Ion binding by synthetic macrocyclic compounds

The existence of synthetic macrocyclic molecules with hydrophilic cavities containing multiple binding atoms and with hydrophobic exteriors gives rise to extraordinary possibilities with respect to the design and synthesis of molecules with specific cation and anion binding properties. The preparation of many new macrocyclic compounds has recently been reported, but few practical applications for them have been suggested. From the information available, it is becoming clear that it should be possible to synthesize macrocycles that will have specified, or selected, ion binding properties. Cavity size can be varied to accommodate only those cations or anions within a specified narrow band of sizes. Numbers and types of coordinating atoms can be chosen to give essentially electrostatic or covalent bonding or a combination of the two in a metalmacrocycle complex. The metal ligand bond appears to be predominantly ionic in the case of the cyclic polyethers but the covalent character increases on substitution of sulfur or nitrogen for oxygen donor atoms. The essential hydrophobic exteriors of the macrocycles can be modified by the addition of side chains and groups to facilitate the solution of anions and cations in organic solvents. The structures of many macrocycles can be made to approximate naturally occurring molecules, that is, cyclic polyethers similar to macrocyclic antibiotics of the valinomycin and nonactin types and cyclic polyamines similar to porphyrins. Macrocycles are also useful as model compounds for the study of metal interactions with biological systems. The synthetic macrocycles thus represent an intriguing new area of coordination chemistry, the systematic study of which should lead to many interesting and useful chemical applications in the field of metal complexation in solution.     

瓜环家族新成员——半瓜环超分子化学研究进展

本文总结了一类新型大环化合物--半瓜环的发展历程,包括半瓜环的合成及结构特点;半瓜环与金属离子、阴离子及小分子主客体作用;半瓜环在超分子催化中的应用及底物结构对其催化性能的影响;新型半瓜环,例如环己基半瓜环和竹节半瓜环的合成及其超分子化学性质;作为一种新型的大环化合物,半瓜环的研究目前处于起步阶段,在超分子化学的基础研究及相关的应用研究方面有着广阔的前景.     

Model studies in molecular recognition

Recognition at the molecular level is a fundamental characteristic of biochemical systems. Recent models developed in bioorganic chemistry have revealed the importance of complementarity in size, shape, and functional groups in molecular recognition. Structures that feature a cleft are particularly effective in regard to complementarity since functional groups attached to the interior of the cleft converge on substrates held inside. The molecular clefts offer the advantage of efficient construction; their surfaces can be tailored for specific applications. This article describes their use for recognition of acids, bases, amino acids, metal ions, and neutral substrates. Their ability to provide microenvironments complementary to asymmetric molecules and their future promise are discussed.     

草炭溶解态有机物质与Cu~(2+)、Cd~(2+)、Pb~(2+)、Zn~(2+)络合物的红外光谱

草炭有机质提取物胡敏酸、富里酸、水溶解态有机质的红外光谱研究显示 ,三者的含氧官能团组成相似 ,但基团含量差异较大 .胡敏酸、富里酸、水溶解态有机质与金属离子 (Cu2 +、Cd2 +、Pb2 +、Zn2 + )络合物的红外光谱表明 ,除 -COOH外 ,-OH、C=O、-NH2 等官能团也参与了对金属离子的络合 ,但不能很好地揭示哪种金属离子具有形成络合物的最大倾向     

Quantitative molecular approach to the permeability changes of excitation

Functional relationships, available from only a few monolayer studies, can be applied to a relatively simple model of the excitable membrane to give permeability-potential curves quite similar to the conductance-potential curves obtained experimentally in voltage-clamped giant axons. Contrary to the usual view in terms of "carrier systems," the present model considers the permeability to sodium and potassium to be reduced by the increase in the surface pressure induced by large lipophilic cations and anions in the outer layer of the lipoidal bimolecular leaflet constituting the living membrane; hence, the increase in permeability during depolarization, for example, is due to a decrease in the amount of the organic anions in this layer, whereas the decrease in sodium permeability during inactivation is caused by a rise in content of organic cations. The present proposal has the advantage that it is in keeping with known phenomena observed in simple physico-chemical systems as well as in excitable systems; moreover, the current actually transferred by the postulated lipophilic ions can be negligible compared to that transferred by the inorganic cations they control. The latter situation, as well as the steepness of the permeability-potential relationships obtained, have been pointed out to be critical requirements of a satisfactory molecular hypothesis.     

