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1.
In the aim of identifying new steroidal cytotoxic agents with potential antiproliferative activity against hepatoma cell lines (Hep-G2), we synthesized modified steroids containing the thiadiazole, pyrazole, or dithiole moiety. Epiandrosterone 1 reacted with carbon disulfide and sodium hydride to furnish α-oxoketene dithio-disodium salt 2. Treatment of 2 with the hydrazonoyl halides 5a–d produced the thiadiazole anellated androstanone 7a–d, respectively. The reaction of 1 with hydrazine hydrate produced the hydrazide adduct 8, which cyclized upon reflux in acetic acid to form the condensed pyrazoloandrostanone derivative 9. Interaction of 8 with carbon disulfide and sodium hydride formed the disodium salt 10, which reacted with ethylchloroacetate to furnish the final adduct, dithioloandrostane derivative, 13. Compounds 7a, 7d, 9, and 13 were examined for their cytotoxicity against a panel of hepatoma cell lines (Hep-G2) using MTT assay. The results provide that, at incubation time 72 h, in DMSO, compound 7d (50 μ mol/mL) showed the most significant cytotoxic effect at P < 0.05. The higher dose (100 μ mol/mL) of compound 7d, at 48 h incubation, reversed the effect causing resistance and the growth rate return to the control level.

Supplemental materials are available for this article. Go to the publisher's online edition of Phosphorus, Sulfur, and Silicon and the Related Elements to view the free supplemental file.  相似文献   
2.
Tyrosinase is a copper-containing monooxygenase catalyzing the O-hydroxylation of tyrosine to 3,4-dihydroxyphenylalanine then to dopaquinone that is profoundly involved in melanin synthesis in eukaryotes. Overactivation of tyrosinase is correlated with hyperpigmentation that is metabolically correlated with severe pathological disorders, so, inhibition of this enzyme is the most effective approach in controlling the overproduction of melanin and its hazardous effects. Thus, searching for a powerful, selective inhibitor of human tyrosinase to limit the hyper-synthesis of melanin is a challenge. Unlike the difficulty of overexpression of human tyrosinase, using fungal tyrosinase as a model enzyme to the human one to evaluate the mechanistics of enzyme inhibition in response to various compounds is the most feasible strategy. Thus, the purification of highly catalytic-efficient fungal tyrosinase, exploring a novel inhibitor, and evaluating the mechanistics of enzyme inhibition are the main objectives of this work. Aspergillus terreus and Penicillium copticola were reported as the most potential tyrosinase producers. The biochemical properties suggest that this enzyme displays a higher structural and catalytic proximity to human tyrosinase. Upon nutritional bioprocessing by Plackett–Burman design, the yield of tyrosinase was increased by about 7.5-folds, compared to the control. The purified tyrosinase was strongly inhibited by kojic acid and A. flavus DCM extracts with IC50 values of 15.1 and 12.6 µg/mL, respectively. From the spectroscopic analysis, the main anti-tyrosinase compounds of A. flavus extract was resolved, and verified as undecanoic acid. Further studies are ongoing to unravel the in vivo effect and cytotoxicity of this compound in fungi and human, that could be a novel drug to various diseases associated with hyperpigmentation by melanin.  相似文献   
3.
A novel series of mixed-ligand complexes of 5,5′-{(1E,1E′)-1,4-phenelynebis(diazene-2,1-diyl)}bis(quinolin-8-ol) (H2L1) as a primary ligand and 4-aminoantipyrine(L2) as a secondary ligand with Mn(II) ion were prepared using two general formulae: [Mn2(H2L1)2(L2)2X4].4Cl (X = OH2( 1 ), ONO2( 2 ), Cl=nil; OAc( 3 ), Cl = nil) and [Mn2(H2L1)(L2)2(O2SO2)2]( 4 ). Free ligands and their complexes were characterized. Electronic absorption spectra of the mixed-ligand complexes indicate a distorted octahedral geometry around the central metal ion, and the anions X are in the axial positions for all compounds. The ligands behave in a neutral bidentate manner, through nitrogen atoms and oxygen atoms of the carbonyl group (L2), whereas H2L1 coordinated through nitrogen and OH groups as a neutral bidentate ligand. All complexes do not contain coordinated water molecules, but complex ( 1 ) contains four water molecules. The water molecules are removed in a single step. The complexes exhibited magnetic susceptibility corresponding to five unpaired electrons. The antimicrobial activity of the Mn(II) mixed-ligand complexes ( 1–4 ) against two gram-positive bacteria, three local gram-negative bacteria, and three fungi species was tested. Mn(II) mixed-ligand complex ( 2 ) exhibited significant antibacterial activity against Bacillus cereus, Staphylococcus aureus, Escherichia coli, Klebsiella pneumoniae, and Pseudomonas sp. Mixed-ligand complex ( 2 ) exhibited a high potential cytotoxicity against the growth of human lung cancer cells.  相似文献   
4.
