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A new pyridine-fused seleno-diazo-lium salt, 3-(phenyl-selan-yl)[1,2,4]selena-diazolo[4,5- a ]pyridin-4-ylium chloride di-chloro-methane 0.352-solvate, C 12 H 9 N 2 Se 2 + ·Cl - ·0.352CH 2 Cl 2 , was obtained from the reaction between 2-pyridyl-selenenyl chloride and phenyl-seleno-cyanate. Single-crystal structural analysis revealed the presence of C-H⋯N, C-H⋯Cl - , C-H⋯Se hydrogen bonds as well as chalcogen-chalcogen (Se⋯Se) and chalcogen-halogen (Se⋯Cl - ) inter-actions. Non-covalent inter-actions were explored by DFT calculations followed by topological analysis of the electron density distribution (QTAIM analysis). The structure consists of pairs of seleno-diazo-lium moieties arranged in a head-to-tail fashion surrounding disordered di-chloro-methane mol-ecules. The assemblies are connected by C-H⋯Cl - and C-H⋯N hydrogen bonds, forming layers, which stack along the c -axis direction connected by bifurcated Se⋯Cl - ⋯H-C inter-actions., (© Temesgen et al. 2024.)

This work focuses on the first use of ultrasonic phenol-ene coupling as a polymer analogous transformation. The ultrasonic reaction was introduced into chitin chemistry, resulting in the fast and convenient preparation of new water-soluble cationic chitin derivatives. Since water-soluble derivatives of fully deacetylated chitin are poorly described in the literature, the synthesis of each new type of these derivatives is a significant event in polysaccharide chemistry. Polycations, or cationic polymers, are of particular interest as antibacterial agents. Consequently, the resulting polymers were tested for their antibacterial activity and toxicity. We found that the highly substituted polymer of medium molecular weight exhibited the most pronounced in vitro antibacterial effect. We prepared nanoparticles using the ionic gelation technique. The most effective in vitro antibacterial chitin-based systems were tested in vivo in rats. These tests demonstrated outstanding antibacterial effects combined with an absence of toxicity. Additionally, we found that the resulting polymers, unlike their nanoparticle counterparts, also exhibited strong antioxidant effects. In summary, we demonstrated the effectiveness of ultrasound in polymer chemistry and highlighted the importance of the sonochemical approach in the chemical modification of polysaccharides. This approach enables the synthesis of derivatives with improved physicochemical and biological properties.

Positively charged ligands are scarce. Here, we report the synthesis of unprecedented cationic selenium-containing triazapentadiene ligand framework. The reaction between 2-pyridylselenyl reagents and NaN(CN) 2 in a 2:1 ratio produces the sodium complexes featuring the cationic selenium-containing triazapentadiene (SeTAP) ligand. The sodium-to-metal transmetalation allows facile preparation of SeTAP metal complexes, as exemplified by the reactions with CuCl 2 , AgNO 3 , NaAuCl 4 , and FeCl 3 . Density functional theory calculations have been used to analyze and characterize the chalcogen bonding interactions observed in the solid state for these compounds. Moreover, antifungal properties of the SeTAP ligand and its metal complexes were screened for in vitro activity against several phytopathogenic fungi. Phoma eupyrena exhibited prominent sensitivity against the action of most of the tested compounds.

The synthesis and structural characterization of α-haloalkyl-substituted pyridinium-fused 1,2,4-selenadiazoles with various counterions is reported herein, demonstrating a strategy for directed supramolecular dimerization in the solid state. The compounds were obtained through a recently discovered 1,3-dipolar cycloaddition reaction between nitriles and bifunctional 2-pyridylselenyl reagents, and their structures were confirmed by the X-ray crystallography. α-Haloalkyl-substituted pyridinium-fused 1,2,4-selenadiazoles exclusively formed supramolecular dimers via four-center Se···N chalcogen bonding, supported by additional halogen bonding involving α-haloalkyl substituents. The introduction of halogens at the α-position of the substituent R in the selenadiazole core proved effective in promoting supramolecular dimerization, which was unaffected by variation of counterions. Additionally, the impact of cocrystallization with a classical halogen bond donor C 6 F 3 I 3 on the supramolecular assembly was investigated. Non-covalent interactions were studied using density functional theory calculations and topological analysis of the electron density distribution, which indicated that all ChB, XB and HB interactions are purely non-covalent and attractive in nature. This study underscores the potential of halogen and chalcogen bonding in directing the self-assembly of functional supramolecular materials employing 1,2,4-selenadiazoles derived from recently discovered cycloaddition between nitriles and bifunctional 2-pyridylselenyl reagents.

In this study, Rhodamine B-containing chitosan-based films were prepared and characterized using their mechanical, photophysical, and antibacterial properties. The films were synthesized using the casting method and their mechanical properties, such as tensile strength and elongation at break, were found to be dependent on the chemical composition and drying process. Infrared spectroscopy and X-ray diffraction analysis were used to examine the chemical structure and degree of structural perfection of the films. The photophysical properties of the films, including absorption spectra, fluorescence detection, emission quantum yields, and lifetimes of excited states, were studied in detail. Rhodamine B-containing films exhibited higher temperature sensitivity and showed potential as fluorescent temperature sensors in the physiological range. The antibacterial activity of the films was tested against Gram-positive bacteria S. aureus and Gram-negative bacteria E. coli , with Rhodamine B-containing films demonstrating more pronounced antibacterial activity compared to blank films. The findings suggest that the elaborated chitosan-based films, particularly those containing Rhodamine B can be of interest for further research regarding their application in various fields such as clinical practice, the food industry, and agriculture due to their mechanical, photophysical, and antibacterial properties.

