Surface order and stability of langmuir-blodgett films

Angstrom-resolution atomic force microscope images of Langmuir-Blodgett monolayers and multilayers of cadmium arachidate in air and under water show a dramatic change from a disordered arrangement to a crystalline lattice by the addition or removal of a single layer of molecules. The disordered surface is less stable than the ordered one to mechanical stresses such as atomic force microscopy tip forces or at the air-water contact line during contact angle measurements. The difference in the degree of order in the alkyl chains is attributed to the strong attractive interaction between headgroups in the presence of the divalent cation.     

X-ray standing waves: a molecular yardstick for biological membranes

Structural information on an atomic scale has been obtained for a Langmuir-Blodgett (LB) trilayer system by means of long-period x-ray standing waves. The LB trilayer of zinc and cadmium arachidate was deposited on a layered synthetic microstructure (LSM) consisting of 200 tungsten/silicon layer pairs with a 25 A period. A 30 A thermally induced inward collapse of the zinc atom layer that was initially located in the LB trilayer at 53 A above the LSM surface has been observed. The mean position and width of the zinc atom layer was determined with a precision of +/- 0.3 A.     

蜡状芽孢杆菌抗重金属性能及对镉的累积

所研究的蜡状芽孢杆菌RC可以在镉浓度为200mg·L-1的固体培养基平板上生长良好,表明菌株具有强抗镉的能力。该菌株在液体培养基中Cd2+、Cr3+、Pb2+浓度均为75mg·L-1和Mn2+浓度为100mg·L-1培养时,菌株生长正常。在重金属Cr3+、Pb2+、Mn2+存在时,采用红外光谱与原子吸收光谱分析菌株对Cd2+的积累,结果表明,培养基中其他重金属离子的加入,会影响菌株对Cd2+的积累率;当Cr3+存在时,Cr3+可以增加细胞壁上有效官能团活性,明显提高RC菌体对Cd2+的积累率,而其他重金属组合对Cd2+吸附积累能力影响不大;RC细胞壁上活性基团-OH、-NH-、-COOH、-PO34-和-M-O(O-M-O)活跃参与Cr3+、Pb2+、Mn2+和Cd2+多种重金属离子的络合作用。通过高温和十二烷基硫酸钠处理菌株进行质粒消除试验,未发现该菌株的抗镉性质与抗性质粒的存在相关。     

镉胁迫下NO对胡杨细胞Cd2+吸收调控机制的研究

本文研究了NO对胡杨愈伤细胞Cd2+耐受性的影响。结果表明:Cd2+(50 μmol/L)显著抑制了胡杨细胞的生长,而硝普钠SNP(NO供体,25 μmol/L)能明显缓解Cd2+对胡杨细胞生长的抑制作用,并减轻镉对细胞膜的伤害以及镉胁迫导致的细胞活力下降。利用非损伤微测技术等研究了NO对Cd2+动态吸收的影响。CdCl2(50 μmol/L)处理之后,胡杨细胞表现出Cd2+内流,而SNP(25 μmol/L,6 h)显著抑制了Cd2+的内流,并降低了Cd2+在细胞内的积累。研究发现,NO是通过调控钙离子通道来抑制胡杨细胞对Cd2+的吸收。镉胁迫下Cd2+内流被钙离子通道专一性抑制剂氯化镧明显抑制,表明Cd2+是通过钙离子通道转运进入细胞。并且发现,NO是通过促进Ca2+的内流来竞争性地抑制胡杨细胞对Cd2+的吸收,从而缓解了镉胁迫对胡杨细胞造成的生长抑制。      