Heavy metal ions are harmful to aquatic life and humans owing to their high toxicity and non‐biodegradability, so their removal from wastewater is an important task. Therefore, this work focuses on designing suitable, simple and economical nanosensors to detect and remove these metal ions with high selectivity and sensitivity. Based on this idea, different types of mesoporous materials such as hexagonal SBA‐15, cubic SBA‐16 and spherical MCM‐41, their chloro‐functionalized derivatives, as well as 4‐(4‐nitro‐phenylazo)‐naphthalen‐1‐ol (NPAN) azo dye have been synthesized, with the aim of designing some optical nanosensors for metal ions sensing applications. The mentioned azo dye has been anchored into the chloro‐functionalized mesoporous materials. The designed nanosensors were characterized using scanning and transmission electron microscopy as well as Fourier transform infrared and UV–visible spectral analysis, nitrogen adsorption–desorption isotherms, low‐angle X‐ray diffraction and thermogravimetric analyses. Their optical sensing to various toxic metal ions such as Cd (II), Hg (II), Mn (II), Fe (II), Zn (II) and Pb (II) at different values of pH (1.1, 4.9, 7 and 12) was investigated. The optimization of experimental conditions, including the effect of pH and metal ion concentration, was examined. The experimental results showed that the solution pH had a major impact on metal ion detection. The optical nanosensors respond well to the tested metal ions, as reflected by the enhancement in both absorption and emission spectra upon adding different concentrations of the metal salts and were fully reversible on adding ethylene diamine tetra acetic acid or citric acid to the formed complexes. High values of the binding constants for the designed nanosensors were observed at pHs 7 and 12, confirming the strong chelation of different metals to the nanosensor at these pHs. Also, high binding constants and sensitivity were observed for NPAN‐MCM‐41 as a nanosensor to detect the different metal ions. From the obtained results, we succeeded in transforming the harmful azo dye into an environmentally friendly form via designing of the optical nanosensors used to detect toxic metal ions in wastewater with high sensitivity.  相似文献   
5.
A dithiolate-containing a carbamate mononuclear cobalt(II) complex namely, [Co(Boc-S)2] (1), was obtained by the reaction of a methanolic solution of cobalt(II) nitrate hexahydrate with two equimolar amounts of the deprotonated form of tert-butyl N-(2-mercaptoethyl)carbamate (Boc-SH). The cobalt(II) complex (1) was characterized in the solid state and in solution by using FT–IR, Raman, UV–visible, and EI–mass spectroscopies, as well as thermal and X-ray diffraction studies. Spectral data showed that the carbamate (Boc-SH) acts as a mono-anionic bidentate ligand coordinating the cobalt(II) ion through two imine nitrogen and two deprotonated thiolate sulfur donor atoms in a distorted tetrahedral geometry. The thermoanalytical data evidence that the complex is stable up to 165 °C and undergoes complete decomposition, resulting in CoO. TEM imaging of the oxide residue shows its nano size clusters, suggesting that the complex (1) may be used as a precursor for nano-oxides. X-ray powder diffraction patterns evidence an isomorphism among the complex. The redox behavior of the cobalt(II) complex was also investigated by cyclic voltammetry. The reaction of the dithiolate cobalt(II) complex (1) with methyl iodide appears to occur intramolecularly with the cobalt-bound dithiolate, forming the cobalt(II)-bound dithioether complex [Co(Boc–SCH3)2]I2 (2), as a dication complex with a clean second-order reaction of 13.24 × 10−2 M−1·s−1.  相似文献   
6.
