Synthesis,characterization, and biological screening of metal complexes of novel sulfonamide derivatives: Experimental and theoretical analysis of sulfonamide crystal

This study reports the synthesis of sulfonamide-derived Schiff bases as ligands L ¹ and L ² as well as their transition metal complexes [VO(IV), Fe(II), Co(II), Ni(II), Cu(II), and Zn(II)]. The Schiff bases (4-{E-[(2-hydroxy-3-methoxyphenyl)methylidene]amino}benzene-1-sulfonamide ( L ¹ ) and 4-{[(2-hydroxy-3-methoxyphenyl)methylidene]amino}-N-(5-methyl-1,2-oxazol-3-yl)benzene-1-sulfonamide ( L ² ) were synthesized by the condensation reaction of 4-aminobenzene-1-sulfonamide and 4-amino-N-(3-methyl-2,3-dihydro-1,2-oxazol-5-yl)benzene-1-sulfonamide with 2-hydroxy-3-methoxybenzaldehyde in an equimolar ratio. Sulfonamide core ligands behaved as bidentate ligands and coordinated with transition metals via nitrogen of azomethine and the oxygen of the hydroxyl group. Ligand L ¹ was recovered in its crystalline form and was analyzed by single-crystal X-ray diffraction technique which held monoclinic crystal system with space group (P2₁/c). The structures of the ligands L ¹ and L ² and their transition metal complexes were established by their physical (melting point, color, yields, solubility, magnetic susceptibility, and conductance measurements), spectral (UV–visible [UV–Vis], Fourier transform infrared spectroscopy, ¹H NMR, ¹³C NMR, and mass analysis), and analytical (CHN analysis) techniques. Furthermore, computational analysis (vibrational bands, frontier molecular orbitals (FMOs), and natural bonding orbitals [NBOs]) were performed for ligands through density functional theory utilizing B3LYP/6-311+G(d,p) level and UV–Vis analysis was carried out by time-dependent density functional theory. Theoretical spectroscopic data were in line with the experimental spectroscopic data. NBO analysis confirmed the extraordinary stability of the ligands in their conjugative interactions. Global reactivity parameters computed from the FMO energies indicated the ligands were bioactive by nature. These procedures ensured the charge transfer phenomenon for the ligands and reasonable relevance was established with experimental results. The synthesized compounds were screened for antimicrobial activities against bacterial (Streptococcus aureus, Bacillus subtilis, Eshcheria coli, and Klebsiella pneomoniae) species and fungal (Aspergillus niger and Aspergillus flavous) strains. A further assay was designed for screening of their antioxidant activities (2,2-diphenyl-1-picrylhydrazine radical scavenging activity, total phenolic contents, and total iron reducing power) and enzyme inhibition properties (amylase, protease, acetylcholinesterase, and butyrylcholinesterase). The substantial results of these activities proved the ligands and their transition metal complexes to be bioactive in their nature.     

Selective aerobic photocatalytic oxidation of benzyl alcohol over spherical structured WO<Subscript>3</Subscript>/TiO<Subscript>2</Subscript> nanocomposite under visible light irradiation

TiO₂/WO₃ nanocomposite with nanodisk morphology was prepared and successfully used as a photocatalyst. The nanocomposite was obtained via sonochemical and hydrothermal methods, using pomegranate juice as a capping agent. The products were characterized by FE-SEM imaging, BET, EDAX spectroscopy, X-ray diffraction, DRS, and FT-IR spectroscopy. TiO₂/WO₃ nanocomposite showed high sensitivity to absorb visible light in compared to TiO₂. In an optimized condition, the yield of the aerobic photocatalytic oxidation of benzyl alcohol derivatives reached to 65% for the TiO₂/WO₃ nanocomposite, while the conversion percent of the derivatives was less than 8% and 50% on the TiO₂ and WO₃ nanoparticles, respectively. Experimental results were supported by density functional theory (DFT) calculations. The DFT results in several solvents of different dielectric constants, confirmed the strong dependence of light absorption and photocatalytic activity to adsorption energy of the substrates on the surface of the nanoparticles (E_ad). In addition, the theoretical results showed an inverse correlation between the adsorption energy of benzyl alcohol and its conversion percent, accordance to the experimental trend.

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Atrane complexes chemistry as a tool for obtaining trimodal UVM-7-like porous silica

Abstract

The use of atrane complexes as hydrolytic precursors enables the homogeneous incorporation of manganese (25 ≤ Si/Mn ≤ 48) throughout the porous walls of the nanoparticles of a surfactant-templated bimodal mesoporous silica (UVM-7). The subsequent leaching of the manganese nanodomains allows adding controlled microporosity to the host silica framework. The resulting final silica material presents three pore systems structured at different length scales: interparticle textural-type macroporosity (ca. 43.2 nm), ordered intraparticle mesoporosity (ca. 2.63 nm; after template removal), and well-dispersed microporosity (< 2 nm; as consequence of the lixiviation of the Mn-rich domains). The good dispersion of the guest element (Mn) in the silica intermediate provided by the atrane route is responsible for the disordered but regular microporosity achieved.     

Integrated Transmission Electron and Single‐Molecule Fluorescence Microscopy Correlates Reactivity with Ultrastructure in a Single Catalyst Particle

Establishing structure–activity relationships in complex, hierarchically structured nanomaterials, such as fluid catalytic cracking (FCC) catalysts, requires characterization with complementary, correlated analysis techniques. An integrated setup has been developed to perform transmission electron microscopy (TEM) and single‐molecule fluorescence (SMF) microscopy on such nanostructured samples. Correlated structure–reactivity information was obtained for 100 nm thin, microtomed sections of a single FCC catalyst particle using this novel SMF‐TEM high‐resolution combination. High reactivity in a thiophene oligomerization probe reaction correlated well with TEM‐derived zeolite locations, while matrix components, such as clay and amorphous binder material, were found not to display activity. Differences in fluorescence intensity were also observed within and between distinct zeolite aggregate domains, indicating that not all zeolite domains are equally active.     