海泡石对典型水稻土镉吸附能力的影响

通过吸附解吸实验研究了添加海泡石后典型水稻土对Cd的吸附解吸特性及其对吸附溶液pH值变化的响应.结果表明,Freundlich方程可以较好地拟合红黄泥、黄泥田和红沙泥3种典型水稻土对Cd的等温吸附过程(R2>0.962).在溶液初始Cd浓度相同的情况下,添加海泡石可使3种水稻土对Cd的吸附量增加20%以上,增强土壤对Cd的吸附强度,有效降低吸附Cd的解吸率.其效果随海泡石添加量的增大而增强.3种水稻十吸附Cd的解吸率均高于70%,而且都随吸附量的增加而上升.溶液的pH值是影响土壤吸附Cd的一个重要因素,在低pH值的条件下(pH<4),随着溶液pH值的降低,土壤对Cd的吸附量迅速降低,当溶液pH值高于5时,pH值的变化对吸附量的影响较小.在溶液初始pH值2～8范围内,添加海泡石均能有效提高3种水稻土对Cd的吸附能力.     

三种天然吸附剂对水中铅镉铬的吸附研究

天然吸附剂对重金属吸附效果不同,对不同种类的天然吸附剂对重金属吸附效果的比较研究较少。本实验进行了香菜种子、蛋壳内膜和人类头发对铅、镉、铬的静态吸附研究。结果表明,三种吸附剂对重金属Cr的吸附率大小顺序为蛋壳内膜＞人类头发＞香菜种子, 对Cd和Pb的吸附率大小顺序均为人类头发＞香菜种子＞蛋壳内膜,人类头发对Pb和Cd的吸附率分别是香菜种子的1. 27倍、1.62倍。人类头发和香菜种子对三种重金属的吸附率顺序大小均为Pb＞Cd＞Cr,蛋壳内膜对三种重金属的吸附率顺序大小为Cr＞Pb＞Cd。因此,净化水中铅和镉时,可优先选择废弃毛发;净化铬时,选蛋壳内膜净化效果更好。     

Electro-optical evidence for the chelate effect at semiconductor surfaces

Monoamines and diamines dissolved in cyclohexane solution reversibly enhance the band-edge photoluminescence (PL) intensity of immersed n-type cadmium sulfide (n-CdS) and n-type cadmium selenide (n-CdSe) substrates through adsorption. The magnitude of the PL increase is used to estimate amine-induced contractions in the semiconductor's depletion width, and the dependence of the PL intensity on amine concentration provides an estimate of the adduct formation constant. Two diamines, ethylenediamine and o-phenylenediamine, exhibit unusually low reductions in depletion width and substantially larger adduct equilibrium constants relative to the other amines studied, consistent with chelation to surface Cd(2+) ions. These studies demonstrate that PL can be used as a contactiess, in situ technique for characterizing the steric and electronic landscape of semiconductor surfaces and for correlating molecular and surface chemistry.     

土壤基本理化性质对外源镉蚯蚓慢性毒性的影响

为了给污染土壤生态风险评价和构建土壤生态筛选基准提供基础参考数据,参考经济合作与发展组织(OECD)颁布的蚯蚓慢性毒性试验方法,研究了镉在我国18种典型土壤中对赤子爱胜蚓(Eisenia fetida)的慢性毒性。结果表明,镉在不同类型土壤中对蚯蚓产茧量最大无影响浓度NOEC变化范围为10~100 mg·kg~(-1),半数有效抑制浓度EC_(50)变化范围为66.5~263.5 mg·kg~(-1)。土壤基本性质显著影响着镉的生物毒性,通过对EC_(50)与土壤的主要理化性质逐步多元回归分析,发现土壤pH值和有机质含量与EC_(50)呈显著正相关关系,黏粒与EC_(50)呈显著负相关关系,三种因子共同控制了EC_(50)预测回归模型变异的89.1%。同时分析不同类型土壤中蚯蚓体内镉积累量变化可知,土壤pH越高,有机质含量越高,土壤中镉生物有效性就越低。     

