Synthesis of 2-(Triazolyl,Oxadiazolyl, and Pyrazolyl) Substituted 1,5-Benzothiazepin-S,S-Dioxide Derivatives of Potential Medicinal Interest

Abstract

The synthetic potential of 2,3,4,5-tetrahydrobenzo[b] [1,5]thiazepine-1,1,4-trione-2-carbohydrazide (5) which resulted from ethyl-4-oxo-2,3,4,5-tetrahydrobenzo[b] [1,5]thiazepine-2-carboxylate (3), on its oxidation with H₂O₂/AcOH followed by treatment with NH₂NH₂.H₂O, was exploited to provide an access to 2-triazolo, 2-oxadiazolo, and 2-pyrazolo substituted derivatives of 1,5-benzothiazepin-4-oxo-1,1-dioxides (6–10), respectively.     

Macroscopic recognition of iodide by polymer appended calix[4]amidocrown resin

ABSTRACT

The current study reveals the synthesis of polymer appended Calix[4]amidocrown-5 with specific binding affinity for iodide at ppm-level. The low detection limits are observed via UV-vis and fluorescence spectroscopy. The time-dependent solution and solid-state ¹²⁷I NMR studies with 18.8 and 19 ppm shifts, indicate a strong sensing nature of resin towards iodide ion. A significant reduction in surface area and pore volume with higher thermostability of resin after iodide uptake indicated iodide inclusion in the amidocrown cavity. The mechanism of iodide sensing may be governed by noncovalent interactions of NH and OH protons present in amidocrown and phenyl ring as observed in terms of emission enhancement in fluorescence spectroscopy. The binding affinity and stoichiometric determinations are determined by Benesi-Hildebrand and Jobs plots, respectively.     

Molecular Cloning and Characteristic Features of a Novel Extracellular Tyrosinase from <Emphasis Type="Italic">Aspergillus niger</Emphasis> PA2

Biofertilizers have been widely used in many countries for their benefit to soil biological and physicochemical properties. A new microbial biofertilizer containing Phanerochaete chrysosporium and Bacillus thuringiensis was prepared to decrease nicotine content in tobacco leaves by regulating soil nitrogen supply. Soil NO₃ ^?-N, NH₄ ⁺-N, nitrogen supply-related enzyme activities, and nitrogen accumulation in plant leaves throughout the growing period were investigated to explore the mechanism of nicotine reduction. The experimental results indicated that biofertilizer can reduce the nicotine content in tobacco leaves, with a maximum decrement of 16–18 % in mature upper leaves. In the meantime, the total nitrogen in mature lower and middle leaves increased with the application of biofertilizer, while an opposite result was observed in upper leaves. Protein concentration in leaves had similar fluctuation to that of total nitrogen in response to biofertilizer. NO₃ ^?-N content and nitrate reductase activity in biofertilizer-amended soil increased by 92.3 and 42.2 %, respectively, compared to those in the control, whereas the NH₄ ⁺-N and urease activity decreased by 37.8 and 29.3 %, respectively. Nitrogen uptake was improved in the early growing stage, but this phenomenon was not observed during the late growth period. Nicotine decrease is attributing to the adjustment of biofertilizer in soil nitrogen supply and its uptake in tobacco, which result in changes of nitrogen content as well as its distribution in tobacco leaves. The application of biofertilizer containing P. chrysosporium and B. thuringiensis can reduce the nicotine content and improve tobacco quality, which may provide some useful information for tobacco cultivation.     

Ultrafast and bias-free all-optical wavelength conversion using III-V-on-silicon technology

Using a 7.5 μm diameter disk fabricated with III-V-on-silicon fabrication technology, we demonstrate bias-free all-optical wavelength conversion for non-return-to-zero on-off keyed pseudorandom bit sequence (PRBS) data at the speed of 10 Gbits/s with an extinction ratio of more than 12 dB. The working principle of such a wavelength converter is based on free-carrier-induced refractive index modulation in a pump-probe configuration. We believe it to be the first bias-free on-chip demonstration of all-optical wavelength conversion using PRBS data. All-optical gating measurements in the pump-probe configuration with the same device have revealed that it is possible to achieve wavelength conversion beyond 20 Gbits/s.     