Concurrent sonolysis of iron pentacarbonyl and poly(ethylene glycol)-400 (PEG-400) in hexadecane solvent proceeds via zero-order kinetics and results in Fe nanoparticles encapsulated in PEG-400 (Fe-PEG). The transmission electron microscopy images show Fe-PEG consisting of <3 nm Fe particles that are evenly dispersed in the PEG matrix. M?ssbauer and X-ray absorption fine structure/X-ray absorption near-edge structure data reveal an ordered PEG assembly that helps protect the zerovalent Fe core. The Fe nanoparticles in Fe-PEG are superparamagnetic with a magnetization value of 45 emu/g-Fe at 10 KOe. The rheology of the synthesized material shows an unusual increase in viscosity with temperature that is likely due to lower critical saturation temperature phase segregation over 40 degrees C. The low-temperature mobility of the PEG-400 moiety in Fe-PEG would allow facile ligation of the Fe0 core with biologically and chemically active groups.  相似文献   
7.
The X-ray structures of three new crystals of nitroxylcobalamin (NOCbl) have been determined. Unlike our earlier reported structure in which NOCbl was partially oxidized (L. Hannibal, C. A. Smith, D. W. Jacobsen and N. E. Brasch, Angew. Chem., Int. Ed. 2007, 46, 5140), the O atom of the nitroxyl ligand is located in a single position with a N=O bond distance of 1.12-1.14 ?, consistent with a double bond. The Co-N-O angle is in the 118.9-120.3 ? range. The α-axial Co-N(dimethylbenzimidazole) (Co-NB3) bond distance is a remarkable 2.32-2.35 ? in length, ~0.1 ? longer than that reported for all other cobalamin structures. The change in the Gibbs free energy for the base-on/base-off equilibrium now correlates extremely well with the Co-NB3 bond distance, as observed for other cobalamins.  相似文献   
8.
Two novel Schiff base ligands of 2-amino-3-cyano-1,5-diphenylpyrrole and salicylaldehyde (HL1) or 2- hydroxy1-naphthylaldehyde (HL2) and their copper(II) complexes have been synthesized and characterized by elemental analyses, spectral (UV-Vis, IR, EPR, Mass (for ligands)), thermal (DTA-TGA) methods, magnetic and conductance measurements. IR results demonstrate the bidentate binding of the Schiff base ligands involving azomethine nitrogen, phenolic or naphtholic oxygen and suggest the presence of HL2 and complexes (1, 2, 4 and 8) in enolimine-ketonamine tautomeric forms in the solid state. The EPR spectral data of complexes (2, 5, 6) show that the metal — ligand bonds have considerable covalent character. The thermal studies show that complexes (1, 2, 4 and 8) that are present in enolimine-ketonamine tautomeric forms exhibit lower thermal stability. The effect of synthesized ligands (HL1, HL2) and complexes (1, 5) were tested on the mortality of entomopathogenic nematodes (EPN) (Heterorhabditis bacteriophora and Steinernema carpocapsae). The study shows that the mortality of the nematodes increased with increasing concentrations of copper(II) ion, ligands and complexes. Copper(II) ion was the most toxic for EPN.   相似文献   
9.
In this paper, we derive the performance measures of the truncated Erlangian service queueing system with state-dependent rate, balking and reneging with fuzzy arrival rate _n\tilde \lambda _n so for the (M/E r /1/N(α, β)), we have obtained P n,s the steady state probabilities in the system with the unit in the service being at stage s (s=1, 2, …, r); k is the boundary state for the number of customer more than the one that the rate of service increases. We treat this queueing system for general values of r, k and N and derive the Fuzzy effective measures for the operation of the system at any time.  相似文献   
10.
Naltrexone HCl (NAL.HCl) has been reduced at the mercury electrode in Britton-Robinson universal buffer of pH values 2-11 with a mechanism involving the quasi-reversible uptake of the first transferring electron followed by a rate-determining protonation step of its C=O double bond at position C-6. Simple, sensitive, selective and reliable linear-sweep and square-wave adsorptive cathodic stripping voltammetry methods have been described for trace quantitation of NAL.HCl in bulk form, commercial formulation and human body fluids without the necessity for sample pretreatment and/or time-consuming extraction steps prior to the analysis. Limits of quantitation of 6.0×10(-9)M and 8.0×10(-10)M NAL.HCl in bulk form or commercial formulation and of 9.0×10(-9) and 1.0×10(-9)M NAL.HCl in spiked human serum samples were achieved by the described linear and square-wave stripping voltammetry methods, respectively. Furthermore, pharmacokinetic parameters of the drug in human plasma samples of healthy volunteers following the administration of an oral single dose of 50mg NAL.HCl (one Revia(?) tablet) were estimated by means of the described square-wave stripping voltammetry method without interferences from the drug's metabolites and/or endogenous human plasma constituents. The estimated pharmacokinetic parameters were favorably compared with those reported in literature.  相似文献   
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