BS 12与Cd2+复合污染对空心菜种子萌发及生长的影响

研究两性表面活性剂BS-12和Cd2+共存对空心菜种子萌发、叶绿素含量及MDA含量等的影响。结果表明,在Cd2+单独作用下,Cd2+质量浓度为5 mg/L时,能促进空心菜种子萌发,Cd2+质量浓度≥10 mg/L时,对其萌发产生毒害作用。BS-12与Cd2+共存时,在同一Cd2+质量浓度条件下,当加入较低质量浓度的BS-12时,能降低Cd2+对空心菜的毒害作用。具体表现为空心菜的发芽率、株高和叶绿素含量都随着BS-12质量浓度的升高呈现先上升后下降的趋势,而MDA含量呈现先下降后上升的趋势。因此,通过以上生理生化指标的测定,可以得知BS-12≤50 mg/L时,能降低Cd2+对空心菜种子萌发的毒害作用。     

二价镉对梨形环棱螺毒理效应的研究

为评价Cd2+对梨形环棱螺的毒理效应,采用暴露重金属的方法,研究了不同质量浓度氯化镉(Cd2+分别为0、0.05、0.10、0.20和0.50 mg/L)在不同暴露时间(0~14 d)下对梨形环棱螺几种抗氧化酶活性及氧化损伤的影响。结果显示:Cd2+对梨形环棱螺肝脏和鳃中过氧化氢酶(CAT)、超氧化物歧化酶(SOD)、谷胱甘肽硫转移酶(GST)、还原性谷胱甘肽(GSH)和丙二醛(MDA)均有显著影响,表现为动态变化过程,并有明显的时间剂量效应;螺肝脏和鳃组织中DNA单链断裂程度随暴露的剂量增加而增加;肝脏在暴露的前4 d内,DNA完整性(F比值)一直下降,鳃组织在暴露的第1天时,DNA损伤显著或极显著,随后F值上升,显示断裂的DNA有一定程度的修复,然后DNA单链断裂程度继续加重,F值持续下降,直至第14天。结论:低浓度的Cd2+暴露可引发梨形环棱螺的氧化应激和脂质过氧化。上述指标对Cd2+污染敏感,可以作为Cd2+污染监测的生物标志物。     

Crystal structure of Cd,Zn metallothionein

The anomalous scattering data from five Cd in the native protein were used to determine the crystal structure of cadmium, zinc (Cd,Zn) metallothionein isoform II from rat liver. The structure of a 4-Cd cluster was solved by direct methods. A 2.3 A resolution electron density map was calculated by iterative single-wavelength anomalous scattering. The structure is folded into two domains. The amino terminal domain (beta) of residues 1 to 29 enfolds a three-metal cluster of one Cd and two Zn atoms coordinated by six terminal cysteine thiolate ligands and three bridging cysteine thiolates. The carboxyl terminal domain (alpha) of residues 30 to 61 enfolds a 4-Cd cluster coordinated by six terminal and five bridging cysteine thiolates. All seven metal sites have tetrahedral coordination geometry. The domains are roughly spherical, and the diameter is 15 to 20 A; there is limited contact between domains. The folding of alpha and beta is topologically similar but with opposite chirality. Redundant, short cysteine-containing sequences have similar roles in cluster formation in both alpha and beta.     

