Toxic effect of transition metal complexes on Salmonella typhi,Escherichia coli and Serratia marcescens

The present article describes the synthesis, structural features and toxicological studies of the complexes of the type [M(L)(dipy-amine)(H₂O)] or [M(L)(bendan)(H₂O)] where M?=?Mn(II), Co(II), Ni(II), Cu(II), Zn(II) and Cd(II), H₂L?=?salicylidene-o-aminothiophenol, dipy-amine?=di(2-pyridyal)amine, or bendan?=?bis(benzylidene)1,8-diaminonaphthalene. The complexes have been characterized on the basis of elemental analyses, electronic spectra, magnetic measurement and thermogravimetric analyses. The nature of the bonding has been discussed on the basis of infrared spectral data. A thermal study of the complexes has been carried out to ascertain their thermal stability. Magnetic susceptibility measurements and electronic spectral data suggest a six-coordinated octahedral structure for these complexes. The complexes of Mn(II), Co(II), Ni(II), Cu(II) are paramagnetic, while Zn(II) and Cd(II) are diamagnetic in nature. The toxic effects of the investigated complexes were tested against three Gram-negative bacteria, Salmonella typhi, Escherichia coli and Serratia marcescens by the “Disc Diffusion Method”. It is observed that the complexes show higher toxic effects as compared to the ligands, metal salts and control (DMSO), but moderate toxic effects as compared to the standard drug (tetracycline) and the results are discussed.     

Synthesis,structural elucidation,electro-chemical behaviour and fungitoxic activity of transition metal(II) mixed-ligand complexes with some Schiff bases

The Schiff bases, potassium salt of salicylidene-β-alanine [KHL], bis(benzylidene)ethylenediamine [SB¹] and thiophene-o-carboxaldene-p-toluidine [SB²], and mixed-ligand complexes with Mn(II), Co(II), Ni(II), Cu(II), Zn(II), and Cd(II) have been prepared. They were characterized by elemental analyses, magnetic susceptibility measurements, thermogravimetric analyses (t.g.a.), infrared spectra and electronic spectra. The mixed-ligand complexes were found to have the general composition [M(L)(SB)(H₂O)]. All the mixed-ligand complexes were found to have six-coordinated octahedral geometry. The fungitoxic activity of the ligands, metal salts, control (DMSO), bavistin, emcarb, and mixed-ligand complexes were screened against Aspergillus niger, Fusarium oxysporum and Aspergillus flavus. All the mixed-ligand complexes show higher fungitoxic activity as compared to the Schiff bases, metal nitrate and control (dimethyl sulphoxide, DMSO), and moderate fungitoxic activity as compared to the fungicides (bavistin and emcarb).     

Synthesis and biological activities of new azacrown ether Schiff bases and spectrophotometric studies of their complexation with [60]fullerene

A series of novel azacrown ether Schiff bases 1–3 have been synthesized in good yield and in a simple way. Their host–guest interaction with [60]fullerene has been studied in toluene by absorption spectroscopic method. All the complexes are found to be stable with 1:1 stoichiometry. Because of their potential applications in industry, agriculture and medicine, they were investigated for their mutagenic and antimutagenic activities using the spot test and the plate incorporation assay of Ames. Compounds 1, 2 and 3 were found to be nonmutagenic in the Ames test using strains TA 1535, TA100 and TA97a of Salmonella typhimurium. However, using strain TA102 revealed that, although both compounds 1 and 2 were nonmutagenic, compound 2 gave a positive response indicating that it acts as an oxidative mutagen. The structure-activity relationship may throw some light on the biological activity of such series of compounds.     

Spectroscopic studies and biological evaluation of some transition metal complexes of a novel Schiff base ligands derived from 5-arylazo-salicyladehyde and o-amino phenol