Discovery of novel inhibitors for <Emphasis Type="Italic">Leishmania</Emphasis> nucleoside diphosphatase kinase (NDK) based on its structural and functional characterization

Nucleoside diphosphate kinases (NDKs) are ubiquitous enzymes that catalyze the transfer of the γ-phosphate moiety from an NTP donor to an NDP acceptor, crucial for maintaining the cellular level of nucleoside triphosphates (NTPs). The inability of trypanosomatids to synthesize purines de novo and their dependence on the salvage pathway makes NDK an attractive target to develop drugs for the diseases they cause. Here we report the discovery of novel inhibitors for Leishmania NDK based on the structural and functional characterization of purified recombinant NDK from Leishmania amazonensis. Recombinant LaNDK possesses auto-phosphorylation, phosphotransferase and kinase activities with Histidine 117 playing an essential role. LaNDK crystals were grown by hanging drop vapour diffusion method in a solution containing 18% PEG-MME 500, 100 mM Bis-Tris propane pH 6.0 and 50 mM MgCl₂. It belongs to the hexagonal space group P6₃22 with unit cell parameters a?=?b?=?115.18, c?=?62.18 Å and α?=?β?=?90°, γ?=?120°. The structure solved by molecular replacement methods was refined to crystallographic R-factor and R_free values of 22.54 and 26.52%, respectively. Molecular docking and dynamics simulation-based virtual screening identified putative binding compounds. Protein inhibition studies of selected hits identified five inhibitors effective at micromolar concentrations. One of the compounds showed ~45% inhibition of Leishmania promastigotes proliferation. Analysis of inhibitor-NDK complexes reveals the mode of their binding, facilitating design of new compounds for optimization of activities as drugs against leishmaniasis.     

Basic Ionic Liquid Promoted Domino Knoevenagel–Thia‐Michael Reaction: An Efficient and Multicomponent Strategy for Synthesis of 1,3‐Thiazines

An efficient, three‐component strategy for synthesis of 1,3‐thiazines with high atom economy in one‐pot mediated by room temperature basic ionic liquid is described here. The strategy involves basic ionic liquid, [bmim]OH‐catalyzed Knoevenagel condensation between ethyl cyanoacetate and aromatic aldehyde and subsequent thia‐Michael addition with substituted thioureas. The reaction sequence is smooth and quantitative under ambient temperature. [bmim]OH was recovered and reused four times without any appreciable decrease in its reactivity and product yield.     

Tantalum,easy as Pi: understanding differences in metal–imido bonding towards improving Ta/Nb separations

The separation and purification of niobium and tantalum, which co-occur in natural sources, is difficult due to their similar physical and chemical properties. The current industrial method for separating Ta/Nb mixtures uses an energy-intensive process with caustic and toxic conditions. It is of interest to develop alternative, fundamental methodologies for the purification of these technologically important metals that improve upon their environmental impact. Herein, we introduce new Ta/Nb imido compounds: M(^tBuN)(TriNOx) (1-M) bound by the TriNOx³⁻ ligand and demonstrate a fundamental, proof-of-concept Ta/Nb separation based on differences in the imido reactivities. Despite the nearly identical structures of 1-M, density functional theory (DFT)-computed electronic structures of 1-M indicate enhanced basic character of the imido group in 1-Ta as compared to 1-Nb. Accordingly, the rate of CO₂ insertion into the M N_imido bond of 1-Ta to form a carbamate complex (2-Ta) was selective compared to the analogous, unobserved reaction with 1-Nb. Differences in solubility between the imido and carbamate complexes allowed for separation of the carbamate complex, and led to an efficient Ta/Nb separation (S_Ta/Nb = 404 ± 150) dependent on the kinetic differences in nucleophilicities between the imido moieties in 1-Ta and 1-Nb.

