Search

The title complex, [ZnCl(C12H15N3O2)2][ZnCl3(CH3CN)], was synthesized and its structure was fully characterized through single-crystal X-ray diffraction analysis. The complex crystallizes in the orthorhombic system, space group Pbca (61), with a central zinc atom coordinating one chlorine atom and two pyrrolidinyl-4-methoxyphenyl azoformamide ligands in a bidentate manner, utilizing both the nitrogen and oxygen atoms in a 1,3-heterodiene (N N--C O) motif for coordinative bonding, yielding an overall positively (+1) charged complex. The complex is accompanied by a [(CH3CN)ZnCl3]- counter-ion. The crystal data show that the harder oxygen atoms in the heterodiene zinc chelate form bonding interactions with distances of 2.002 (3) and 2.012 (3) A °, while nitrogen atoms are coordinated by the central zinc cation with bond lengths of 2.207 (3) and 2.211 (3) A. To gain further insight into the intermolecular interactions within the crystal, Hirshfeld surface analysis was performed, along with the calculation of two-dimensional fingerprint plots. This analysis revealed that H. . .H (39.9%), Cl. . .H/H. . .Cl (28.2%) and C. . .H/H. . .C (7.2%) interactions are dominant. This unique crystal structure sheds light on arrangement and bonding interactions with azoformamide ligands, and their unique qualities over similar semicarbazone and azothioformamide structures. [ABSTRACT FROM AUTHOR]

A rare case of sclerosing hemangioma (SH) of the lung is described in a 23‑year‑old gentleman, who presented with cough with expectoration, breathlessness, and left‑sided chest pain with recurrence. We present a brief review of SH, an uncommon but histologically distinctive neoplasm of the lung. SH of the lung is generally considered to be a benign lesion, and surgical excision is curative without the need for additional treatment. [ABSTRACT FROM AUTHOR]

The kinetics of hydrogen atom abstraction reactions of methyl difluoroacetate (CF2HCOOCH3) by OH radical has been studied by quantum mechanical method. The geometry optimisation and frequency calculation of the titled compound was performed with density functional theory using hybrid meta density functional MPWB1K with 6-31+G(d,p) basis set. Transition states have been determined and intrinsic reaction coordinate (IRC) calculation has been performed to ascertain that the transition from reactants to products was smooth through the corresponding transition state. Energy values are refined by making single point energy calculation at G3B3 level of theory and an energy level diagram is constructed. The standard enthalpies of formation of reactants and other species formed during the reaction were calculated using isodesmic method. The rate constants are calculated using canonical transition state theory and the overall rate constant is determined to be 1.35×10−13cm3molecule−1s−1at 298 K and 1 atmospheric pressure. Tunnelling has been taken into account in the determination of the rate constant because it plays a critical role at low temperature especially when transfer of hydrogen takes place. The calculated value is found to be in good agreement with the experimentally determined value of 1.48×10−13cm3molecule−1s−1. [ABSTRACT FROM PUBLISHER]

Hydrofluoroethers (HFEs) are developed as a suitable for the replacement of environmentally hazardous CFCs and are termed as third generation refrigerants. One of the major products of decomposition of HFEs in the atmosphere is a fluoroester. The present study relates to the OH and Cl initiated oxidation of CF3C(O)OCH2CF3 formed from the oxidation of HFE-356mff. The latter is used as a solvent in the industry and reaches the atmosphere without any degradation. Kinetics of the titled molecule has been studied at MPWB1K/6-31+G(d,p) level of theory. Single point energy calculations have been made at G2(MP2) level of theory and barrier heights are determined. The rate constants are calculated using canonical transition state theory. Tunnelling correction are made using one-dimensional Eckart potential barrier. The rate constant calculated during the present study are compared with the experimental values determined using relative rate method and FTIR detection technique. [ABSTRACT FROM AUTHOR]

Hydrofluoroethers (HFEs) are developed as a suitable for the replacement of environmentally hazardous CFCs and are termed as third generation refrigerants. One of the major products of decomposition of HFEs in the atmosphere is a fluoroester. The present study relates to the OH and Cl initiated oxidation of CF3C(O)OCH2CF3 formed from the oxidation of HFE-356mff. The latter is used as a solvent in the industry and reaches the atmosphere without any degradation. Kinetics of the titled molecule has been studied at MPWB1K/6-31+G(d,p) level of theory. Single point energy calculations have been made at G2(MP2) level of theory and barrier heights are determined. The rate constants are calculated using canonical transition state theory. Tunnelling correction are made using one-dimensional Eckart potential barrier. The rate constant calculated during the present study are compared with the experimental values determined using relative rate method and FTIR detection technique. [ABSTRACT FROM AUTHOR]

Finding new sources of biologically active compounds for anticancer or antimicrobial therapies remains an active area of research. Azothioformamides (ATFs) with a 1,3 N=N-C=S heterodiene backbone are a new class of biologically active compounds that chelate metals (e.g., Cu) forming stable ATF metal coordination complexes. In this study, ATF ligands were prepared with pyrrolidine, piperidine, N -methylpiperazine, and morpholine substituents on the formamide as to add more heterocyclic drug-like character for biological studies. Formamide derivatives were then complexed with various Cu(I) salts to form coordination complexes. Cu(I) salts were selected as to create potential bioactive compounds with less toxicity. Binding association constants of each Cu(I) salt to ATF ligands were extrapolated from UV-vis titration studies and were corroborated with DFT calculations using a hybrid functional B3LYP method. It was observed that the smaller pyrrolidine functionalized ATFs bound to the Cu(I) salts had stronger binding than any of the larger six-membered-ring heterocycles with association values in the 10 4 - 10 5 M -1 range. The ATF-Cu(I) salt coordination complexes were then evaluated for antimicrobial activity against two bacteria ( Staphylococcus aureus , Escherichia coli ), one yeast ( Candida albicans ), four human cancer lines (A-549, K-562, HT-1080, MDA-MB-231), and two normal human lines (MRC-5, HFF). The ATF ligands themselves were inactive against all microbes and most human lines except K-562 cells, which were sensitive to three of the four ligands (IC 50 's = 7.0-25.5 μM). Most ATF-Cu(I) complexes showed low to medium micromolar activity against Candida albicans (IC 50 's 2.6-24.8 μM) and Staphylococcus aureus (IC 50 's = 3.4-37.7 μM), with increasing activity corresponding to complexes with higher binding association constants. The antiproliferative properties of ATF-Cu(I) metal salt complexes against mammalian cells were mixed, with low to medium micromolar activity across all cell lines. Notably, several ATF-Cu(I) salt coordination complexes showed submicromolar activity against the HT-1080 fibrosarcoma line (0.52-0.69 μM). The results demonstrate promising activity of ATF-Cu(I) complexes, particularly with pyrrolidine as the formamide component. These studies suggest that the stronger binding association values correlate to higher levels of biological activity., Competing Interests: The authors declare no competing financial interest., (© 2024 The Authors. Published by American Chemical Society.)