Utilization of thiazolylacetonitriles in the synthesis of thiophene,thiazole, pyrazolo[1,5‐a]pyrimidine and pyrazolo [5,1‐c]triazine derivatives

Thiazolylcyanothioacetanilides react with α‐haloketones and haloesters to give the corresponding thiophene or thiazole derivatives according to the reaction conditions. Pyrazolo[1,5‐a]pyrimidines and pyrazolo[5,1‐c]triazines were synthesized by reaction of 3‐amino‐4‐(4′‐arylthiazol‐2′‐yl)‐5‐phenylaminopyrazole with different reagents. Structures of the new compounds were confirmed by elemental analyses, spectral data, and alternative methods of synthesis whenever possible. © 1999 John Wiley & Sons, Inc. Heteroatom Chem 10: 508–516, 1999     

Thermolysis of 3-phenyl-5-arylamino-1,2,4-oxadiazole and thiadiazole derivatives

Thermal reactions of 3-phenyl-5-arylamino-1,2,4-oxadiazoles I and II were investigated. Neat heating at ca. 250°C for 6 hours afforded H₂O, benzonitrile, arylcyanamides, arylamines, azobenzene, benzimidazole derivatives, and 3,3′-diphenyl-5,5′-bis[1,2,4-oxadiazolyl]. Analogous results were obtained by the thermolysis of 3-phenyl-5-anilino-1,2,4-thiadiazole III at ca. 200°C for 2 hours. In addition to H₂S, NH₃, and HNCS, phenyl isothiocyanate and thiocarbanilide were obtained. Thermolysis of III in quinoline as a radical trap gave analogous resuLts but also 2-anilinoquinoline. A free-radical mechanism has been suggested to account for the identified products. © 1997 John Wiley & Sons, Inc.     

Reactivity of 6-anisyl-5-cyano-4-oxo-2-thioxo-1,2,3,4-tetrahydro-pyrimidine to wards some electrophiles and nucleophiles

The title compound was subjected to react with some electrophiles and nucleophiles, such as alkyl halides, ethyl chloroacetate or amines, hydrazines etc. The resulting compounds were used in further syntheses for the purpose of obtaining some new types of heterocycles with possible biological and pharmaceutical activities.     

Novel VO (IV) complexes derived from a macrochelates: Synthesis,characterization, molecular modeling and in vivo insulin-mimic activity studies

For the development of extensive investigations into a potential medicinal application of vanadium coordination compounds for the oral treatment of diabetes, new mono and bimetallic VO (IV) complexes with N,N′-(2,2′-(9,10-dihydro-9,10-ethanoanthracene-11,12-dicarbonyl) bis (hydrazine-1-carbonothioyl)) dibenzamide (H₆EBT) and 2,2′-((9S,10S,11R,12R)-9,10-dihydro-9,10-ethanoanthracene-11, 12-dicarbonyl) bis (N-phenylhydrazine-1-carboxamide) (H₆EPH) have been isolated and characterized. The FTIR and NMR spectral data revealed that H₆EBT acts as neutral tridentate and dibasic hexadentate while H₆EPH as dibasic tridentate and tetrabasic hexadentate. The electronic and ESR spectra indicated that complexes has octahedral geometry. ESR spectrum of [(VO)(H₆EBT)(SO₄)].5H₂O gives a well resolved hyperfine eight-line pattern typical spectrum for mononuclear vanadyl complexes with g˃ g_⊥ = 1.9 suggesting that the ligand donor atoms ONS are coplanar with the two chelate rings forming octahedral geometry. Also, the high parallel hyperfine splitting value, A = 0.0108, than perpendicular one (A_⊥ = 0.0087) indicated that the single d- electron is in a σ-nonbonding orbital and aiming away from the equatorial ligands. On the other hand, the EPR spectra of the binuclear [(VO)₂(H₄EBT)(SO₄)]3H₂O and [(VO)₂(H₂EPH)(H₂O)₂].10H₂O complexes gave a single broad line centered at g = 2.05 and 2.07, respectively, without resolved hyperfine structure paramagnetic triplet (S = 1) is consistent with the anomalous value of the magnetic moment value (μ_eff = 1.100 and 0.99 B.M.) supporting a binuclear nature. The TG analyses confirmed the existence of solvent molecules inside and/or outside the coordination sphere. The DFT molecular modeling of ligands and its VO (IV) complexes supported the suggested geometries. Also, all compounds were screened for in vivo insulin-mimetic activity.     