A selective separation of the critical metals tantalum and niobium was accomplished from π-bonding-based reactivity differences of imido complexes. New insights into Ta/Nb separations were gained through detailed kinetic and computational studies.     

2-Nitrobenzaldehyde Thiocarbohydrazone Assisted Precise Extraction Spectrophotometric Method for the Determination of Ruthenium(III) in Alloy and Catalysts

A simple, rapid, selective, sensitive and reliable extractive spectrophotometric method was developed for the determination of ruthenium(III) using 2-nitrobenzaldehyde thiocarbohydrazone (2-NBATCH) as a chromogenic chelating ligand. The ruthenium(III)?2-NBATCH complex is formed in aqueous acetic acid media (0.7 M) containing an organic solvent after 5 min heating on a water bath. The red colored complex is extracted into 1,2-dichloroethane and absorbance is measured at 445 nm against reagent blank. The Beer’s law is obeyed within 1?6 g/mL of ruthenium(III), the optimum concentration range was 2?5 g/mL of ruthenium(III) evaluated by Ringbom’s plot. Molar absorptivity and Sandell’s sensitivity of complex were 1.41 × 10⁴ L/mol/cm and 0.0075 μg/cm², respectively. The stoichiometry of complex was 1: 3 established from Job’s method of continuous variation, molar ratio method and logarithmic slope method. The proposed method was applied for determination of ruthenium(III) in binary and ternary, synthetic mixtures corresponding to fission product elements alloy and ruthenium(III) catalysts.     

Partially bio‐based poly(amide imide)s by polycondensation of aromatic diacylhydrazides based on lignin‐derived phenolic acids and aromatic dianhydrides: Synthesis,characterization, and computational studies

Two new bio‐based diacylhydrazide monomers, namely, 4,4′‐(propane‐1,3‐diylbis(oxy))bis(3‐methoxybenzohydrazide) and 4,4′‐(propane‐1,3‐diylbis(oxy))bis(3,5‐dimethoxybenzohydrazide) were synthesized starting from lignin‐derived phenolic acids, namely, vanillic acid and syringic acid. A series of poly(amide imide)s was synthesized by polycondensation of these diacylhydrazide monomers with commercially available aromatic dianhydrides. Poly(amide imide)s showed inherent viscosity in the range 0.44–0.56 dL g^?1 and exhibited good solubility in organic solvents. Poly(amide imide)s could be cast into transparent, flexible, and tough films from their N ,N‐dimethylacetamide solutions. Poly(amide imide)s showed 10% weight loss in the temperature range 340–364 °C indicating their good thermal stability. Glass transition temperature (T _g) of poly(amide imides)s were measured by DSC and DMA which were in the range 201–223 °C and 214–248 °C, respectively. The T _g values of poly(amide imide)s were dependent on the number methoxy substituents on aromatic rings of diacylhydrazide monomers. Molecular dynamics simulation studies revealed that chain rigidity is the dominant factor for observed trends in T _g. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017 , 55 , 3636–3645     

Birkhoff Centre of a Poset

In this paper, it is proved that the Boolean centre of a semigroup S with sufficiently many commuting idempotents is isomorphic to the inverse limit of the directed family of Birkhoff centres (or Boolean centres) of a class of bounded semigroups. The Birkhoff centre is defined for any poset and proved that it is a relatively complemented distributive lattice whenever it is nonempty. It is observed that for a semilattice S, the Birkhoff centres as a semigroup and as a poset coincide. Also it is observed that for a Lattice (L, , ), the Birkhoff centres of the semilattices (L, ) and (L, ) coincide with the Birkhoff centre of L. Finally it is proved that for a lattice (L, , ), the Boolean centres of the semilattices (L, ) and (L, ) coincide with the Boolean centre of L.AMS Subject classification (1991): 06A12, 20M15