The reaction between 2-pyridyl-selenenyl chloride and isobutyro-nitrile results in the formation of the corresponding cationic pyridinium-fused 1,2,4-seleno-diazole, namely, 3-(propan-2-yl)-1,2,4-[1,2,4]selena-diazolo[4,5-a]pyridin-4-ylium chloride, C 9 H 11 N 2 Se + ·Cl - , in high yield (89%). The structure of the compound, established by means of single-crystal X-ray analysis at 100 K, has monoclinic ( P 2 1 / c ) symmetry and revealed the presence of bifurcated chalcogen-hydrogen bonding Se⋯Cl - ⋯H-Cl, and these non-covalent contacts were analysed by DFT calculations followed by a topological analysis of the electron-density distribution (ωB97XD/6-311++G** level of theory)., (© Temesgen et al. 2024.)

Background: This study explores the regional variations in toxic metal accumulation among RUDN University students from various global regions., Methods: This comparative analysis examined hair samples from students hailing from different regions, including Russia, Asia, the Middle East, Africa, and Latin America. The concentrations of Aluminium (Al), Arsenic (As), Cadmium (Cd), Mercury (Hg), Lead (Pb), and Tin (Sn) were measured in the hair samples. The data was then evaluated using regression models to assess the link between the region of residence and toxic metal content in the hair., Results: The analysis indicated significant regional variations in the levels of toxic metals in the students' hair. The highest content of Al, Cd, and Pb was observed in students from Africa (13.542, 0.028, 0.794 µg/g) and Latin America (9.947, 0.025, 0.435 µg/g). Arsenic levels in students from all regions exceeded that of Russian students by over two-fold. No substantial group differences were found in the Sn content. The regression models suggested that residing in Asia, Africa, and Latin America was a predictor of high Hg levels in hair (0.130, 0.096, 0.227 µg/g). Living in Africa was significantly associated with higher Pb levels (0.794 µg/g), and living in Latin America was close to significantly associated with the Cd level in the hair (0.025 µg/g)., Conclusion: This study confirmed an increased accumulation of toxic metals, especially Hg, Cd, and Pb, in students primarily from Latin America and Africa. The findings highlighted the importance of understanding the regional variations in toxic metal accumulation to address associated health risks and the potential impact on students' well-being and academic performance. These insights may guide the development of targeted interventions to reduce exposure to toxic metals in students from various regions around the world., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 Elsevier GmbH. All rights reserved.)

When azo coupling of aryldiazonium salts with indoles was carried out in aprotic nonpolar solvent on air, a pseudo-three-component reaction has been discovered. Azo coupling is followed by a nucleophilic addition of a second indole unit to the indolium intermediate; aromatization and oxidation are achieved under air.

This comprehensive review illuminates the various methods of chitosan extraction, its antibacterial properties, and its multifarious applications in diverse sectors. We delve into chemical, physical, biological, hybrid, and green extraction techniques, each of which presents unique advantages and disadvantages. The choice of method is dictated by multiple variables, including the desired properties of chitosan, resource availability, cost, and environmental footprint. We explore the intricate relationship between chitosan's antibacterial activity and its properties, such as cationic density, molecular weight, water solubility, and pH. Furthermore, we spotlight the burgeoning applications of chitosan-based materials like films, nanoparticles, nonwoven materials, and hydrogels across the food, biomedical, and agricultural sectors. The review concludes by highlighting the promising future of chitosan, underpinned by technological advancements and growing sustainability consciousness. However, the critical challenges of optimizing chitosan's production for sustainability and efficiency remain to be tackled.

In this work, we focused on synthesizing and assessing novel chitosan-based antibacterial polymers and their nanoparticles by incorporating benzothiazole substituents. The growing resistance to antibiotics has necessitated the search for alternative antimicrobial compounds. This study aimed to synthesize and evaluate chitosan-based polymers and nanoparticles with benzothiazole substituents for their antibacterial properties and toxicity. The benzothiazole derivatives of chitosan and their nanoparticles were synthesized through electrochemical coupling. The in vivo antibacterial efficacy was tested on white rats with induced peritonitis using a microbial suspension containing S. aureus and E. coli . Additionally, in vitro and in vivo toxicity assessments were conducted. The chitosan-based antibacterial systems showed significant in vivo antibacterial activity, surpassing that of unmodified chitosan and commercial antibiotics. Moreover, the toxicity studies revealed low toxicity levels of the synthesized derivatives, which did not differ significantly from native chitosan. The synthesized chitosan-based polymers and nanoparticles demonstrated potent antibacterial activity and low toxicity, highlighting their potential as effective alternatives to traditional antibiotics. Further investigations in pharmacology and preclinical trials are recommended to explore their application in clinical settings.

In this study, we elaborated new chitosan-based films reinforced by iron(III)-containing chitosan nanoparticles Fe(III)-CS-NPs at different concentrations. We found that the optimum concentration of Fe(III)-CS-NPs for the improvement of antibacterial and mechanical properties of the films was 10% (σ b = ca. 8.8 N/mm 2 , ε b = ca. 41%, inhibition zone for S. aureus = ca. 16.8 mm and for E. coli = ca. 11.2 mm). Also, using the click-chemistry approach (thiol-ene reaction), we have synthesized a novel water-soluble cationic derivative of chitin. The addition of this derivative of chitin to the chitosan polymer matrix of the elaborated film significantly improved its mechanical (σ b = ca. 11.6 N/mm 2 , ε b = ca. 75%) and antimicrobial (inhibition zone for S. aureus = ca. 19.6 mm and for E. coli = ca. 14.2 mm) properties. The key mechanism of the antibacterial action of the obtained films is the disruption of the membranes of bacterial cells. The elaborated antibacterial films are of interest for potential biomedical and food applications.