Trapping of ultracold atoms in a 3He/4He dilution refrigerator

We describe the preparation of ultracold atomic clouds in a dilution refrigerator. The closed-cycle ³He/⁴He cryostat was custom made to provide optical access for laser cooling, optical manipulation and detection of atoms. We show that the cryostat meets the requirements for cold atom experiments, specifically in terms of operating a magneto-optical trap, magnetic traps and magnetic transport under ultrahigh vacuum conditions. The presented system is a step toward the creation of a quantum hybrid system combining ultracold atoms and solid-state quantum devices.     

Nicotinic acid adsorption thermodynamics study on carboxymethyl cellulose Ce(IV) molybdophosphate composite cation-exchanger

The thermodynamics of nicotinic acid adsorption from aqueous solution on carboxymethyl cellulose Ce(IV) molybdophosphate composite cation exchanger were studied. The composite cation exchanger was synthesized by sol–gel method and thereby characterized using scanning electron microscopy, thermogravimetric analysis, X-ray powder diffraction and fourier transform infra red spectroscopy. The analytical applicability and thermodynamic parameters, such as Freundlich constant, thermodynamic equilibrium constant (K _ο), standard free energy changes (ΔG°), standard enthalpy changes (ΔH°) and standard entropy changes (ΔS°) of this composite cation exchanger have been evaluated. The thermodynamic parameters showed that the adsorption of nicotinic acid onto composite cation exchanger is feasible, spontaneous and exothermic, suggesting their suitability for the potential application of nicotinic acid removal from waste water.     

Regulatory Role of Nano-Curcumin against Tartrazine-Induced Oxidative Stress,Apoptosis-Related Genes Expression,and Genotoxicity in Rats

The present study evaluates the regulatory effect of Nano-Curcumin (Nano-CUR) against tartrazine (TZ)-induced injuries on apoptosis-related gene expression (i.e., p⁵³, CASP-3 and CASP-9), antioxidant status, and DNA damages in bone marrow in treated rats. Male rats were arbitrarily separated into five groups, and each group was comprised of 10 rats each. The 1st group served as control (G1). The 2nd group ingested 7.5 mg TZ/kg. b.w. (body weight). The 3rd group ingested Nano-CUR 1 g/kg b.w. The 4th and 5th groups were respectively administered with (1 g Nano-CUR + 7.5 mg TZ/kg. b.w.) and (2 g Nano-CUR + 7.5 mg TZ/kg. b.w.). At the end of the experiment, blood samples, livers, and kidneys were collected. Livers and kidneys were homogenized and used for the analysis of reduced glutathione, malonaldhyde, total antioxidant capacity, lipid peroxide antioxidant enzyme activities, apoptosis-related gene expression, and genotoxicity by comit test. The ingestion of TZ for 50 days resulted in significant decreases in body, and kidney weights in rats and a relative increase in the liver weight compared to control. In contrast, the ingestion of Nano-CUR with TZ remarkably upgraded the body weight and relative liver weight compared to the normal range in the control. Aditionally, TZ ingestion in rats increased the oxidative stress biomarkers lipid peroxide (LPO) and malonaldehyde (MDA) significantly, whereas it decreased the reduced glutathione (GSH) levels and total antioxidant capacity (TAC). Similarly, the levels of glutathione peroxidase (GPx), superoxide dismutase (SOD), and catalase (CAT) significantly deteriorated in response to TZ ingestion. Moreover, the results revealed a remarkable up-regulation in the level of expression for the three examined genes, including p⁵³, CASP-3, and CASP-9 in TZ-ingested rats compared to the control. On the other hand, the comet assay result indicates that the ingestion of TZ induced DNA damage in bone marrow. Notably, the administration of Nano-CUR protected the kidney and liver of TZ-ingested rats as evidenced by a significant elevation in all antioxidant activities of tested enzymes (i.e, SOD, GPx, and CAT), vital recovery in GSH and TAC levels, and a statistical decrease in LPO and MDA compared to TZ-ingested rats. Interestingly, the ingestion of rats with TZ modulates the observed up-regulation in the level of expression for the chosen genes, indicating the interfering role in the signaling transduction process of TZ-mediated poisoning. The results indicate that the administration of Nano-CUR may protect against TZ-induced DNA damage in bone marrow. According to the results, Nano-CUR exerted a potential protective effect against oxidative stress, DNA damage, and the up-regulation of apoptosis-related genes induced by TZ ingested to rats.     