Synthesis and characterization of Cu(II), Ni(II), and Zn(II) Schiff bases complexes resulted from the condensation of salicylaldehyde derivatives with o-amino phenol were discussed using elemental analysis (carbon, hydrogen, and nitrogen), molar conductance, magnetic measurements, mass spectra, and electronic spectra. The essential bands of infrared, ¹HNMR, and UV-Vis spectra as well as thermogravimetric analysis corresponding to the active groups within the three ligands and their complexes were interpreted. The dehydration and decomposition processes of the [Cu(H₂L₁)(H₂O)](OAc)₂, [Ni(H₂L₁)(H₂O)]SO₄ · H₂O, [Zn(H₂L₁)(H₂O)]SO₄ · H₂O, [Cu(H₂L₂)(H₂O)](OAc)₂, [Ni(H₂L₂)(H₂O)]SO₄ · H₂O, [Zn(H₂L₂)(H₂O)]SO₄ · 2H₂O, [Cu(H₂L₃)(H₂O)](OAc)₂ · H₂O, [Ni(H₂L₃)(H₂O)]SO₄ · 2H₂O, [Zn(H₂L₃)(H₂O)]SO₄ complexes were studied thermodynamically using the integral method applying the Coats–Redfern and Horowitz–Metzger equations and the thermodynamic parameters were calculated. It was found from the elemental analysis and the thermal studies, that the ligand behaves as tridentate ligand forming chelates with 1 : 1 (metal : ligand) stoichiometrically. The molar conductance measurements of the complexes in dimethyl sulfoxide solvent indicate that the complexes have an electrolytic nature. The biological activities of the three ligands in comparison with metal(II) complexes were studied against different Gram positive and Gram negative bacteria.     

In vitro fungitoxic activity of some Schiff bases and their oxovanadium(IV) complexes

The oxovanadium(IV) (VO(IV)) complexes, Schiff bases, vanadyl sulphate, standard fungicides (bavistin and emcarb) and control (dimethyl sulphoxide) were tested for their in vitro fungitoxic activity on A. niger, F. oxysporum and A. flavus. The oxovanadium(IV) complexes show higher fungitoxic activity as compared with the free ligands, vanadyl sulphate and control (dimethyl sulphoxide), but moderate fungitoxic activity as compared with the standard fungicides (bavistin and emcarb). Oxovanadium(IV) complexes have been prepared with biologically active Schiff bases viz. the potassium salt of salicylidene-DL-alanine (sal-ala), 2,2′-bipyridylamine (bipym), bis(benzylidene)ethylenediamine (benen), thiophene-o-carboxaldeneaniline (tca), thiophene-o-carboxaldene-p-toluidine (tct), bis(benzylidene)-1,8-diaminonaphthalene (bendan) or bis(acetophenone)ethylenediamine (acphen). They have been characterized on the basis of elemental analysis, thermogravimetric analysis, magnetic measurements, electronic and infrared spectra. An octahedral geometry has been tentatively assigned to all the complexes.     

The chelation of metal ions by the acylpolyamine toxins from the web-spider Nephilengys cruentata: effects in the intoxication/detoxification of preys

Summary. Orb-web-spiders present a series of different strategies for prey capture, involving the use of different types of silk for web building, the use of adhesive traps in the webs, the secretion of toxic compounds to the spider’s preys in the adhesive coating of the capture web and the biosynthesis of a wide range of structurally related acylpolyamine toxins in their venoms. The polyamine toxins usually block neuromuscular junctions and/or the central nervous system (CNS) of Arthropods, targeting specially the ionotropic glutamate receptors; this way these toxins are used are as chemical weapons to kill / paralyze the spider’s prey. Polyamine toxins contain many azamethylene groups involved with the chelation of metal ions, which in turn can interact with the glutamate receptors, affecting the toxicity of these toxins. It was demonstrated that the chelation of Ni⁺², Fe⁺², Pb⁺², Ca⁺² and Mg⁺² ions by the desalted crude venom of Nephilengys cruentata and by the synthetic toxin JSTX-3, did not cause any significant change in the toxicity of the acylpolyamine toxins to the model-prey insect (honeybees). However, it was also reported that the chelation of Zn⁺² ions by the acylpolyamines potentiated the lethal / paralytic action of these toxins to the honeybees, while the chelation of Cu⁺² ions caused the inverse effect. Atomic absorption spectrometry and Plasma-ICP analysis both of N. cruentata venom and honeybee’s hemolymph revealed that the spider’s venom concentrates Zn⁺² ions, while the honeybee’s hemolymph concentrates Cu⁺² ions. These results are suggesting that the natural accumulation of Zn⁺² ions in N. cruentata venom favors the prey catching and/or its maintenance in the web, while the natural accumulation of Cu⁺² ions in prey’s hemolymph minimizes the efficiency of the acylpolyamine toxins as killing/paralyzing tool.     

The effect of limiting nutrient on metal toxicity to selenastrum capricornutum

Metal toxicity on selenastrum capricornutum were examined by batch culture and chemostat culture system. EC₅₀ values under nutrient‐limited condition and saturated condition were compared. The two EC_5Os differed by a factor of 10.6 for Cd in batch test, and differed by a factor of 6.5 in continuous test. Both batch and continuous test results indicate that inhibition on algal growth is more severe under nutrient‐limited conditions compared to that under near saturation conditions.

