Radioprotectant Activity of Dicopper(II) Tetrakis(3,5- Diisopropylsalicylate) and Manganese(II) bis(3,5- Diisopropylsalicylate) Alone and in Combination

Dicopper(ll) tetrakis(3,5-diisopropylsalicylate), (Cu(II)(2)(3,5-DIPS)(4), manganese(II) bis(3,5-diisopropylsalicylate), Mn(II)3,5-DIPS)(2) or combinations of them were used to treat gamma-irradIated mice in examining the possibility that combination treatments might be more effective in increasing survival than treatment with either complex alone. Doses of 0, 10, 20, or 40 mumol of each complex per kilogram of body mass were administered subcutaneously in a factorial design before 9 Gy gamna irradiation, an LD(90) dose of irradiation. Doses of 0, 10, 20, or 40 mumol Cu(II)(2)(3, 5-DIPS)(4) per kg of body mass produced 12, 28, 28, or 36 % survival, respectively, while doses of 0, 10, 20, or 40 mumol (II)(3), 5-DIPS)(2) per kg of body mass prduced 12, 36, 20, or 24 % survival, respectively. However, the combination of 20 mumol Cu(II)(2)(3, 5-DIPS)(4) and 10 mumol Mn(II)(3, 5-DIPS)(2) produced the greatest survival, 48 %, which was 300 % greater than vehicle-treated mice (P=0.01). It is concluded that specific combination treatments can be used to maximize survival of lethally irradiated mice.     

3-(3,5-二甲氧基苯乙烯基)苯酚的合成及抗肿瘤活性研究

以3-甲氧基苄基磷酸二乙酯(Ⅰ)为原料,首先经三溴化硼脱甲基得到3-羟基苄基磷酸二乙酯(Ⅱ),随后在甲醇钠的催化下与3,5-二甲氧基苯甲醛(Ⅲ)发生Wittig-Horner反应得到3-(3,5-二甲氧基苯乙烯基)苯酚(Ⅳ),采用核磁共振氢谱表征其结构,并优化了反应条件.确定最佳的脱甲基化反应条件为:BB r3为脱甲基...     

用溶剂萃取法回收电镀废水中的铜和镍(英文)

The solvent extraction technology was applied to recover Cu2+ and Ni2+ from plating wastewater. Lix984N was chosen as the extractant due to its good extraction performance. The influence parameters were examined. The results show that the separation of Cu2+ and Ni2+ from sulphate medium can be realized by adjusting pH value with the help of Lix984N. For extracting Cu2+ and Ni2+, the optimal pH values are 4 and 10.5, and the maximal extraction percentages are 92.9% and 93.0%, respectively. With recovered Cu2...     

Cu(II) Adsorption of Activated Carbon Fibers Produced by Radiation-Induced Graft Polymerization

In this work, the adsorption behaviors of activated carbon fibers (ACFs) containing chelating functional groups were studied in heavy metal ion removal. The ACFs were modified by electron beam and glycidyl methacrylate (GMA, CH₂—CCH₃COOCH₂CHOCH₂) graft polymerization in order to induce chelating functional groups, such as iminodiacetate (IDA, NH(CH₂COOH)₂) groups on the ACF surfaces. Fourier transform-infrared spectrometry (FT-IR) and X-ray photoelectron spectroscopy (XPS) were used to characterize the surface properties of the ACFs. The specific surface area and the pore structure were evaluated from nitrogen adsorption data at 77 K. The adsorbed amount of heavy metal ions was measured by using inductively coupled plasma-atomic emission spectrometer (ICP-AES). Results of FT-IR and XPS showed that the relative intensity of oxygen peaks increased with increasing the dose of electron beam. The results indicated that the radicals were increased as the dose of electron beam irradiation increased, and increased radicals led to the increase of the IDA groups. Also, the adsorption of heavy metal ions was increased by increasing the dose of electron beam irradiation. It was explained that the IDA groups of the treated ACF surfaces were introduced by radiation-induced graft polymerization and the increased IDA groups led to an increase of the adsorption of heavy metal ions.     

Dicopper(I) and disilver(I) complexes of a thiophene-derived Schiff base macrocycle

Dicopper(I) and disilver(I) complexes of a tetraimine Schiff base macrocycle derived from the cyclocondensation of thiophene-2,5-dicarbaldehyde with 1,4,7-triazaheptane (1) have been synthesised and characterised. The structure of Cu₂(1)(BF₄)₂·2CH₃CN is given.     