一些含三氮杂茂偶氮染料O,N供体的Zr(Ⅱ)配合物的合成、表征和抗微生物活性(英文)

合成了9种3-(2-羟基萘基-1-偶氮)-1,2,4-三氮唑(HL1),3-(2,4-二羟苯基-1-偶氮)-1,2,4-三氮唑(HL2),3-(2-羟基-3-羧基萘基-1-偶氮)-1,2,4-三氮唑(HL3),3-(2-羟基-5-溴苯基-1-偶氮)-1,2,4-三氮唑(HL4)和3-(2-羟基-5-甲基苯基-1-偶氮)-1,2,4-1,2,4-三氮唑(HL5)的Zr(Ⅱ)配合物并用元素分析,摩尔电导,磁矩,IR,UV-Vis,1H-NMR以及热分析(TGA和DTA)对其进行了表征。结果表明HL1-HL5以二齿一元配体方式通过偶氮的氮原子和羟基基团的氧原子与Zr(Ⅱ)离子配位生成单核配合物。用4种革兰氏阴性菌,即大肠杆菌(Escherichia coli),粘质沙雷氏菌(Serratia marcescens),阴沟肠杆菌(Enterobacter cloacae)和普通变形杆菌(Proteus vulgaris),以及2种真菌,即白色念珠菌(Candida albicans)和黑曲霉菌(Aspergillus niger)对配体及其配合物的生物学活性进行了研究。最小抑菌浓度(MICs)用纸上杯碟琼脂扩散法测定,结果表明在大多数情况下,金属化的配合物的抗微生物活性与自由配体相比有所增强。     

Synthesis,structural, spectroscopic,biological and catalytic activity of Co(II), Ni(II) and Cu(II) complexes of benzilic hydrazide (BH)

Co(II), Ni(II) and Cu(II) chloro complexes of benzilic hydrazide (BH) have been synthesized. Also, reaction of the ligand (BH) with several copper(II) salts, including NO₃ ^?, AcO^?, and SO₄ ^? afforded metal complexes of the general formula [CuLX(H₂O) _n ]·nH₂O, where X is the anion and n = 0, 1 or 2. The newly synthesized complexes were characterized by elemental analysis, mass spectra, molar conductance, UV–vis, IR spectra, magnetic moment, and thermal analysis (TG/DTG). The physico-chemical studies support that the ligand acts as monobasic bidentate towards metal ion through the carbonyl and hydroxyl oxygen atoms. The spectral data revealed that the geometrical structure of the complexes is square planar for Cu (II) complexes and tetrahedral for Co(II) and Ni(II) complexes. Structural parameters of the ligand and its complexes have been calculated. The ligand and its metal complexes are screened for their antimicrobial activity. The catalytic activities of the metal chelates have been studied towards the oxidative decolorization of AB25, IC and AB92 dyes using H₂O₂. The catalytic activity is strongly dependent on the type of the metal ion and the anion of Cu(II) complexes.     

Thermal fragmentation and rearrangement of N-arylbenzamidoxime and O-phenylsulfonyloxime derivatives

Thermal fragmentation of N-arylbenzamide oximes I, II (Ar = Ph, p-tolyl) under nitrogen gives rise to benzanilide and 2-phenylbenzoxazole as the major products, in addition to benzonitrile, arylamines, phenols, benzoic acid, o- and p-aminophenols and benzimidazole derivatives. In the presence of naphthalene as radical scavenger, I gave - and β-naphthols beside the previous products. Also, heating N-arylbenzamide O-phenylsulfonyloximes III under reflux in boiling tetralin lead to the formation of benzonitrile, arylamines, diphenylamine, benzenesulfonic acid, diphenyl sulfone, 1-hydroxytetralin, -tetralone, and 1,1′-bitetralyl as the major products. Analogous results are obtained on heating III in the presence of isoquinoline as a radical trap which formed 1-phenylisoquinoline. The isolated products have been interpreted in terms of a free radical mechanism involving the homolysis of NO and/or CN bonds.