New (trifluorosilyl)propyl derivatives of cyclic dicarboxylic acid imides 1-[3-(trifluorosilyl)propyl]pyrrolidine2,5-dione, 1-[3-(trifluorosilyl)propyl]piperidine-2,6-dione and 2-[3-(trifluorosilyl)propyl]-1H-isoindole-1,3 (2H)-dione were synthesized and structurally characterized by FTIR, NMR spectroscopy, mass spectrometry and elemental analysis. Intramolecular coordination interaction O-*Si and the influence of the hydrocarbon chain length on the strength of the coordination interaction in Si-fluoroethyl and Si-fluoropropyl derivatives of cyclic imides of dicarboxylic acids were characterized by DFT calculations. The geometric, energetic and electronic characteristics of the investigated molecules were also determined. The intramolecular O-*Si coordination bond, closing the six-membered chelate cycle SiCCN(C=O), is observed in the (trifluorosilyl)ethyl derivative phthalimide in the gas, and in the (trifluorosilyl)ethyl derivative succinimide the O-*Si coordination bond is observed both in the gas phase and in DMSO solution. The coordination bond O-*Si, closing the seven-membered chelate cycle SiCCCN(C=O), is found in the (trifluorosilyl)propyl derivative succinimide in the gas phase. Quantum chemical calculations were carried out at the M06/6-311G** and MP2/6-311++G**//M06/6-311G** levels with the 6-311G** basis set.

At present, sulfonamides and their metal complexes have received a new impetus for development. Of particular interest is the study of molecular and crystal structures, which takes into account weak non-valent interactions. Despite the low energy of such interactions, in many cases, they act collectively, and the sum of their actions can play a significant role. As a result, the spectrum of medical and biological activity of new metal complexes is expanded. In this regard, the synthesis and study of the molecular and crystal structure of sulfonamides and their metal complexes is of undoubted relevance. In this work, we studied non-valent intra- and intermolecular interactions in ligands of sulfonamide-substituted imidazo[2,1-b]thiazoles and their previously unknown complexes with CuCl2. The performed analysis of the data obtained by X-ray diffraction analysis made it possible to establish the intramolecular π-stacking interaction in imidazothiazole ligands, which is retained in their complexes with CuCl2. Within the framework of QTAIM topological analysis of electron density and DORI analysis, stereoelectronic and topological structures were studied. In the complexes, tetral, chalcogen, and pnycogen new interligand non-valent interactions were established. The energies of all established types of non-valent interactions have been calculated, and their comparative evaluation has been made. X-ray data of new arylsulfonylamino-substituted derivatives of imidazo[2,1-b]thiazoles and their metal complexes with CuCl2 have been studied. To determine the theoretical prerequisites for the occurrence of π-stacking in the molecules under study, the QTAIM method was used in the framework of the DFT/B3LYP/6–311 + G(d) calculation using the GAUSSIAN 09 program. In addition, the DORI electron density region overlap indicator and the Multiwfn program were used to analyze non-valent interactions.

By the interaction of CuI with bis(2-pyridyl)phosphine oxides (2-Py)2RP(O) containing E-1-phenyl-2-aroylethenyl–C(Ph)=CHC(O)R′ (R′ = Ph, 2-thienyl) substituents, [Cu2I2L2] complexes are synthesized. Their structures are based on the rhomboidal Cu2I2 moiety whose copper atoms are N,N′-chelated by the indicated ligands. At room temperature, the crystalline samples of these complexes exhibit dark red photoluminescence (λmax = 680-685 nm) with a charge transfer from the Cu2I2 moiety to the ligand.

The peculiarities of a spatial structure of new representatives of arylsulfonylamino-substituted derivatives of imidazo[2,1-b][1,3]thiazoles were studied by X-ray diffraction analysis. All presented molecules are "closed" systems due to efficient intramolecular pi-stacking and compact arrangement of fragments. The features of weak intramolecular stacking interactions were revealed based on X-ray structural investigation and QTAIM analysis. A theoretical study of the stereo electronic structure based on the electron density distribution in the XRD experiment was carried out. The energies of pi-stacking interaction were estimated by theoretical methods based on the value of the potential energy density at the bond critical point (3, -1) type. (C) 2021 Elsevier B.V. All rights reserved.