2,6-二氨基-3,5-二硝基吡啶-1-氧化物Ni(II)和Cu(II)含能配合物的燃烧催化性能

按照文献方法,制备了2,6-二氨基-3,5-二硝基吡啶-1-氧化物(ANPyO)Ni(II)和Cu(II)两种含能配合物,用激光粒度测试仪及GJB772A-97法测试了粒度和感度,用密闭爆发器分别测试了含ANPyO Ni(II)和Cu(II)配合物发射药的燃烧性能,用靶线法测试了含两种配合物双基推进剂的燃烧催化性能。研究了两种配合物在双基发射药、三基发射药和双基推进剂中的燃烧作用。结果表明,ANPyO Ni(II)和Cu(II)两种配合物粒度都为微米级,爆速大于8 200m/s,爆压大于32GPa,优于TATB、HNS和PYX;两种含能配合物能够提高双基发射药的燃速,使其压强指数分别降低7.61%和3.29%,对双基发射药的燃烧性能具有明显的促进效果;ANPyO Cu(II)配合物使双基推进剂在10~20MPa下燃速提高20%,压强指数降低17.78%~55.84%,对双基推进剂的燃烧性能具有良好的催化效果。     

Dehydrated Carbon Fiber for the Recovery of Pd(II) and Pt(II) From Chloride Aqueous Solution

Cellulose fiber was separated from date palm leaflets and was carbonized by dehydration using dilute sulfuric acid at 150°C. Produced dehydrated carbon fiber (DCF) was tested for the sorption of Pd(II) and Pt(II) at different pH, contact time, metal concentration, and temperature. With the rise in pH, sorption was found to increase for Pd(II) but decreases for Pt(II). The optimum pH ranges of 1-3 for Pt(II) and 3-3.5 for Pd(II). Approximate equilibrium was obtained within 50 hr for both metals with sorption data fitting the pseudo second order model well. Activation energy, Ea, was found to be higher than 40 kJ/mol for the sorption of both metals, indicating the involvement of chemical processes in metal sorption. The Langmuir isotherm was found to fit the sorption data more than other isotherms. Thermodynamic parameters were calculated and showed an involvement of chemical processes in metal sorption with stronger interaction for the carbon with Pb(II) than with Pt(II). Both of Pd(II) and Pt(II) were reduced to their respective elemental forms on the surface of the fiber as confirmed by scanning electron microscopy and x-ray diffraction.     

合成抗氧剂1010酯交换反应的工艺研究

以有机锡为催化剂的合成抗氧剂1010工艺为背景,实验研究了温度、压力和搅拌对酯交换反应的影响,得到了最佳的工艺操作条件,研究能为工业生产的优化操作和合理选用搅拌桨型提供依据。     

Homogenous and Heterogeneous Catalytic Activity of Azo-Linked Schiff Base Complexes of Mn(II), Cu(II) and Co(II)

Abstract  

Azo linked Schiff-base[L] complexes of Mn(II)(1), Cu(II)(2) and Co(II)(3) obtained by template method, in the reaction of 4-(benzeneazo) salicylaldehyde with 1,2-propanediamine in the present of metal acetate, respectively. Complexes are used as catalyst for oxidation of cyclohexene with tert-butylhydroperoxide (TBHP); oxidation of cyclohexene catalyzed by these complexes gave 2-cyclohexene-1-one and 2-cyclohexene-1-ol as major products. Conversion of cyclohexene achieved was 95–100% with (1), (2) and (3), with selectivity of 57, 92 and 100% for 2-cyclohexene-1-one, respectively. The encapsulated Cu(II) complex (Cu–NaY) catalyzes the oxidation of cyclohexene using TBHP as oxidant in good yield. (Cu–NaY) under optimized reaction condition gave three reaction products. A maximum of 100% conversion of cyclohexene has been achieved where selectivity of 2-cyclohexene-1-one was 83%.     

Synthesis, Characterization and Antiproliferative Activity of the Co(II), Ni(II), Cu(II), Pd(II) and Pt(II) Complexes of 2-(4-Thiazolyl)Benzimidazole (Thiabendazole)

Complexes of 2-(4-thiazolyi)benzimidazole (thiabendazole, THBD) with Co(II), Ni(II), Cu(ll) of general formula ML(2)(NO(3))(2) H(2)O and complexes of Pd(II) and Pt(II) of general formula ML2Cl(2) H(2)O have been obtained and characterized by elemental analyses, IR and far IR spectroscopy and magnetic measurements. The X-ray crystal structure of the copper(II) complex has been determined. The in vitro cell proliferation inhibitory activity of these compounds was examined against human cancer cell lines A 549 (lung carcinoma), HCV-29 T (urinary bladder carcinoma), MCF-7 (breast cancer), T47D (breast cancer), MES-SA (uterine carcinoma) and HL-60 (promyelocytic leukemia). Pt-THBD has been found to exhibit an antileukemic activity of the HL-60 line cells matching that of an arbitrary criterion.     