Antibacterial chitosan films, versatile and eco-friendly materials, have garnered significant attention in both the food industry and medicine due to their unique properties, including biodegradability, biocompatibility, and antimicrobial activity. This review delves into the various types of chitosan films and their distinct applications. The categories of films discussed span from pure chitosan films to those enhanced with additives such as metal nanoparticles, metal oxide nanoparticles, graphene, fullerene and its derivatives, and plant extracts. Each type of film is examined in terms of its synthesis methods and unique properties, establishing a clear understanding of its potential utility. In the food industry, these films have shown promise in extending shelf life and maintaining food quality. In the medical field, they have been utilized for wound dressings, drug delivery systems, and as antibacterial coatings for medical devices. The review further suggests that the incorporation of different additives can significantly enhance the antibacterial properties of chitosan films. While the potential of antibacterial chitosan films is vast, the review underscores the need for future research focused on optimizing synthesis methods, understanding structure-property relationships, and rigorous evaluation of safety, biocompatibility, and long-term stability in real-world applications.

The mol-ecular and crystal structures of the title compound, [Cu 2 I 2 (C 18 H 12 N 2 ) 2 ], were examined by single-crystal X-ray diffraction and Hirshfeld surface analysis. The Cu atom is coordinated in a distorted tetra-hedral geometry by two N atoms from the 2,2'-bi-quinoline ligands and the two μ 2 -bridging iodide ligands. The mol-ecules are in contact via π-π-stacking inter-actions. Hirshfeld surface analysis showed that the most important contributions to the inter-molecular inter-actions are H⋯H (39.7%), H⋯I/I⋯H (17.8%), C⋯H/H⋯C (17.5%), C⋯C (16.5%), N⋯C/C⋯N (3.9%) and N⋯H/H⋯N (3.5%)., (© Temesgen et al. 2023.)

Microorganisms, fermentation processes, and the resultant metabolic products are a key driving force in biotechnology and, in particular, in food biotechnology. The quantity and/or quality of final manufactured food products are directly related to the efficiency of the metabolic processes of producer microorganisms. Food BioTech companies are naturally interested in increasing the productivity of their biotechnological production lines. This could be achieved via either indirect or direct influence on the fundamental mechanisms governing biological processes occurring in microbial cells. This review considers an approach to improve the efficiency of producer microorganisms through the use of several types of substances or complexes affecting the metabolic processes of microbial producers that are of interest for food biotechnology, particularly fermented milk products. A classification of these supplements will be given, depending on their chemical nature (poly- and oligosaccharides; poly- and oligopeptides, individual amino acids; miscellaneous substances, including vitamins and other organic compounds, minerals, and multicomponent supplements), and the approved results of their application will be comprehensively surveyed.

Ciprofloxacin is one of the most effective antibiotics, but it is characterized by a range of side effects. Elaboration of drug-releasing systems which allow to diminish toxicity of ciprofloxacin is a challenging task in medicinal chemistry. The current study is focused on development of new ciprofloxacin releasing systems (CRS). We found that ultrasound efficiently promotes N,N' -dicyclohexyl carbodiimide-mediated coupling between COOH and NH 2 functionalities in water. This was used for conjugation of ciprofloxacin to chitosan. The obtained ciprofloxacin/chitosan conjugates are capable of forming their self-assembled nanoparticles (SANPs) in aqueous medium. The SANPs can be additionally loaded by ciprofloxacin to form new CRS. The CRS demonstrated high loading and encapsulation efficiency and they are characterized by extended release profile (20 h). The elaborated CRS were tested in vivo in rats. The in vivo antibacterial effect of the CRS exceeded that of the starting ciprofloxacin. Moreover, the in vivo acute and subacute toxicity of the nanoparticles was almost identical to that of the chitosan, which is considered as the non-toxic biopolymer., Competing Interests: The authors declare no conflict of interest.

The series of benzylic-substituted 1,2,4-selenodiazolium salts were prepared via cyclization reaction between 2-pyridylselenyl chlorides and nitriles and fully characterized. Substitution of the Cl anion by weakly binding anions promoted the formation supramolecular dimers featuring four center Se 2 N 2 chalcogen bonding and two antiparallel selenium⋯π interactions. Chalcogen bonding interactions were studied using density functional theory calculations, molecular electrostatic potential (MEP) surfaces, the quantum theory of atoms-in-molecules (QTAIM), and the noncovalent interaction (NCI) plot. The investigations revealed fundamental role of the selenium⋯π contacts that are stronger than the Se⋯N interactions in supramolecular dimers. Importantly, described herein, the benzylic substitution approach can be utilized for reliable supramolecular dimerization of selenodiazolium cations in the solid state, which can be employed in supramolecular engineering.

A practical method for the synthesis of 2-selenoxo-1,2,3,4-tetrahydro-4-quinazolinone was reported. The latter compounds were found to undergo facile oxidation with H 2 O 2 into corresponding diselenides. Novel organoselenium derivatives were characterized by the 1 H, 77 Se, and 13 C NMR spectroscopies, high-resolution electrospray ionization mass spectrometry, IR, elemental analyses (C, H, N), and X-ray diffraction analysis for several of them. Novel heterocycles exhibited multiple remarkable chalcogen bonding (ChB) interactions in the solid state, which were studied theoretically.