作物根系镉滞留作用及其生理生化机制

一定程度的镉胁迫严重影响了作物的生长发育和农产品的产量及品质。文中全面综述了重金属镉胁迫对作物和人类的危害,以及镉在作物体内的吸收、转运和积累特征及其相关的主要调控基因和功能。简要概述了作物抗镉耐镉机制,重点讨论了其中的根系镉滞留作用的生理和生化机制。重金属镉主要通过根部吸收进入植株,在根中,Cd~(2+)首先进入由细胞间隙、细胞壁微孔以及细胞壁到质膜之间的空隙等构成的"自由空间",然后通过主动或被动吸收跨膜进入胞质,再经共质体或质外体途径运输到木质部导管中。水稻等作物主要通过下列途径来适应镉胁迫:细胞壁的滞留作用、原生质体的螯合作用、液泡的区室化作用、逆境蛋白和脯氨酸的积累、抗氧化酶系统活性的提高、根系的滞留作用。根系镉滞留作用作为一种重要的抗耐镉毒害的方式,在调控作物对镉的吸收、转运和分配积累,阻碍镉进入植株地上部和原生质体,减少镉对作物自身生长发育及农产品产量和品质的影响等方面起着非常重要的作用。主要包括根茎间低转运量导致的镉滞留、根系细胞壁滞留和液泡滞留。(1)根茎间低转运量导致的镉滞留。该种滞留作用主要受到根系木质部的镉装载能力和镉长距离运输载体——植物螯合肽(PCs)含量的影响;它们主要受到质膜上跨膜离子转运蛋白HMA2和HMA4以及细胞中的PCs合成酶及其相应基因(如HMA2、HMA4、PCs1等)的调控。这些蛋白和基因对木质部的镉滞留起到负调控作用。(2)细胞壁滞留作用。根系细胞壁滞留发生在质外体部分(包括细胞壁和胞间层),主要与质外体的组成成分和结构相关,其中起关键作用的是果胶多糖,半纤维素也起到一定作用。根据果胶和半纤维素滞留镉的作用方式的不同,细胞壁滞留作用可分为物理滞留和化学滞留。物理滞留主要与细胞壁的孔隙度和厚度有关,此二者均受到细胞壁果胶含量和果胶甲酯酶PME活性的影响。而化学滞留则是由半纤维素和低酯化果胶上的带负电荷基团,如-COO-等,与Cd2+发生静电结合作用所致。它们会受到PME14和XCD1等基因的调控。(3)液泡滞留作用。液泡滞留作用与细胞质和液泡中的PCs以及液泡膜上的转运蛋白密切相关,其对镉的滞留能力大小受到液泡分隔容量大小(VSC)的限制。在液泡的镉滞留中,不同分子量大小的PCs起到了重要作用,它们参与了胞质中镉的螯合、胞质与液泡间镉的转移及最终液泡中镉的沉积。而液泡膜上的转运蛋白则负责将胞质溶液中的低分子量PC-Cd复合物通过主动运输转移到液泡内,使镉被隔离在活跃生理区之外。作物根系中,这三种重金属滞留机制先后联合作用,降低了镉向原生质体和地上部的转移,从而减轻了镉对地上部的毒害,降低了籽实等收获器官中的镉含量。然而,由于木质部中PC-Cd占总镉比例以及细胞壁电荷总量和液泡VSC大小的有限性,从而使得根系镉滞留作用的强度和效果都存在着一定的限度。     

锌镉互作对水稻幼苗镉和矿物质积累的影响

研究分析了在浓度梯度的Zn×Cd胁迫下两个水稻品种黄华占和IR68144幼苗根部和地上部Cd和矿物质的积累特征.结果表明:(1)随着营养液Cd2+浓度的上升,黄华占和IR68144根部和地上部的Cd含量都大幅增加.中等浓度的Zn2+能有效地减少高浓度Cd胁迫时水稻根系对Cd的吸收,但低浓度Cd胁迫时表现为协同吸收,而高浓度Zn2+则主要促进Cd的吸收.中等浓度的Z2++在一定条件下也能有效减少水稻地上部的Cd积累量,但其作用与Cd2+浓度和水稻基因型都有关,而高浓度Zn2+则完全表现为促进Cd的积累.(2)黄华占和IR68144根部和地上部的Zn含量都随着营养液Zn2+浓度的提高而增加.Cd对水稻Zn积累的影响与Zn2+浓度和基因型都有关,但大多数情况下Cd胁迫明显降低了水稻对Zn的积累.(3)在正常Zn2+浓度(0μmol/L)营养液中,Cd2+浓度上升时,黄华占和IR68144根部Fe积累量都保持相对平稳,但两者地上部Fe积累量明显持续降低;两品种根部Mn含量都不断增加,但黄华占地上部Mn积累量持续下降,而IR68144中保持平稳.Zn×Cd互作对水稻Fe积累的影响在根部主要表现为促进作用,在地上部则主要显示出抑制作用,但两品种的Mn积累量表现出复杂的Cd2+、Zn2+浓度和基因型相关性.说明锌镉互作能有效调控水稻幼苗对镉的吸收与转运,但其互作效应与Zn2+和Cd2+浓度有关,且表现出明显的基因型差异;同时还改变了水稻幼苗中锌、铁、锰等的积累.     