NH4I-catalyzed chalcogen(S/Se)-functionalization of 5-membered N-heteroaryls under metal-free conditions

Herein, we described the NH₄I-catalyzed CH bond chalcogenation of N-heteroaryls in the presence of a minimum amount of DMSO/H₂O/acetic acid as additives (2.5/2.5/1?M equiv., respectively), under metal-free conditions. Under optimized conditions, a wide variety of sulfenyl/selenyl imidazo[1,2-α]pyridines were prepared in very good yields. Moreover, the present approach was also highly efficient for the chalcogenation of different 5-membered N-heteroaryls, e.g., indole, imidazothiazole, indazole and imidazopyrimidine derivatives.     

Supramolecular assemblies based on organometallic quinonoid linkers: a new class of coordination networks

Self-assembly of coordination frameworks exhibiting original architectures is an active area of research. Generally, such assemblies are constructed from organic spacers and transition metals of different geometrical structures. Herein, we report a novel class of supramolecular coordination assemblies with organometallic linkers based on metalated quinonoid and thioquinonoid complexes that serve as spacers. The organometallic ligands are stable and have the general formula [Cp*M(eta(4)-benzoquinone)] (o- and p-benzoquinone, Cp*=C(5)Me(5), M=Rh, Ir) and [Cp*Ir(eta(4)-thiobenzoquinone)] (o- and p-thiobenzoquinone). These units bind through both oxygen or sulfur atoms to metal ions of different coordination geometry, such as Cu(I), Ag(I), and Pt(II), to generate supramolecular coordination networks, with the metalated quinonoid or thioquinonoid linkers acting as backbones and the metal centers as nodes. This novel family of supramolecular assemblies exhibits short pi-pi and MM interactions. These results illustrate successfully the role of the organometallic linkers to produce an impressive range of novel supramolecular architectures that hold promise for the development of functional materials.     

Interaction of methyl beta-D-xylopyranoside with metal ions: density functional theory study of cationic and neutral bridging and pendant complexes

Density functional theory calculations on complexes of 4C1, 1C4 and 2SO ring conformations of methyl beta-D-xylopyranoside 1 with divalent metal cations, M = Mg2+, Ca2+, Zn2+, and Cd2+, are presented. Bridging and pendant cationic, [M(H2O)41]2+ and [M(H2O)(5)1]2+, as well as neutral complexes, [M(OH)2(H2O)(2)1] and [M(OH)2(H2O)(3)1], and neutral complexes involving a doubly deprotonated sugar, [M(H2O)(4)1(2-)], are considered. In aqueous and chloroform solution the stability of cationic and pendant neutral complexes is greatly diminished compared with gas-phase results. In contrast, bridging neutral complexes [M(OH)2(H2O)(2)1] and those of type [M(H2O)(4)1(2-)], are stabilized with increasing solvent polarity. Solvation also profoundly influences the preferred binding position and ring conformation. Compared with complexes of bare metal cations, additional ligands, e.g., H2O or OH-, significantly reduce the stability of 1C4 ring complexes. Irrespective of the cation, the most stable structure of bridging complexes [M(H2O)(4)1]2+ results from coordination of the metal to O3 and O4 of methyl beta-D-xylopyranoside in its 4C1 ring conformation.     

Chemical Validation of Mycobacterium tuberculosis Phosphopantetheine Adenylyltransferase Using Fragment Linking and CRISPR Interference**

The coenzyme A (CoA) biosynthesis pathway has attracted attention as a potential target for much-needed novel antimicrobial drugs, including for the treatment of tuberculosis (TB), the lethal disease caused by Mycobacterium tuberculosis (Mtb). Seeking to identify inhibitors of Mtb phosphopantetheine adenylyltransferase (MtbPPAT), the enzyme that catalyses the penultimate step in CoA biosynthesis, we performed a fragment screen. In doing so, we discovered three series of fragments that occupy distinct regions of the MtbPPAT active site, presenting a unique opportunity for fragment linking. Here we show how, guided by X-ray crystal structures, we could link weakly-binding fragments to produce an active site binder with a K_D <20 μM and on-target anti-Mtb activity, as demonstrated using CRISPR interference. This study represents a big step toward validating MtbPPAT as a potential drug target and designing a MtbPPAT-targeting anti-TB drug.     

Stress Degradation Behavior of Desipramine Hydrochloride and Development of Suitable Stability-Indicating LC Method

A simple reverse phase liquid chromatographic method was developed for the quantitative determination of desipramine hydrochloride and its related impurities in bulk drugs which is also stability-indicating. During the forced degradation at hydrolysis, oxidative, photolytic and thermal stressed conditions, the degradation results were only observed in the oxidative stress condition. The blend of the degradation product and potential impurities were used to optimize the method by an YMC Pack Pro C₁₈ stationary phase. The LC method employs a linear gradient elution with the water–acetonitrile–trifluoroacetic acid as mobile phase. The flow rate was 1.0 mL min^?1 and the detection wavelength 215 nm. The stressed samples were quantified against a qualified reference standard and the mass balance was found close to 99.0% (w/w) when the response of the degradant was considered to be equal to the analyte (i.e. desipramine). The developed RP-LC method was validated in agreement with ICH requirements.