Nitro functionalized dibromodiazadiene dyes were prepared and fully characterized including X-ray single crystal analysis. Electron deficient dibromodiazadienes were found to be able to act as donors of halogen bonding (XB), while the nitro group acted as an acceptor of the XB. Depending on the substituents, the Br···O XB competed with other weak interactions, and for some of the dyes, they even outcompeted the XB involving the nitro group. However, the nitro functionalized dibromoalkenes 6a and 10a , which had only the nitro moiety as the most plausible acceptor of the XB, reliably formed 1D chains via Br⋯O XB. Experimental work was supported by the DFT calculations and topological analysis of the electron density distribution within the framework of Bader's theory (QTAIM method).

The synthesis and structural characterization of a series of supramolecular complexes of bicyclic cationic pyridine-fused 1,2,4-selenodiazoles with various anions is reported. The binding of trifluoroacetate, tetrachloroaurate, tetraphenylborate, perrhenate, and pertechnetate anions in the solid state is regarded. All the anions interact with selenodiazolium cations exclusively via a pair of "chelating" Se⋯O and H⋯O non-covalent interactions, which make them an attractive, novel, non-classical supramolecular recognition unit or a synthon. Trifluoroacetate salts were conveniently generated via novel oxidation reaction of 2,2'-dipyridyl diselenide with bis(trifluoroacetoxy)iodo)benzene in the presence of corresponding nitriles. Isolation and structural characterization of transient 2-pyridylselenyl trifluoroacetate was achieved. X-ray analysis has demonstrated that the latter forms dimers in the solid state featuring very short and strong Se⋯O and Se⋯N ChB contacts. 1,2,4-Selenodiazolium trifluoroacetates or halides show good solubility in water. In contrast, (AuCl 4 ) - , (ReO 4 ) - , or (TcO 4 ) - derivatives immediately precipitate from aqueous solutions. Structural features of these supramolecular complexes in the solid state are discussed. The nature and energies of the non-covalent interactions in novel assembles were studied by the theoretical methods. To the best of our knowledge, this is the first study that regards perrhenate and pertechnetate as acceptors in ChB interactions. The results presented here will be useful for further developments in anion recognition and precipitation involving cationic 1,2,4-selenodiazoles.

Ultrasonic approach to the synthesis of the first selenium-containing derivatives of chitin and chitosan has been developed. The synthetic procedure is simple, provides high yields, does not require harsh conditions, and uses water as the reaction medium. The elaborated chitin and chitosan derivatives and their based nanoparticles are non-toxic and possess high antibacterial and antifungal activity. Their antimicrobial activity exceeds the effect of the classic antibiotics (Ampicillin and Gentamicin) and the antifungal drug Amphotericin B. The obtained selenium-containing cationic chitin and chitosan derivatives exhibit a high transfection activity and are promising gene delivery vectors. Nanoparticles of the synthesized polymers are highly efficient catalysts for the oxidation of 1-phenylethyl alcohol to acetophenone by bromine at room temperature., (Copyright © 2022 Elsevier B.V. All rights reserved.)

Understanding the effect of heteroatom doping is crucial for the design of carbon nanodots (CNDs) with enhanced luminescent properties for fluorescence imaging and light-emitting devices. Here, we study the effect and mechanisms of luminescence enhancement through nitrogen doping in nanodots synthesized by the bottom-up route in an intense femtosecond laser field using the comparative analysis of CNDs obtained from benzene and pyridine. We demonstrate that laser irradiation of aromatic compounds produces hybrid nanoparticles consisting of a nanocrystalline core with a shell of surface-bonded aromatic rings. These nanoparticles exhibit excitation-dependent visible photoluminescence typical for CNDs. Incorporation of nitrogen into pyridine-derived CNDs enhances their luminescence characteristics through the formation of small pyridine-based fluorophores peripherally bonded to the nanoparticles. We identify oxidation of surface pyridine rings as a mechanism of formation of several distinct blue- and green-emitting fluorophores in nanodots, containing pyridine moieties. These findings shed additional light on the nature and formation mechanism of effective fluorophores in nitrogen-doped carbon nanodots produced by the bottom-up route., Competing Interests: The authors declare no competing financial interest., (© 2022 The Authors. Published by American Chemical Society.)

Chalcogenodiazoles have been intensively studied in recent years in the context of their supramolecular chemistry. In contrast, the newly discovered cationic 1,2,4-selenodiazole supramolecular building blocks, which can be obtained via coupling between 2-pyridylselenyl halides and nitriles, are virtually unexplored. A significant advantage of the latter is their facile structural tunability via the variation of nitriles, which could allow a fine tuning of their self-assembly in the solid state. Here, we explore the influence of the substituent (which derives from the nitrile) and counterions on the supramolecular assembly of cationic 1,2,4-selenodiazoles via chalcogen bonding.

Copper(II) complexes with 1,1,1-trifluoro-4-(4-methoxyphenyl)butan-2,4-dione (H L1 ) were synthesized and characterized by elemental analysis, FT-IR spectroscopy, and single crystal X-ray diffraction. The biological properties of H L1 and cis -[Cu( L1 ) 2 (DMSO)] ( 3 ) were examined against Gram-positive and Gram-negative bacteria and opportunistic unicellular fungi. The cytotoxicity was estimated towards the HeLa and Vero cell lines. Complex 3 demonstrated antibacterial activity towards S. aureus comparable to that of streptomycin, lower antifungal activity than the ligand H L1 and moderate cytotoxicity. The bioactivity was compared with the activity of compounds of similar structures. The effect of changing the position of the methoxy group at the aromatic ring in the ligand moiety of the complexes on their antimicrobial and cytotoxic activity was explored. We propose that complex 3 has lower bioavailability and reduced bioactivity than expected due to strong intermolecular contacts. In addition, molecular docking studies provided theoretical information on the interactions of tested compounds with ribonucleotide reductase subunit R2, as well as the chaperones Hsp70 and Hsp90, which are important biomolecular targets for antitumor and antimicrobial drug search and design. The obtained results revealed that the complexes displayed enhanced affinity over organic ligands. Taken together, the copper(II) complexes with the trifluoromethyl methoxyphenyl-substituted β-diketones could be considered as promising anticancer agents with antibacterial properties.