Взаимодействием CuI с бис(2-пиридил)фосфиноксидами (2-Py)2RP(O), содержащими E-1-фенил-2-ароилэтенильные заместители —С(Ph)=CHC(O)R′ (R′ = Ph, 2-тиенил), синтезированы комплексы состава [Cu2I2L2]. В основе структуры последних лежит ромбоидный фрагмент Cu2I2, атомы меди которого хелатированы указанными лигандами по N,N'-типу. При комнатной температуре кристаллические образцы этих комплексов проявляют темно-красную фотолюминесценцию (λмакс = 680—685 нм), имеющую характер переноса заряда с фрагмента Cu2I2 на лиганд.

In this review, the principles of the formation of polyelectrolyte microcapsules by the layer-by-layer assembly method have been considered, the intermolecular interactions that take part in the systems have been described, and the factors that affect the parameters of the resulting structures have been listed. Works devoted to tuning the internal structure of polyelectrolyte shells by means of variations in environmental conditions have been presented, in particular, the effect of temperature on polyelectrolyte shells of various compositions has been considered. Examples of changing the permeability of the shells, as well as imparting desired optical properties to the capsules by incorporating dyes and nanoparticles into polyelectrolyte multilayers have been presented. Possible approaches to remote control of shell permeability under the action of external physical stimuli, such as laser and microwave radiations and a low-frequency magnetic field, have been described. One of the sections of the review has been devoted to the methods of encapsulating emulsion droplets via layer-by-layer deposition of polyelectrolytes.

The aim of this work was to investigate the antibacterial and antiviral properties of a riboflavin derivative (Vitamin B2), flavin mononucleotide and its derivative, synthesized by conjugation with polyethylene glycol (Rf–PEG). Flavin mononucleotide and conjugate of riboflavin with polyethylene glycol were investigated. Staphylococcus aureus, Pseudomonas aeruginosa, Escherichia coli, and Salmonella typhimurium were used as clinical isolates. Due to the growing number of antibiotic-resistant microorganisms, it is necessary to search for new strategies aimed at inactivating pathogens and preventing them from becoming drug-resistant. Antimicrobial photodynamic therapy (aPDT) is a promising approach to inactivate pathogens regardless of their antibiotic resistance status. The work investigated the antibacterial and antiviral properties of the derivative of riboflavin (Vitamin B2), flavin mononucleotide and its derivative synthesized by conjugation with polyethylene glycol (Rf–PEG). It has been shown that hydrophilic riboflavin derivatives are effective photosensitizers and provide inactivation of both gram-positive and -negative microorganisms during aPDT in vitro.

Строение комплекса [Pd(acac){P(NEt2)3}2]BF4 (I) определено методом РСА. В кристаллической структуре I координационная сфера палладия характеризуется значительным искажением плоскоквадратной геометрии центрального атома. На основе данных РСА и ТФП оценена стерическая затрудненность лиганда P(NEt2)3 (конический угол по Толману составляет 170—175°). Установлено, что пара лигандов P(NEt2)3 в координационной сфере палладия представлена двумя изомерами, различающимися геометрией окружения атомов азота (планарной и пирамидальной). Теоретическое исследование в рамках ТФП на уровне BP86/def2-TZVP позволило предположить, что различие геометрии заместителей в лиганде обусловлено стерическими препятствиями. Комплексное соединение I в сочетании с BF3·OEt2 демонстрирует каталитическую активность в реакции аддитивной полимеризации норборнена, характеризуемую значением средней активности до 3.6·105 г(НБ)/(моль(Pd)·ч) при температуре реакции 100 °C.

The structure of complex [Pd(acac){P(NEt2)3}2]BF4 (I) is determined by XRD. In the crystal structure of I, the coordination sphere of palladium is characterized by a significantly distorted planar-square geometry of the central atom. Steric hindrance of the P(NEt2)3 ligand is determined using the XRD and DFT data (the Tolman cone angle is 170-175°). It is established that the pair of P(NEt2)3 ligands in the coordination sphere of palladium is represented by two isomers differing by the geometries (planar and pyramidal) of the nitrogen atom environment. DFT calculations at the BP86/def2-TZVP level of theory suggest that the difference between the substituent geometries in the ligands is due to steric hindrances. In combination with BF3·OEt2, compound I demonstrates catalytic activity in the addition polymerization of norbornene whose average activity reaches 3.6·105 g(NB)/(mol(Pd)·h) at 100 °C.