Strong correlation, as characterized by the correlation coefficient ρ, were found between the activation level (nutrient requirement) and the tolerance of microorganisms to the toxicant. ρ is equal to 0.9 for the case of Cd in batch test and 0.6 in continuous test. The theory in this study provides generally good estimations to the dose‐response relationship at limiting nutrient conditions. The study indicate that nutrient conditions constitute an important factor in algal toxicity tests.     

基于密度泛函理论模拟单壁碳纳米管对五种核酸碱基的吸附

基于密度泛函理论,模拟了单壁碳纳米管(SWNTs)对5种碱基的吸附作用.考察了SWNTs直径、电荷转移量、碱基最高占据分子轨道能(EHOMO)和最低未占据分子轨道能(ELUMO)与SWNTs吸附碱基的吸附能之间的关系.结果表明,随着SWNTs直径的增大,SWNTs吸附碱基的吸附能降低.SWNT(6,6)吸附5种碱基的最低吸附能Emin与由碱基转移到SWNTs的电荷转移量(Q)及碱基的EHOMO线性负相关,相关系数分别为-0.966和-0.804(P<0.05).吸附后SWNTs与碱基的前线轨道无重叠,且SWNTs电子结构未受影响,表明吸附行为属于物理吸附.     

镍对蔬菜毒害临界值的研究

采用水培＋土培的方法研究了镍对蔬菜的毒害临界值。先采用水培法从18种福建常见蔬菜中筛选出对镍毒害的高敏感蔬菜,再通过土培试验确定土壤镍对高敏感蔬菜的毒害临界值。结果表明,在水培条件下镍对蔬菜生长存在低浓度的刺激效应和高浓度的抑制效应。综合表观症状和蔬菜地上部生物量降低20％的效应浓度值（EC20）确定清江白（Brassica chinensis L．）和蕹菜（Lpomoea aquatica Forsk．）为镍毒害的高敏感蔬菜。以蕹菜为指示作物的土培试验表明,随着镍添加量的增加,蕹菜地上部生物量显著下降。以土培条件下蕹菜地上部生物量降低10％为依据,确定土壤有效镍毒害临界值为2．21mg·kg^-1（DTPA提取）;根据野外采集的菜园土壤DTPA提取镍和全镍的回归关系,求得土壤全镍毒害临界值为43．67mg·kg^-1。     

四种农药对蛙类的毒性与评价

测定了甲基异柳磷等四种新农药对泽蛙蝌蚪的毒性，作出了安全性预评价。结果表明：四种农药对蛙类均为无实际危害的低毒农药。克草胺施药期与蛙类蝌蚪期正相吻合，因此在使用时应采取措施，尽量避免对蛙类蝌蚪的毒害。     

长江口南支沉积物对卤虫的毒性效应研究

以Ⅱ-Ⅲ龄卤虫幼体（Artemia salina）为受试生物,开展生物检测试验,研究长江口南支沉积物的毒性效应。生物检测结果表明长江口南支部分站位的沉积物对卤虫幼体已产生毒性效应,其中,2、5、8三站沉积物对卤虫体长和体内SOD酶活性具有显著影响（p〈0.05）,1号和2号站沉积物对卤虫体内LDH活性有显著影响（p〈0.05）。对多个毒性效应指标运用因子分析法得到长江口南支各站因子得分F,F值大小可表征各站沉积物对卤虫综合毒性的强弱,各站F值排序为：2号（-1.59）〈5号（-0.76）〈8号（-0.42）〈1号（0.06）〈6号（0.62）〈7号（0.78）〈3号（1.31）,2号站沉积物毒性最强,3号站毒性最弱。经逐步回归分析,因子得分F与沉积物中Cu、Cd含量具有显著相关关系（R=0.91,p〈0.05）,表明长江口南支沉积物中Cu和Cd是对卤虫产生毒性效应的关键污染物。     

活性污泥SBR系统对四环素耐药菌和总四环素的去除特性

通过模拟运行SBR工艺,比较不同四环素进水浓度、运行周期以及氧环境条件对四环素耐药菌及痕量四环素的去除特性.结果表明,痕量四环素的存在会对活性污泥中微生物耐药性产生影响,SBR进水四环素浓度为250μg.L-1时活性污泥中的微生物会逐步变成耐药微生物,而进水中不含四环素时,耐药的微生物会逐步变成非耐药微生物.总四环素的去除效果在好氧条件下周期为12 h时最好,达到90%以上.好氧条件下周期为8 h时每克污泥增加的四环素耐药菌数最多,约为2.89×109CFU.g-1;好氧条件下周期为20 h时为最少,约为1.0×108CFU.g-1,有利于缓解四环素耐药菌的产生.     