Synthesis,crystal structures and properties of two Pd(II) and Pt(II) complexes involving 3,5-diphenylpyrazole and NO2 donor ligands

A pyrazolate bridged binuclear Pd(II) complex [Pd₂(μ-dppz)₂(Hida)₂] · CH₃OH · 2H₂O (1) (dppz = 3,5-diphenylpyrazolate) with monoprotonated iminodiacetate (Hida) and a mononuclear Pt(II) complex containing Hdppz and 2,6-pyridinedicarboxylate (2,6-dipic) [Pt(Hdppz)(2,6-dipic)] · CH₃OH (2) have been synthesized and characterized by elemental analysis, ¹H NMR, ESI-MS and single crystal X-ray diffraction studies. The molecular packing for 1 shows a 2D network while that for 2 constitutes a left-handed 1D helix. Moderate luminescence property and antimicrobial activity against Bacillus subtilis have been noted for both.     

Dithiooxamide-Immobilized Microalgal Residue for the Selective Recovery of Pd(II) and Pt(IV)

Microalgal residue was chemically modified by immobilizing a functional group of dithiooxamide to prepare a novel type of adsorbent. This adsorbent exhibited high adsorption affinity and selectivity for Pd(II) and Pt(IV) whereas the adsorption of coexisting base metal ions was negligible. From the adsorption isotherms, this adsorbent was found to exhibit remarkably high adsorption capacity. The thermodynamic parameters indicated that the adsorption is governed by an endothermic reaction. The effective separation of Pd(II) and Pt(IV) from Cu(II) was confirmed also by a dynamic adsorption test. The effectiveness of elution of adsorbed Pd(II) and Pt(IV) was 85% and 96%, respectively.     

Down-Regulation of Porcine Heart Diaphorase Reactivity by Trimanganese Hexakis(3,5-Diisopropylsalicylate), Mn(3)(3,5-DIPS)6, and Down-Regulation of Nitric Oxide Synthase Reactivity by Mn(3)(3,5-DIPS)(6) and Cu(II)(2)(3,5-DIPS)(4)

Purposes of this work were to examine the plausible down-regulation of porcine heart diaphorase (PHD) enzyme reactivity and nitric oxide synthase (NOS) enzyme reactivity by trimanganese hexakis(3,5-diisopropylsalicylate), [Mn(3)(3,5-DIPS)(6)] as well as dicopper tetrakis(3,5- diisopropylsalicylate, [Cu(II)(2)(3,5-DIPS)(4)] as a mechanistic accounting for their pharmacological activities.Porcine heart disease was found to oxidize 114 muM reduced nicotinamide-adenine- dinucleotide-'(3)-phosphate (NADPH) with a corresponding reduction of an equivalent concentration of 2,6-dichlorophenolindophenol (DCPIP). As reported for Cu(II)(2) (3,5-DIPS)(4), addition of Mn(3)(3,5-DIPS)(6) to this reaction mixture decreased the reduction of DCPIP without significantly affecting the oxidation of NADPH. The concentration of Mn(3)(3,5-DIPS)(6) that produced a 50% decrease in DCPIP reduction (IC(50)) was found to be 5muM. Mechanistically, this inhibition of DCPIP reduction with ongoing NADPH oxidation by PHD was found to be due to the ability of Mn(3)(3,5-DIPS)(6) to serve as a catalytic electron acceptor for reduced PHD as had been reported for Cu(II)(2)(3,5-DIPS)(4). This catalytic decrease in reduction of DCPIP by Mn(3)(3,5-DIPS)(6) was enhanced by the presence of a large concentration of DCPIP and decreased by the presence of a large concentration of NADPH, consistent with what had been observed for the activity of Cu(II)(2)(3,5-DIPS)(4)Oxidation of NADPH by PHD in the presence of Mn(3)(3,5-DIPS)(6) and the absence of DCPIP was linearly related to the concentration of added Mn(3)(3,5-DIPS)(6) through the concentration range of 2.4 muM to 38muM with a 50% recovery of NADPH oxidation by PHD at a concentration of 6 muM Mn(3)(3,5-DIPS)(6)Conversion of [(3)H] L-Arginine to [(3)H] L-Citrulline by purified rat brain nitric oxide synthase (NOS) was decreased in a concentrated related fashion with the addition of Mn(3)(3,5-DIPS)(6) as well as Cu(II)(2)(3,5-DIPS)(4) which is an extention of results reported earlier for Cu(II)(2)(3,5-DIPS)(4). The concentration of these two compounds required to produce a 50% decrease in L-Citrulline synthesis by NOS, which may be due to down-regulation of NOS, were 0.1 mM and 8muM respectively, consistent with the relative potencies of these two complexes in preventing the reduction of Cytochrome c by NOS.It is concluded that Mn(3)(3,5-DIPS)(6), as has been reported for Cu(II)(2) (3,5-DIPS)(4) , serves as an electron acceptor in down-regulating PHD and both of these complexes down-regulate rat brain NOS reactivity. A decrease in NO synthesis in animal models of seizure and radiation injury may account for the anticonvulsant, radioprotectant, and radiorecovery activities of Mn(3)(3,5-DIPS)(6) and Cu(II)(2)(3,5-DIPS)(4).     