2-Pyridylselenyl halides undergo facile coupling with a triple CN bond of unactivated nitriles. Unprecedented heterocyclization allowed the preparation of a novel class of cationic 1,2,4-selenadiazoles in remarkably high yields. Cationic 1,2,4-selenadiazoles form supramolecular dimers in the crystal via SeN chalcogen bonding, which was studied theoretically.

The synthesis of new chitin derivatives through ultrasound-assisted treatment of the chitin with 1-azido-3-chloropropan-2-ol under Green Chemistry conditions is described. This is the first example of ultrasound-assisted polymer analogues transformation of chitin unaccompanied by noticeable backbone degradation or deacetylation. The obtained water-soluble azido chitin derivatives are characterized by high antibacterial activity, which is comparable with that of commercial antibiotics ampicillin and gentamicin. At the same time, they were demonstrated almost identical in vitro toxicity as unmodified chitin and chitosan. The antibacterial activity of the obtained polymers is mainly provided by azido moiety in their macromolecules. The conjugation of azido moiety to chitin backbone strongly diminishes the toxicity of the azido pharmacophore, but preserves its antibacterial properties. The most potent chitin derivative was used for the film coating of Ricotta cheese samples. This food coating proved to be efficient for the prolongation of shelf life of Ricotta cheese., (Copyright © 2020 Elsevier Ltd. All rights reserved.)

Arylazoimidazoles are important dyes which were intensively studied in the past. In contrast, triarylazoimidazoles (derivatives which carry aryl substituents at the imidazole core) received almost no attention in the scientific literature. Here, we report a new family of simple and easily accessible triarylazoimidazole-group 12 metal complexes, which feature highly efficient photo-luminescence emission (Φ up to  0.44). Novel compounds exhibit bright red emission in solution, which could be excited with a visible light.

The title compound, C 23 H 19 BrN 4 O 2 , is a product of an azo coupling reaction between 3,4-bis-(4-meth-oxy-phen-yl)imidazole and 4-bromo-phenyl-diazo-nium tetra-fluoro-borate. Its crystal structure was determined using data collected at 120 K. The mol-ecule adopts a trans configuration with respect to the N=N double bond. The imidazole and aryl rings attached to the azo linkage are coplanar within 12.73 (14)°, which indicates significant electron delocalization within the mol-ecule. In the crystal, the mol-ecules form centrosymmetric dimers via pairs of N-H⋯O hydrogen bonds., (© Temesgen et al. 2021.)

For the first time the possibility of chitin use as an accessible and easily-modifiable support for an efficient Pd(II) catalyst has been demonstrated. The modification of chitin avoiding a noticeable chain scission or deacetylation, is achieved by sonochemical alkylation with 1-azido-3-chloropropan-2-ol followed by a convenient azido-alkyne click reaction. The obtained polymer represents an extremely rare case of the chitin derivative soluble both in water and organic solvents. The treatment of that derivative with imino-isonitrile Pd(II) complex solution yielded a chitin-supported Pd(II) complex. The latter could be obtained as a powder or as uniform nanoparticles in different size ranges. The nanoparticles with a hydrodynamic diameter of 30 nm were shown to be the most efficient form of catalyst for the copper- and phosphine-free Sonogashira cross-coupling in water., (Copyright © 2020 Elsevier Ltd. All rights reserved.)

The title compound, C 21 H 23 NO 4 S, obtained by alkaline treatment of 1,5-bis-(1-phen-oxy)-3-aza-pentane at moderate heating, is a N -tosyl-ated secondary vinyl-amine. An intra-molecular S=O⋯H-C hydrogen bond generates a 13-membered ring. The benzalacetone moiety adopts a trans conformation with respect to the C=C double bond, which is slightly longer than usual due to the conjugation with a neighbouring acetyl group. Theoretical predictions of potential biological activities were performed, suggesting that the title compound can inhibit gluconate 2-de-hydrogenase (85% probability), as well as to act as a mucomembranous protector (73%)., (© Temesgen et al. 2020.)

Novel halogenated aromatic dichlorodiazadienes were prepared via copper-mediated oxidative coupling between the corresponding hydrazones and CCl 4 . These rare azo-dyes were characterized using 1 H and 13 C NMR techniques and X-ray diffraction analysis for five halogenated dichlorodiazadienes. Multiple non-covalent halogen···halogen interactions were detected in the solid state and studied by DFT calculations and topological analysis of the electron density distribution within the framework of Bader's theory (QTAIM method). Theoretical studies demonstrated that non-covalent halogen···halogen interactions play crucial role in self-assembly of highly polarizable dichlorodiazadienes. Thus, halogen bonding can dictate a packing preference in the solid state for this class of dichloro-substituted heterodienes, which could be a convenient tool for a fine tuning of the properties of this novel class of dyes.