Electron diffraction and imaging of uncompressed monolayers of amphiphilic molecules on vitreous and hexagonal ice

A new approach is described for probing domains of ordered self-assemblies of amphiphilic monolayers at the aqueous solution interface. The method has potential importance for the study of membrane structure, Langmuir-Blodgett films, and nucleation processes of two-and three-dimensional crystals. Electron diffraction (ED) patterns indicative of two-dimensional crystalline self-assembly were obtained from samples, which were examined by cryo-electron microscopy, of monolayers of water-insoluble amphiphiles on vitrified aqueour substrates. The apparent hexagonal symmetry of an ED pattern from a C(16)H(33)OH monolayer was interpreted in terms of multiple twinning. Monolayers of the CL(31)H(63)OH and cadmium salt of C(19)H(39)CO(2)H that were studied by dark-field techniques displayed faceted two-dimensional crystallites with a maximal size of 1 to 2 micrometers. Epitaxial nucleation of hexagonal ice by the C(31)H(63)OH monolayer has also been demonstrated by ED.     

缺氧和充氧栽培对水稻Cd积累及OsHMA2基因表达的影响

【目的】研究缺氧和充氧栽培对水稻重金属Cd的吸收和转运及OsHMA2基因在茎中表达的影响,为降低水稻中重金属的吸收和累积奠定基础。【方法】以水稻品种五丰优2168为试验材料,通过营养液缺氧和营养液充氧的水培盆栽试验,分析Cd质量浓度为0、0.6、1.2mg·L~(-1)时,Cd的吸收累积以及茎中OsHMA2基因表达水平。【结果】缺氧栽培条件下,水稻生长发育受Cd抑制作用不显著,而充氧栽培条件下水稻生长受到显著抑制,表现为根、地上部干质量显著下降。在0.6和1.2mg·L~(-1)Cd处理条件下,缺氧栽培的水稻根部和地上部Cd累积量均低于充氧栽培。2种栽培条件下,根部Cd累积量均随Cd处理浓度的增大而增大。水稻地上部对Cd的累积在缺氧栽培条件下,0.6和1.2mg·L~(-1)Cd处理无显著差异,充氧栽培的水稻地上部Cd累积随处理浓度增大而增大。与对照相比,水稻茎OsHMA2表达量在缺氧和充氧栽培下,0.6mg·L~(-1)Cd处理上调,而1.2mg·L~(-1)Cd处理下调;在Cd处理下,OsHMA2表达量缺氧栽培高于充氧栽培。【结论】缺氧栽培能抑制水稻对Cd的吸收和累积;Cd累积量达到一定值时能够下调OsHMA2的表达。     

Effect of Cadmium Stress on the Growth,Antioxidative Enzymes and Lipid Peroxidation in Two Kenaf (Hibiscus cannabinus L.) Plant Seedlings

The effects of cadmium stress on the growth, antioxidative enzymes and lipid peroxidation in two kenaf plants, Fuhong 991 and ZM412, were analysed under control (0.5-strength Hoagland's nutrient solution) or five levels of cadmium stress (0.5-strength Hoagland's nutrient solution containing different concentrations of Cd²⁺). The leaves and roots of control and cadmium-stressed plants were harvested after 3 wk. At the same Cd concentration, the Cd tolerance index of Fuhong 991 was higher than that of ZM412, indicating that Fuhong 991 may be more tolerant to Cd than ZM412. The superoxide dismutase (SOD), catalase activity (CAT) and peroxidase (POD) activities fluctuated in the leaves of the Cd-stressed plants compared to the control, whereas the glutathione reductase activity (GR) was much larger than the control for Fuhong 991, ensuring that sufficient quantities of GSH were available to respond to the cadmium stress. In comparison to the control, the dynamic tendency of the SOD, CAT and POD activities in roots of the Cd-stressed plants all increased and then declined, but the POD activity of Fuhong 991 remained nearly unchanged at all of the stress levels. The increase in the enzyme activities demonstrated that Fuhong 991 was more tolerant to cadmium than ZM 412. The lipid peroxidation was enhanced only in the leaves of Cd-stressed ZM 412. These findings indicated that antioxidative activities may play important roles in Cd-stressed Fuhong 991 and ZM 412 and that the leaf and root cell membranes of Fuhong 991 have a greater stability than those of ZM 412. For pollution monitoring purposes, the GR activity in the roots and leaves may serve as a biomarker of Cd for Fuhong 991, whereas lipid peroxidation may serve as biomarker for ZM 412.     