The novel stable organosilicon compound containing pentacoordinated silicon atom, named as (trifluorosilyl)methyl 2-methylacrylate, was synthesized and fully characterized including single-crystal X-ray diffraction. The asymmetric unit of the title compound contains two independent molecules, one of which adopting the s cis configuration and the other has the s-trans configuration with respect to the C = O and C = C bonds. In the crystal, conformers form cis-and trans-dimeric pairs due to tetrel-bonding interaction and hydrogen bonds C -H middotmiddotmiddot F. Energetic and geometric characteristics for these dimers were calculated by DFT methods at M06-2X/6-311G(d,p) level of theory using QTAIM analysis. The calculations in the polar medium (DMSO) for two dimeric fragments of crystal packing were performed with Onsager self consistent reaction field method. (c) 2021 Elsevier B.V. All rights reserved.

Реакцией Pd(acac)2 с BF3·OEt2 в присутствии TFP в толуоле получен комплекс [Pd(acac)(TFP)2]BF4 (I) (где TFP — три-2-фурилфосфин), строение которого определено методом РСА. В кристаллической структуре I наблюдаются короткие контакты типа H⋯F. Энергии данных контактов изучены с помощью квантово-химических методов в рамках DFT. Комплексное соединение I в сочетании с BF3·OEt2 в подобранных концентрациях и растворителе демонстрирует каталитическую активность в реакции аллильного алкилкилирования морфолина, характеризуемую числом оборотов катализатора от 198 моль до 268 моль 4-аллилморфолина на моль палладия и интегральной селективностью по основному продукту в диапазоне 88—99 %.

The photochromic compounds are of great interest due to their unique ability to undergo reversible intramolecular transformations under the influence of light, accompanied by changes in the absorption spectrum. The aim of the present work is the development of the polymer system for encapsulation of the photochromic compounds with maintaining the photochromic properties. The core-shell capsules were produced by a versatile one-step ultrasound treatment. The capsules possess positive or negative photochromic effects depending on the nature of the photochromic systems to be encapsulated. The capsules are demonstrated a noticeable photochromic reaction, which could find a broad application in various fields including information and biomedical technologies.

Reaction of Pd(acac)2 with BF3·OEt2 in the presence of tri(2-furyl)phosphine in toluene yields complex [Pd(acac)(TFP)2]BF4 (I) (TFP is tri(2-furyl)phosphine) whose structure is determined by XRD. The crystal structure of I contains short H⋯F contacts. The energies of these contacts are studied using DFT quantum chemical methods. Coordination complex I in combination with BF3·OEt2 in appropriate concentrations and solvents demonstrates catalytic activity in the reaction of morpholine allylic alkylation characterized by the catalyst turnover number from 198 mol to 268 mol of 4-allylmorpholine per mole of palladium and an integral selectivity to the main product of 88-99%.

DNA-containing biodegradable microcapsules based on vaterite CaCO3 polycrystalline particles and polyelectrolyte complex polyarginine–dextran sulfate are obtained and characterized. The enzymatic degradation of the microcapsules induced by pronase is studied using scanning electron microscopy, laser confocal microscopy, and spectrophotometry. It is shown that microcapsules the shell of which is formed by polypeptide–polysaccharide polyelectrolyte complexes are sensitive to pronase-induced enzymatic hydrolysis leading to the release of encapsulated DNA.

Dynamic light scattering was utilized to characterize bactericidal colloidal nanoparticles, food pathogen bacterial isolates in planktonic form. The method was proposed to study cultures of food pathogenic bacteria Staphylococcus aureus, Pseudomonas aeruginosa, Listeria monocytogenes, Escherichia coli, Salmonella and their interaction with nanoparticles. The zeta potentials of silver nanoparticles and bacteria were obtained using electrophoretic light scattering. Nanoparticles and bacteria were characterized by transmittance electron microscopy and the mechanism of antibacterial action was suggested.

The migration and accumulation of manganese ions during the growing season of Solanum tuberosum L. potatoes have been studied. The complex form and content of the metal in potatoes cultivated under factor-static conditions are determined using elemental analysis and electron paramagnetic resonance (EPR) technique. The toxic effect of the metal manifests itself in biometric indicators with an increase of manganese salt content in the nutrient medium, which is accompanied by growth of the EPR signal and the accumulation of metal in plant organs. In addition, the EPR spectra show a narrow signal characteristic of stable semiquinone radicals.