The bis-(anil) mol-ecule of the title compound, C 47 H 32 N 2 O 2 ·C 6 H 4 Cl 2 , contains two anil fragments in the enol-enol form, exhibiting intra-molecular O-H⋯N hydrogen bonds. The two hy-droxy-naphthalene ring systems are approximately parallel to each other with a dihedral angle of 4.67 (8)° between them, and each ring system makes a large dihedral angle [55.11 (11) and 48.50 (10)°] with the adjacent benzene ring. In the crystal, the bis-(anil) mol-ecules form an inversion dimer by a pair of weak C-H⋯O inter-actions. The dimers arrange in a one-dimensional column along the b axis via another C-H⋯O inter-action and a π-π stacking inter-action between the hy-droxy-naphthalene ring system with a centroid-centroid distance of 3.6562 (16) Å. The solvent 1,2-di-chloro-benzene mol-ecules are located between the dimers and bind neighbouring columns by weak C-H⋯Cl inter-actions. Theoretical prediction of potential biological activities was performed, which suggested that the title anil compound can exhibit histone de-acetyl-ase SIRT2, histone de-acetyl-ase class III and histone de-acetyl-ase SIRT1 activities, and will act as inhibitor to aspulvinone di-methyl-allyl-transferase, de-hydro-l-gulonate deca-rboxylase and gluta-thione thiol-esterase., (© Wodajo et al. 2020.)

The title compound, C 27 H 24 N 2 O 5 , is a product of the deamination reaction from aza-14-crown-4 ether containing the γ-piperidone subunit. The title mol-ecule contains a 16-membered macrocycle with the conformation of the C-O-C-C-O-C-C-O-C polyether chain being t - g (-) - t - t - g (+) - t ( t = trans , 180°; g = gauche , ±60°). The dihedral angle between the planes of the benzene rings fused to the aza-14-crown-4-ether moiety is 31.11 (14)°. The cavity size inside the macrocycle is 4.72 Å. The macrocycle is significantly flattened as a result of the extended conjugated system. Steric repulsion between the pyridyl-carboxamide fragment and the benzene ring results in a slight deviation of macrocycle from planarity. The structure also features intra-molecular hydrogen bonding, which results in a deviation of the angle between the planes of amide and pyridyl groups from planarity: this angle is 16.32 (18)°. In the crystal, the mol-ecules are linked into infinite zigzag chains via inter-molecular C-H⋯π contacts. The chains are bound into layers parallel to (100) by weak inter-molecular C-H⋯O hydrogen bonds., (© Wodajo et al. 2020.)

The metal-assisted nitrone-nitrile cycloaddition reaction is apply to empower chitosan chemistry. The ultrasonic irradiation has proven to efficiently accelerate the cycloaddition affording new heterocyclic (1,2,4-oxadiazoline) chitosan derivatives and avoiding ultrasonic degradation of the chitosan macromolecules. By varying the nitrone nature, both water- and toluene-soluble chitosan derivatives were successfully synthesized. Relying on the ionic gelation approach nanoparticles of heterocyclic chitosan derivatives were prepared. Water-soluble chitosan derivative demonstrated a high antibacterial activity coupled with low toxicity. The toxicity of the synthesized heterocyclic chitosan derivatives and their based nanoparticles are comparable with those of the starting chitosan, while their antibacterial activity is superior. Toluene-soluble derivatives are shown to be efficient homogeneous catalysts towards monoglyceride synthesis via the epoxide ring opening. They efficiently catalyze selective conversion of fatty acids and glycidol into corresponding monoglycerides allowing one to simplify significantly the procedure for separating the reaction product from the catalyst for its recovery and reusage., (Copyright © 2020 Elsevier B.V. All rights reserved.)

In this work, we demonstrate that the thiol-yne click reaction could be efficiently mediated by ultrasonic irradiation and implement the ultrasound-assisted thiol-yne click reaction to chitosan chemistry as a polymer-analogous transformation. We optimize power and frequency of ultrasound to preserve selectivity of the click reaction and avoid ultrasonic degradation of the chitosan polymer chain. Thus, we obtain a new water-soluble betaine. Using ionic gelation of the obtained betaine derivatives of chitosan, we prepare nanoparticles with a unimodal size distribution. Furthermore, we present results of antibacterial and transfection activity tests for the chitosan derivatives and their based nanoparticles. The derivative with a medium molecular weight and a high degree of substitution demonstrated the best antibacterial effect. It derived nanoparticles with a size of ca. 100 nm and ζ-potential of ca. +69 mV revealed even higher antibacterial activity, slightly superior to commercial antibiotics ampicillin and gentamicin. On the contrary, the obtained polymers possess a much more pronounced transfection activity as compared with their based nanoparticles and species with a low degree of substitution acts as the most efficient transfecting agent. Moreover, the obtained betaine chitosan derivatives as well as their derived nanoparticles are non-toxic., (Copyright © 2019 Elsevier B.V. All rights reserved.)

In this work, we developed a simple method for the preparation of N-(3-azido-2-hydroxypropyl)chitosan. We compared the antibacterial activity of N-(3-azido-2-hydroxypropyl)chitosans and previously synthesized N-(2-azidoethyl)chitosans. N-(3-azido-2-hydroxypropyl)chitosans possess higher antibacterial effect which is comparable with that of ampicillin and gentamicin. The effect is due to azido pharmacophore -CH 2 -CH(OH)-CH 2 -N 3 (for N-(3-azido-2-hydroxypropyl)chitosan) or -CH 2 -CH 2 -N 3 (for N-(2-azidoethyl)chitosan) introduced in chitosan chain, since the corresponding organic azides NH 2 -CH 2 -CH 2 -N 3 and NH 2 -CH 2 -CH 2 -N 3 are characterized by high antibacterial activity. However, high antibacterial organic azides NH 2 -CH 2 -CH 2 -N 3 and NH 2 -CH 2 -CH 2 -N 3 are characterized by high toxicity. Their conjugation to the chitosan chain saves their antibacterial effect, but strongly diminishes their toxicity, and the toxicity of the resulting derivatives is comparable with that of the starting chitosan. These findings are of interest to food science, since novel effective food coatings can be developed on basis of prepared derivatives., (Copyright © 2019. Published by Elsevier Ltd.)