稀土元素的脑部蓄积性、毒性及其对人群健康的潜在危害

论述了稀土元素在动物脑部的蓄积性、对脑的毒性以及稀土区人群的脑部毒性效应,分析了稀土农业应用和稀土厂“三废”对生态环境和人群健康的潜在危害。     

菲、芘、1,2,4-三氯苯对蚯蚓的急性毒性效应

测定了草甸棕壤条件下 ,菲、芘和 1,2 ,4-三氯苯单一与复合污染对蚯蚓的急性致死及亚致死效应。结果表明 ,3种化学品的浓度与蚯蚓死亡率显著相关 (α =0 .0 5 ,r菲 =0 .87,r芘 =0 .85 ,r三氯苯 =0 .95 ) ,与蚯蚓亚致死效应的相关性稍低 (α =0 .0 5 ,r菲 =0 .75 ,r芘 =0 .72 ,r三氯苯 =0 .85 )。蚯蚓个体对 3种有机物毒性的耐受程度差别较大。引起蚯蚓死亡的毒性阈值浓度菲和 1,2 ,4-三氯苯均为 2 0mg·kg-1,芘为 2 0 0 0mg·kg-1;引起蚯蚓体重增长率下降的亚急性毒性阈值浓度分别为菲 2 0mg·kg-1、1,2 ,4-三氯苯 3 0 0mg·kg-1、芘 10 0 0mg·kg-1;LC10 0 分别为菲 10 0mg·kg-1,1,2 ,4-三氯苯 3 5 0mg·kg-1。由于芘的低水溶性和低毒性 ,无法计算LC10 0 。实验还表明 ,复合污染主要表现为协同和拮抗作用     

Influence of some parameters on adsorption rate and toxicity of cadmium in activated sludge

The influence of pH, competitor ions (NaNO₃) and aerobic and anaerobic stabilization of activated sludge on the cadmium uptake by activated sludge solids was investigated. Above 0.08 mg L^‐1 cadmium in solution, biosorption was found to follow the Freundlich isotherm. Active cellular uptake of soluble cadmium does not appear to be a significant mechanism of the biosorption. In addition, the cadmium uptake is not completely reversible. The adsorption of cadmium by activated sludge seems to involve a physico‐chemical mechanism with especially weak electrostatic interactions with ion‐exchange reaction. The optimum adsorption pH was 7.5. Adsorption is influenced by sodium ion concentrations up to an equivalent conductivity of 10 000 μS cm^‐1. Aerobic and anaerobic stabilization of activated sludge increase systematically the initial adsorption capacities. Respirometric measurements were done to evaluate the inhibitive effects of cadmium on activated sludge. Monod's equation and the equation of non‐competitive inhibition were used to describe the toxicity related to cadmium uptake. These two equations appear to be complementary.     

藻红外测试多元有机毒物急性毒性的初步分析

藻红外测试法是利用毒物引起敏感藻红外辐射变化可被测试的一种急性毒性分析方法。敏感藻是指急性毒性藻红外测试中对毒害物质响应温差大、时间快、药品多、剂量低的特殊藻种。在藻红外测试多元有机毒物时,由于毒物毒性的联合作用将直接影响敏感藻的敏感性,因此敏感藻对多元有机毒物浓度的敏感性在联合毒性测试分析时需要首先认知。实验通过测试敏感藻对5种有机毒物不同组合的响应,为联合毒性测试分析时敏感藻敏感性不变提供了多元有机毒物浓度设计依据。实验用羊角月牙藻（Selenastrum capricornutum）作敏感藻,苯（C6H6）、甲苯（C7H8）、二甲苯（C8H10）、氯苯（C6H5Cl）、三氯甲烷（CHCl3）为实验药品。结果表明：有机毒物混合后确实产生了温差的变化,的确有联合作用存在。5种有机毒物的一元、二元、三元、四元、五元组合,其藻液中多元有机毒物质量浓度为100~500 mg.L-1时,敏感藻均有温度响应且可被测试出,表明该质量浓度范围内敏感藻具有敏感性,可作有机毒物联合毒性分析的参照质量浓度,但100~200 mg.L-1为宜。     

稀土元素的脑部蓄积性、毒性及其对人群健康的潜在危害

论述了稀土元素在动物脑部的蓄积性、对脑的毒性以及稀土区人群的脑部毒性效应，分析了稀土农业应用和稀土厂“三废”对生态环境和人群健康的潜在危害。     

Comparative effects of five chelating agents on testicular toxicity in mice induced by acute exposure to cadmium