The Pd(II)complexes [Pd(acac)(PR3)(PhCN)][BF4] and [Pd(acac)(S)2][BF4] (acac = acetylacetonate; R = phenyl, 2-methoxyphenyl; S = benzonitrile, pyridine, CD3CN) were synthesized by the reaction of Pd(acac)2 or Pd(acac)2·PR3 with 2 equiv. of BF3·OEt2 in the presence of appropriate ligands (S). The structural features of the complexes were analyzed by NMR and FTIR spectroscopies. Computed FTIR spectra was in agreement with the corresponding experimental data, the correlation between ν(CN) of the κ1-nitrile ligands and DFT-calculated geometrical features of the complexes was proposed. Complex Pd (κ2-O,O′-acac)(κ1-C-acac)(TOMPP) (TOMPP = tris(ortho-methoxyphenyl)phosphine) was characterized by X-ray diffractometry. XRD, 1H and 31P NMR analyses were consistent with formation of three unequally populated rotamers of Pd(κ2-O,O′-acac)(κ1-C-acac)(TOMPP) in CDCl3 which differ in the orientation of the endo-(2-methoxy)phenyl ring in exo2 conformation of coordinated TOMPP. Reaction of [Pd(acac)(PR3)(PhCN)]BF4 with L (L = pyridine, morpholine, TOMPP) in the majority of cases gave mixtures of [Pd(acac)(PR3)(L)]BF4, [Pd(acac)(L)2]BF4, and [Pd(acac)(PR3)2]BF4 as result of sequence of ligand substitution reactions. The cationic palladium catalyst precursors were found to be active catalysts for phenylacetylene polymerization and oligomerization. Only cationic pre-catalysts with bulky TOMPP ligand gave high-molecular weight polyphenylacetylene. Catalysts with less bulky substituents mostly formed phenylacetylene oligomers. When activated with BF3⋅OEt2, these palladium complexes can also be used as catalysts for the vinyl addition polymerization of norbornene with activities 104–107 gpolymer molPd h−1.

The Pd(II) complexes [Pd(acac)(L)(n)]BF4 were synthesized by the reaction of [Pd(acac)(MeCN)(2)]BF4 with L (n = 2: L = PCyPh2, PCy2Ph, P(NMe2)(3), P(NEt2)(3), tri-2-furylphosphine, tri-2-thienylphosphine; n = 1: L = 2 dicyclohexylphosphino-2',6'-dimethoxybiphenyl, 2-dicyclohexylphosphino-2',4',6'-triisopropylbiphenyl). The structural features of the complexes were analyzed by NMR and FTIR spectroscopies. Complexes [Pd(acac)(PCyPh2)(2)]BF4 and [Pd(acac)(PCy2Ph)(2)]BF4 were characterized by X-ray diffractometry. The cationic palladium catalyst precursors were found to be active catalysts for telomerization of 1,3- butadiene with methanol under base-free conditions. Complexes [(acac)Pd(PCy2Ph)(2)]BF4 and [(acac) Pd(TOMPP)(2)]BF4 in terms of yield, selectivity, and stability are effective for the catalytic telomerization (TOMPP = tris(2-methoxyphenyl)phosphine). Using 0.001-0.0025 mol% palladium loading methoxy-2,7-octadienes were obtained with chemoselectivities of 76-94% and TON up to 60000 mol 1,3-butadiene per mol Pd. (C) 2020 Elsevier B.V. All rights reserved.

Polyelectrolyte microcapsules have been prepared by sequential adsorption of oppositely charged sodium polystyrene sulfonate and polyallylamine hydrochloride molecules on the surface of calcium carbonate particles. The capsule shells are functionalized with Fe3O4 magnetic nanoparticles to provide control over the localization of microcapsules and the permeability of their shells. The control of microcapsule permeability using a low-frequency non-heating magnetic field is based on the magneto-mechanical actuation, which, due to its high penetration ability, locality and safety, is preferable for application in vivo to magnetic hyperthermia. Here we report on the results of analysis of the effect of a low-frequency pulsed sinusoidal magnetic field with a frequency of 50 Hz on the permeability of the microcapsule shell for fluorescently labeled dextran molecules. It was found that the permeability of the shell increases with a decrease in the duration of the pause between magnetic field pulses, causing an increase in the amount of dextran in the shell.