Gold carbenes of the general type [LAu=CR 2 ] + are sufficiently long-lived for spectroscopic inspection only if the substituents compensate for the largely missing stabilization of the carbene center by the [LAu] + fragment. π-Donation by two fluorine substituents (R=F) is insufficient; rather, difluorocarbene complexes are so deprived in electron density that they sequester even "weakly coordinating" anions such as triflate or triflimide. This particular bonding situation translates into unmistakable carbenium ion chemistry upon reaction with stilbene as a model substrate., (© 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

The synthesis of the industrially important polymer parylene is achieved by polymerization of p -quinodimethane ( p -QDM). The polymerization is thought to proceed via a biradical p -QDM dimer, but isolation or characterization of such a biradical has remained elusive. Here, we describe the synthesis of an aza-analogue of this p -QDM dimer. The biradical is formed by base-induced dimerization of an azoimidazolium dye. Due to the presence of sterically shielded aminyl radicals instead of terminal H 2 Ċ groups, the stability of this dimer is sufficient for analyses by ESR spectroscopy and X-ray crystallography. A similar Csp 3 -Csp 3 coupling was observed for an azotriazolium dye, suggesting that base-induced C-C coupling reactions can be realized for different types of azo dyes.

Two highly labile silver carbene cluster complexes are described, which are unique in that they mark the transition point at which the carbene center transmutes from a fairly common NHC-like nucleophilic behavior to an electrophilic character befitting reactive silver carbene intermediates of relevance in various catalytic transformations. This amphoteric character is the distinguishing attribute of a μ-bridged donor/donor carbene entity that connects two silver atoms of triangular or tetrahedral metallic core units., (© 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Well-defined diazotates are scarce. Here we report the synthesis of unprecedented homoleptic palladium(II) diazotate complexes. The palladium(II)-mediated nitrosylation of 2-aminopyridines with NaNO 2 results in the formation of metal-stabilized diazotates, which were found to be cytotoxic to human ovarian cancer cells.

The synthesis and characterization of a new class of neutral aminyl radicals is reported. Monoradicals were obtained by reduction of azoimidazolium dyes with potassium. Structural, spectroscopic, and computational data suggest that the spin density is centered on one of the nitrogen atoms of the former azo group. The reduction of a dimeric dye with an octamethylbiphenylene bridge between the azo groups resulted in the formation of a biradical with largely independent unpaired electrons. Both the monoradicals and the biradical were found to display high stability in solution as well as in the solid state.

A new method for the synthesis of industrially important azoimidazolium dyes is presented. The procedure is based on a reagent which is rarely used in the context of synthetic organic chemistry: nitrous oxide ("laughing gas"). N2O is first coupled to N-heterocyclic carbenes. Subsequent reaction with aromatic compounds through an AlCl3-induced C-H activation process provides azoimidazolium dyes in good yields., (© 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Metal-mediated cleavage of the N-N bond is a rarely observed phenomenon in the chemistry of nitrous oxide (N2O). We demonstrate that, upon activation of N2O with N-heterocyclic carbenes, zerovalent nickel is able to insert into the N-N bond to give nitrosyl complexes.

N-Heterocyclic carbenes (NHCs) react at ambient conditions with nitrous oxide to give covalent adducts. In the crystal, all compounds show a bent N2O group connected via the N-atom to the former carbene carbon atom. Most adducts are stable at room temperature, but heating induces decomposition into the corresponding ureas. Kinetic experiments show that the thermal stability of the NHC-N2O adducts depends on steric as well as electronic effects. The coordination of N2O to NHCs weakens the N-N bond substantially, and facile N-N bond rupture was observed in reactions with acid or acetyl chloride. On the other hand, reaction with tritylium tetrafluoroborate resulted in a covalent modification of the terminal O-atom, and cleavage of the C-N2O bond was observed in a reaction with thionyl chloride. The coordination chemistry of IMes-N2O (IMes = 1,3-dimesitylimidazol-2-ylidene) was explored in reactions with the complexes CuOTf, Fe(OTf)2, PhSnCl3, CuCl2, and Zn(C6F5)2. Structural analyses show that IMes-N2O is able to act as a N-donor, as an O-donor, or as a chelating N,O-donor. The different coordination modes go along with pronounced electronic changes as evidenced by a bond length analysis.

