of aqueous solutions of 2-CEGS. Lithium half-cell anodes based on 2-CEGS show a capacity of ≈400 mAh g-1 for microforms and up to ≈700 mAh g-1 for nanoforms, which is almost two times higher than the maximal theoretical capacity of graphite. These anodes are stable during the cycling at various rates. The results of DFT simulations suggest that Li atoms form the stable Li2 O with the oxygen atoms of 2-CEGS, and actual charge-discharge cycles involve deoxygenated GeC3 H5 molecules. Thus, C3 chains loosen the anode structure compared to pure Ge, improving its ability to accommodate Li ions.

Upconversion of Reductants.

The many applications of photon upconversion-conversion of low-energy photons into high-energy photons-raises the question of the possibility of "electron upconversion". In this Review, we illustrate how the reduction potential can be increased by using the free energy of exergonic chemical reactions. Electron (reductant) upconversion can produce up to 20-25 kcal mol-1 of additional redox potential, thus creating powerful reductants under mild conditions. We will present the two common types of electron-upconverting systems-dissociative (based on unimolecular fragmentations) and associative (based on the bimolecular formation of three-electron bonds). The possible utility of reductant upconversion encompasses redox chain reactions in electrocatalytic processes, photoredox cascades, design of peroxide-based medicines, firefly luminescence, and reductive repair of DNA photodamage.

Halogen-free GeO2 conversion: electrochemical reduction vs. complexation in (DTBC)2Ge[Py(CN)n] (n = 0 2) complexes.

3,5-di-tert-Butylcatecholate (DTBC) germanium complexes (DTBC)2Ge[Py(CN)n]2 (n = 0…2) have been synthesized from GeO2, 3,5-di-tert-butylcatechol and cyano-substituted pyridines Py(CN)n and characterized by elemental analysis, NMR, IR and UV-VIS spectroscopy. The structure of 1 (with 4-cyanopyridine) has been determined by X-ray single crystal analysis. UV-VIS spectra have shown that these complexes are stable in CH3CN, toluene and CH2Cl2 solutions; in contrast, they are rapidly decomposed by dimethylformamide and tetrahydrofuran. Complexes 1 and 2 (with 4-cyano and 3-cyanopyridine) are electrochemically reducible in toluene/1 M Bu4NPF6 at E = -1.3…-1.7 V vs. AgCl. The quantum-chemical study of these complexes is in accordance with the unsuccessful attempts to obtain analogous derivatives with 2-cyanopyridine and 2,6-dicyanopyridine.