褐土中镉的化学形态及其对植物的毒性研究

通过土培试验研究了褐土中不同有机质处理(即去除有机质与未去除土壤按1∶1、1∶2、1∶3混合)对外源镉的化学形态及其植物毒性的影响,以期为镉污染土壤的防治和修复提供依据。结果表明,在外源添加镉浓度相同时,不同有机质处理对土壤中镉的植物毒性影响不显著。土壤中弱酸提取态的镉含量随着镉浓度的升高而增大,残渣态的镉含量随镉浓度的升高而减小;可还原态的镉占总量的百分比随镉浓度升高变化不大,均在28%左右;可氧化态的镉占总量百分比最小,最高为2.62%。除残渣态外,土壤中其他3种形态的镉与其植物毒性显著相关(R2≥0.70)。     

Stable ordering in Langmuir-Blodgett films

Defects in the layering of Langmuir-Blodgett (LB) films can be eliminated by depositing from the appropriate monolayer phase at the air-water interface. LB films deposited from the hexagonal phase of cadmium arachidate (CdA2) at pH 7 spontaneously transform into the bulk soap structure, a centrosymmetric bilayer with an orthorhombic herringbone packing. A large wavelength folding mechanism accelerates the conversion between the two structures, leading to a disruption of the desired layering. At pH > 8.5, though it is more difficult to draw LB films, almost perfect layering is obtained due to the inability to convert from the as-deposited structure to the equilibrium one.     

耐镉细菌与土壤胶体作用对镉形态的影响

【目的】探讨耐镉细菌对红壤、赤红壤和棕色石灰土3类型土壤胶体镉吸附性能的影响及细菌—土壤胶体复合体上所吸附镉形态的变化,为重金属污染土壤的生物修复提供理论依据。【方法】从矿区镉污染土壤中筛选分离出一株耐镉细菌,同时提取红壤、赤红壤和棕色石灰土3种土壤胶体,研究接种耐镉细菌后3种土壤胶体吸附镉的变化及细菌—土壤胶体复合体上所吸附镉形态的变化。【结果】接种耐镉细菌能提高3种土壤胶体对镉的吸附,以红壤有机—无机复合胶体的提高幅度最大;接种耐镉细菌使3种类型土壤胶体上弱酸可溶态和残渣态的镉含量降低,而可还原态和可氧化态含量则提高。接菌后,红壤胶体和赤红壤（自然土）无机胶体上不同形态镉含量为残渣态〉可还原态〉弱酸可溶态〉可氧化态,而赤红壤（耕作土）胶体和棕色石灰土胶体则为可还原态〉残渣态〉弱酸可溶态〉可氧化态。【结论】接种耐镉细菌能促进土壤胶体上镉形态由无效态向有效态转化,提高镉的有效性。     

硅对土壤外源镉活性和玉米吸收镉的影响

 通过土培试验，研究了外源硅对土壤镉形态组成的影响，以及与玉米吸镉量的关系。结果表明，经0.1和1.0 mmol·kg-1（以CdSO4·8/3H2O加入）镉处理的土壤加入2.0 g·kg-1 硅酸钠（以Na2SiO3·9H2O加入，pH调至6.0）后可显著减轻镉对玉米的毒害，降低玉米吸镉量。加硅处理显著降低土壤中的交换态和铁锰结合态镉量，但显著提高碳酸盐结合态和残渣态镉的量。硅降低镉对玉米毒害的机制之一是硅改变了根外土壤中镉的形态，降低了镉的活性和生物有效性。