Chemically induced bond cleavage of nitrous oxide typically proceeds by rupture of the N-O bond with concomitant O-atom transfer and liberation of dinitrogen. On a few occasions, N-N bond scission has been observed instead. We report a reaction sequence involving an N-heterocyclic carbene and a vanadium complex that results in cleavage of both the N-O bond and the N-N bond., (© 2012 American Chemical Society)

The consecutive addition of AgSO(3)CF(3) (1 or 2 equiv) and cyanoguanidine (1 or 2 equiv, respectively) to the platinum(II) precursor [PtI(2)(tmeda)] leads to the cis-[PtI(tmeda){NCN=C(NH(2))(2)}](SO(3)CF(3)) (1.(SO(3)CF(3))) or cis-[Pt(tmeda){NCN=C(NH(2))(2)}(2)](SO(3)CF(3))(2) (2.(SO(3)CF(3))(2)) complexes. The reaction between 1.(SO(3)CF(3)) or 2.(SO(3)CF(3))(2) and the excess of R(2)NH (R = H, R(2) = C(5)H(10)) in EtOH gives the triazapentadiene compounds cis-[Pt(tmeda){NHC(NR(2))NC(NH(2))NH}](SO(3)CF(3)) (3.(SO(3)CF(3)) and 4.(SO(3)CF(3)), correspondingly). Protonation of these species results in cis-[Pt(tmeda){NHC(NR(2))NHC(NH(2))NH}](SO(3)CF(3))(2) ([3.H](SO(3)CF(3))(2) and [4.H](SO(3)CF(3))(2), respectively). The interaction of solid 2.(SO(3)CF(3))(2) and the gaseous RNH(2) (R = H, Me) leads to cis-[Pt(tmeda){NHC(NHR)NHC(NH(2))NH}(2)](SO(3)CF(3))(2) (5.(SO(3)CF(3))(2) and 6.(SO(3)CF(3))(2), respectively). Treatment of an acetone solution of 2.(SO(3)CF(3))(2) with an aqueous NH(3) or the reaction of 5.(SO(3)CF(3))(2) with Me(2)CO produces the triazine complex cis-{Pt(tmeda){NH=CNHC(Me)(2)}NHC(NH)(2)N}(2)(SO(3)CF(3))(2) (7.(SO(3)CF(3))(2)). The reaction of 5.(SO(3)CF(3))(2) with Me(2)CO also leads to 7.(SO(3)CF(3))(2). All new complexes were characterized by elemental analyses (C, H, N), electrospray ionization mass spectrometry, IR, and (1)H and (13)C NMR spectroscopies. The structures of 1.(SO(3)CF(3)), 2.(SO(3)CF(3))(2), 3.(SO(3)CF(3)), [4.H](SO(3)CF(3))(2), 5.(SO(3)CF(3))(2), and 7.(SO(3)CF(3))(2) were determined by single-crystal X-ray diffraction.

The reactions between equimolar amounts of cis-[PdCl(2)(C[triple bond]NR)(2)] (R = cyclohexyl (Cy) 1, tBu 2, 2,6-Me(2)C(6)H(3) (Xyl) 3) and the acyclic nitrones O(+)N(R(2))=C(H)R(3) (R(2) = Me 5, R(2) = CH(2)Ph 6, R(3) = 4-MeC(6)H(4)) proceeded in C(6)H(6) at 5 degrees C for around 4 h and then the reaction systems were maintained at 20-25 degrees C for 20 h to provide the carbene complexes [PdCl(2){C(ONR(2)C(c)HR(3)) = N(d)R}(C[triple bond]NR)(C(c)-N(d))] (8-13) in good yields (54-70%). The latter species originated from the previously unreported metal-mediated [2+3] cycloaddition of nitrones to coordinated isonitriles. For the reactions of cis-[PdCl(2)(C[triple bond]NR)(2)] (1-3) and 5 or 6 performed in C(6)H(6) at 20-25 degrees C, the selectivity of the cycloaddition was lost, and the reactions gave mixtures of 8-13 and the complexes [PdCl(2){N(R(2))=CHR(3)}(C[triple bond]NR)] (14-19, ca. 75%) derived from intramolecular deoxygenation of the nitrones. The reactions of equimolar amounts of cis-[PdCl(2)(C[triple bond]NR)(2)] (1-3 and R = 4-MeOC(6)H(4) 4) and the nonaromatic cyclic nitrone (-)O(+)N(a)=CHCH(2)CH(2)C(b)Me(2)(N(a)-C(b)) (7) in CHCl(3) at 5 degrees C for around 2 h led to the carbene species [PdCl(2){C(ON(a)CMe(2)CH(2)CH(2)C(b)H) = N(e)R}(C[triple bond]NR)(N(a)-C(b))(C(b)-N(e))] (21-24), isolated in yields of 78-92%. When the reactions of cis-[PdCl(2)(C[triple bond]NR)(2)] (1-4) and 7 (1:1 molar ratio) were performed in CHCl(3) at 20-25 degrees C for around 1 h, the carbenes 21-24 and the complexes [PdCl(2){N(f)CMe(2)CH(2)CH(2)C(g)H}(C[triple bond]NR)(N(f)-C(g))] (25-28, ca. 35%), derived from the deoxygenation of 7, were identified by ESI(+)-MS and (1)H NMR analysis (after redissolution in CDCl(3)). The reactions of cis-[PdCl(2)(C[triple bond]NR)(2)] (1-4) and 7 (1:2 molar ratio) in CHCl(3) at 5 degrees C furnished mixtures of [PdCl(2){C(ON(a)CMe(2)CH(2)CH(2)C(b)H)=N(e)R}(N(f)CMe(2)CH(2)CH(2)C(g)H)(N(a)-C(b))(C(b)-N(e))(N(f)-C(g))] (29-32; ca. 25-30%), 25-28 (ca. 10-15%), and [PdCl(2)(ON(a)CMe(2)CH(2)CH(2)C(b)H)(2)(N(a)-C(b))]. The same reactions at room temperature afforded the complex [PdCl(2)(N(f)CMe(2)CH(2)CH(2)C(g)H)(2)(N(f)-C(g))] (33; ca. 20 %) in a mixture with 29-32 (ca. 5-10%) and 25-28.