The aim of this study was to develop new antidotes for cadmium (Cd) since this metal is known to produce mammalian toxicity. N-p-hydroxymethylbenzyl-D-glucamine dithiocarbamate (HBGD), N-benzyl-D-glucamine dithiocarbamate (BGD), diethyldithiocarbamate (DDTC), 2,3-dimercaptopropanol (BAL), and ethylenediamine-tetraacetic acid (EDTA) were studied for their ability to inhibit the adverse effects induced by Cd on mouse testes. The parameters examined included concentrations of Cd, calcium (Ca), iron (Fe), and zinc (Zn) in testes, lipid peroxidation (LPO) levels in testes, lactate dehydrogenase (LDH) activity in serum and reproductive ability of male mice. Mice injected intraperitoneally (ip) with CdCl₂ (2.5?mgCd?kg^?1) after 30?min or 24?h, were then injected ip with chelating agents (400?µmol?kg^?1). Cd increased the concentrations of testicular Ca, Cd, Fe, Zn, and LPO levels as well as the activity of LDH in serum. HBGD and BGD effectively prevented the increase in above indices, and improved the reproductive ability weakened by exposure to Cd. The results suggested that HBGD and BGD are more effective detoxificants in the case of testicular toxicity in mice induced by acute exposure to Cd.     

短链氯化石蜡暴露对HepG2细胞代谢的影响

短链氯化石蜡(short-chain chlorinated paraffins,SCCPs)是一组成分复杂的氯代正构烷烃,在环境中普遍存在。然而有关其毒性机理的信息十分有限,限制了对其健康风险的评估。本研究采用液相色谱–串联质谱(LC-MS/MS)分析技术,研究了不同剂量的SCCPs暴露(0、1.0、10.0和100.0μg·L-1;C13-CPs;55.0%Cl)对人体肝癌细胞Hep G2的糖代谢、氨基酸代谢和脂肪酸代谢的影响。通过偏最小二乘判别分析(PLS-DA)鉴别各组代谢产物谱差异,发现3个SCCPs暴露剂量组均能够与对照组完全分开,表明SCCPs短期暴露能够引起细胞代谢活动的显著改变。SCCPs的低剂量暴露可明显刺激Hep G2细胞对氨基酸的吸收。与对照组相比,SCCPs低剂量暴露组(1.0μg·L-1)培养基中谷氨酰胺、色氨酸和丝氨酸的含量显著(P0.05)降低。而高剂量SCCPs(100.0μg·L-1)暴露抑制了细胞对氨基酸和葡萄糖吸收,但促进了乳酸、丙氨酸、半胱氨酸的生成。氨基酸吸收的抑制不可避免地会影响蛋白质的合成。同时,SCCPs的暴露使饱和脂肪酸代谢紊乱,使不饱和脂肪酸水平上调。为确定SCCPs的毒性作用方式,有必要从转录组和蛋白组层面进一步研究其毒性机制。     

几种典型土壤中铜对赤子爱胜蚓的毒性差异比较研究

土壤污染物基础生态毒理数据是开展污染土壤生态风险评价和构建土壤生态筛选基准的重要依据.以湖南红壤、北京潮土、吉林黑土和经济合作与发展组织(OECD)推荐的人工土壤为测试介质,按照国际标准化组织(ISO)颁布的测试方法,研究了铜在4种不同土壤中对赤子爱胜蚓(Eisenia fetida)的急性和慢性毒性.结果表明,铜在4种不同类型土壤中对赤子爱胜蚓的毒性效应差异较大,在湖南红壤、北京潮土、吉林黑土和人工土壤中的半致死浓度(14d LC50)分别为134.4、557.7、715.2和867.0mg·kg-1;赤子爱胜蚓体重对较低浓度铜污染响应相对不敏感,而较高浓度铜污染(接近引起蚯蚓死亡的高浓度)则可导致蚯蚓体重显著降低;铜对赤子爱胜蚓生殖(产茧量)的影响较为明显,其在湖南红壤、北京潮土、吉林黑土和人工土壤中对蚯蚓产茧量产生50%抑制作用的有效中浓度(28d EC50)分别为58.2、140.1、258.9和150.4mg·kg-1,无可见效应浓度(NOECs)分别为50、50、200和100mg·kg-1.鉴于我国土壤类型的多样性十分丰富,不同地区土壤性质差异较大等特点,在制定土壤筛选基准时需考虑污染物在不同土壤中生物有效性与毒性的差异。