Adsorptive Recovery of Palladium(II) and Platinum(IV) on the Chemically Modified-Microalgal Residue

A biomass waste of microalgae was chemically modified by immobilizing the functional group of polyethyleneimine to prepare a new type of adsorbent. The adsorption test revealed that this adsorbent exhibited remarkably high selectivity for Pd(II) and Pt(IV) over base metal ions in HCl solution. From the adsorption isotherm, its maximum adsorption capacity for Pd(II) and Pt(IV) was evaluated as 2.0 and 0.8 mmol/g, respectively. This adsorbent also exhibited high affinity and selectivity for Pd(II) and Pt(IV) even in the presence of high concentrations of base metals in actual leach liquor.     

Activity of Nickel(II) Oxide in Silicate Melts

Activity–composition relations of NiO have been determined at 1435°C in melts of the system CaO–NiO–SiO₂ and at 1400°C in melts of the systems CaO–MgO–NiO–SiO₂, CaO–MgO–NiO–Al₂O₃–SiO₂, and CaO–MgO–NiO–K₂O–SiO₂. In the CaO–NiO–SiO₂ and CaO–MgO–NiO–SiO₂ systems the activity coefficient of NiO (γ_NiO) decreases as the polymerization of the melt increases (basicity decrease). γ_NiO stays contant up to several weight percent NiO for melts with similar basicity, an indication of Henry's law behavior. Minima in the NiO activity coefficient are observed in melts of the CaO–MgO–NiO–Al₂O₃–SiO₂ and CaO–MgO–NiO–K₂O–SiO₂ systems at NBO/Si ratios between 1.0 and 1.5; i.e., γ_NiO decreases with decreasing basicity for NBO/Si ratios >1.5 and increases with decreasing basicity for melts with NBO/Si ratios <1.0 (NBO/Si; nonbridging oxygens per silicon). The addition of Al₂O₃ and K₂O to the CaO–MgO–NiO–SiO₂ system results in an increase in the activity coefficient of NiO.     

Antifungal Activity of Ag(I) and Zn(II) Complexes of Sulfacetamide Derivatives

Reaction of sulfacetamide with arylsulfonyl isocyanates afforded a series of derivatives which were used as ligands (as conjugate bases) for the preparation of metal complexes containing Ag(I) and Zn(II). The newly synthesized complexes, unlike the free ligands, act as effective antifungal agents against Aspergillus and Candida spp., some of them showing activities comparable to ketoconazole, with minimum inhibitory concentrations in the range of 0.3 - 0.5 mug/mL. The mechanism of antifungal action of these complexes seems to be not connected with the inhibition of lanosterol-14-alpha-demethylase, since the levels of sterols assessed in the fungi cultures were equal in the absence or in the presence of the tested compounds. Probably the new complexes act as inhibitors of phosphomannose isomerase, a key enzyme in the biosynthesis of yeast cell walls.     

Properties of Binuclear Rhodium(II) Complexes and Their Antibacterial Activity

Binuclear rhodium(II) complexes [Rh(2)Cl(2)(mu-OOCR)(2)(N-N)(2)], [Rh(2)(mu-OOCR)(2)(N-N)(2)(H(2)O)(2)](RCOO)(2) and [Rh(2)Cl(2)(mu-OOCCH(3))(terpy)(2)](H(3)O)Cl(2).9H(2)O (R = H, Me, Bu(n), ph, PhCHOH; N-N = 2,2'-bipyridine (bpy), 1,10-phenanthroline (phen), 2,9-dimethyl-1,10-phenanthroline (dmp) and 6,7-dimethyl-2,3- di(2-pyridyl)quinoxaline (dmpq); terpy 2,2':6',2'-terpyridine) have been synthesized and their structure and properties have been studied by electronic, IR and (1)H NMR spectroscopy. Antibacterial activity of these complexes against Staphylococcus aureus and Escherichia coli has been investigated. The most active antibacterial agents against S. aureus were [Rh(2)(OOCPh)(2)(phen)(2)(H(2)O)(2)](2+), [Rh(2)(OOCPh)(2)(dmpq)(2)(H(2)O)(2)](2+), [Rh(2)(OOCBu)(2)(phen)(2)(H(2)O)(2)](2+) and [Rh(2)-(OOCBu)(2)(bpy)(2)(H(2)O)(2)](2+) which were considerably more active than the appropriate nitrogen ligands. The complexes show rather low activity against E. coli.     

Ruthenium(II) and Platinum(II) Complexes with Biologically Active Aminoflavone Ligands Exhibit In Vitro Anticancer Activity

Continuing our studies on the mechanisms underlying the cytotoxicity of potential drugs, we have described several aspects of the in vitro anticancer activity of ruthenium(II) and platinum(II) complexes with bioactive, synthetic aminoflavone ligands. We examined the mechanism of proapoptotic activity of cis-dichlorobis(3-imino-2-methoxyflavanone)ruthenium(II), cis-dichlorobis(3-imino-2-ethoxyflavanone)ruthenium(II), and trans-dichlorobis(3-aminoflavone)platinum(II). Cisplatin was used as a reference compound. The cytotoxicity was investigated by MTT assay. The mechanism of proapoptotic activity of the tested compounds was investigated by evaluation of caspase-8 activity, cytometric analysis of annexin-V positive cells, and mitochondrial potential loss measurement. The results showed that ruthenium compounds break partially or completely the cisplatin resistance by activating the caspase 8-dependent apoptosis pathway and loss of mitochondrial membrane potential. Platinum compounds also have a cytostatic effect, but their action requires more exposure time. Potential mechanisms underlying drug resistance in the two pairs of cancer cell lines were investigated: total glutathione content, P-glycoprotein activity, and differences in the activity of DNA repair induced by nucleotide excision. Results showed that cisplatin-resistant cells have elevated glutathione levels relative to sensitive cells. Moreover, they indicated the mechanisms enabling cells to avoid apoptosis caused by DNA damage. Pg-P activity has no effect on the development of cisplatin resistance in the cell lines described.     

Biological Activity of Some Magnesium(II) Complexes of Quinolones

A new magnesium complex of quinolone antibacterial agent was prepared. This new complex as well as a previously isolated complex of magnesium with ciprofloxacin were tested against various Gram positive and Gram negative microorganisms. Antimicrobial activities were evaluated using the agar diffusion test. The results have shown that all magnesium complexes are significantly less active than the parent quinolone drugs. It was also found that the activity of quinolones is reduced when the solutions of quinolones are titrated with magnesium ions.     

Preclinical Anticancer Activity of an Electron-Deficient Organoruthenium(II) Complex

Ruthenium compounds have been shown to be promising alternatives to platinum(II) drugs. However, their clinical success depends on achieving mechanisms of action that overcome Pt-resistance mechanisms. Electron-deficient organoruthenium complexes are an understudied class of compounds that exhibit unusual reactivity in solution and might offer novel anticancer mechanisms of action. Here, we evaluate the in vitro and in vivo anticancer properties of the electron-deficient organoruthenium complex [(p-cymene)Ru(maleonitriledithiolate)]. This compound is found to be highly cytotoxic: 5 to 60 times more potent than cisplatin towards ovarian (A2780 and A2780cisR), colon (HCT116 p53+/+ and HCT116 p53−/−), and non-small cell lung H460 cancer cell lines. It shows no cross-resistance and is equally cytotoxic to both A2780 and A2780cisR cell lines. Furthermore, unlike cisplatin, the remarkable in vitro antiproliferative activity of this compound appears to be p53-independent. In vivo evaluation in the hollow-fibre assay across a panel of cancer cell types and subcutaneous H460 non-small cell lung cancer xenograft model hints at the activity of the complex. Although the impressive in vitro data are not fully corroborated by the in vivo follow-up, this work is the first preclinical study of electron-deficient half-sandwich complexes and highlights their promise as anticancer drug candidates.