金属离子-质膜相互作用的分子动力学模拟研究

为研究植物根表质膜与土壤溶液界面上的双电层结构对金属离子在质膜上吸附以及吸收的影响,从分子水平探讨质膜表面电势下金属离子与质膜的相互作用,建立了质膜与金属溶液的界面模型,采用分子动力学方法模拟了质膜界面K~+、Na~+、Ca~(2+)、Mg~(2+)等碱/碱土金属阳离子与Cu~(2+)、Cd~(2+)等重金属离子的结合与分布过程。通过对吸附构型、浓度分布等统计分析,发现阳离子在质膜表面主要与质膜头部的羰基和磷酸基团等极性基团结合;二价阳离子吸附作用比一价阳离子更为强烈,并造成质膜表面电势的反转,直接控制着扩散层中离子的分布特征。分子动力学模拟结果与描述界面双电层结构的Gouy-Chapman-Stern(GCS)经典理论很好地吻合,可以从分子水平预测和解释金属阳离子与质膜相互作用的动态过程。     

Self-Assembled Metal Colloid Monolayers: An Approach to SERS Substrates

The self-assembly of monodisperse gold and silver colloid particles into monolayers on polymer-coated substrates yields macroscopic surfaces that are highly active for surface-enhanced Raman scattering (SERS). Particles are bound to the substrate through multiple bonds between the colloidal metal and functional groups on the polymer such as cyanide (CN), amine (NH(2)), and thiol (SH). Surface evolution, which can be followed in real time by ultraviolet-visible spectroscopy and SERS, can be controlled to yield high reproducibility on both the nanometer and the centimeter scales. On conducting substrates, colloid monolayers are electrochemically addressable and behave like a collection of closely spaced microelectrodes. These favorable properties and the ease of monolayer construction suggest a widespread use for metal colloid-based substrates.     

Monodisperse metal clusters 10 angstroms in diameter in a polymeric host: the "monomer as solvent' approach

A general methodology is presented for the dispersion of an inorganic compound within an organic polymer host through the use of solubilizing and polymerizable ligands. The dispersion of metal cluster cations 10 angstroms in diameter within a polymer host is achieved by free-radical polymerization of the hexafunctional metal cluster [Mo(6)Cl(8)(NVI)(6)](triflate)(4) with bound polymerizable ligands in N-vinylimidazole (NVI) solutions. Copolymerization of the activated cluster-bound ligands with the surrounding medium probably plays a key role in preventing aggregation and produces near monodisperse molecular clusters within the polymer matrix.     

鄱阳湖湿地土壤中Cu Zn Pb Cd的形态研究

针对乐安河上游铜矿开采带来的鄱阳湖湖体东部重金属污染的问题，采用Tessier法对鄱阳湖湿地土壤中Cu、Zn、Pb、Cd的化学形态以及重金属形态与植物富集的相关关系进行了研究。结果表明。鄱阳湖土壤中Cu、Pb、Zn主要以有机结合态和残渣态为主，水溶态和交换态等生物有效性态含量很少。Cd的水溶态、交换态和铁锰氧化物态较其他元素高。相关分析和偏相关分析均显示植物中重金属含量与其生存环境中的重金属含量直接相关．植物对重金属的富集能力表现出Zn〉Cu〉Cd〉Pb的趋势。     

Solubilized adenosine receptors in the brain: regulation of guanine nucleotides

Adenosine receptors associated with a reduction of adenylate cyclase and labeled by tritium-labeled cyclohexyladenosine can be solubilized from brain membranes with sodium cholate. Regulation of receptor binding by guanine nucleotides is retained in the soluble state. Influences of cations observed in membrane preparations of adenosine receptors are no longer detected with the solubilized receptors. The apparent retention of a complex of receptors and guanosine triphosphate binding but not cation binding protein in the soluble state may permit a molecular analysis of receptor regulation.     

天然有机质和金属离子在矿物表面的共吸附

天然有机质(NOM)在土壤、沉积物和水体等环境中无处不在,其中富里酸和胡敏酸是主要形态。富里酸及胡敏酸活性高,易与天然矿物颗粒和金属离子发生相互作用,影响矿物的表面化学特性以及金属离子的形态与迁移性,进而在控制环境中金属离子的生物有效性和毒性等方面起重要作用。本文主要综述了富里酸和胡敏酸等NOM和金属离子在矿物表面共吸附特性与主要影响因素,归纳了表面络合模型和现代光谱技术在上述三元体系研究中的应用及其反应机制研究进展。NOM在较大程度上改变了金属离子在矿物表面的吸附特性和反应机制,并受体系pH、金属离子类型和浓度、NOM浓度、NOM和金属离子的添加顺序、矿物类型等因素的影响。低pH时,NOM通常促进矿物对金属离子的吸附。NOM和金属离子在矿物表面的共吸附机制包括:NOM和金属离子竞争吸附表面活性吸附位点;在溶液中形成NOM-金属离子络合物;形成金属离子桥接矿物表面位点与NOM的A型三元络合物(矿物-金属离子-NOM)或NOM联接矿物表面与金属离子的B型三元表面络合物(矿物-NOM-金属离子);静电作用改变表面电荷特征。最后展望了天然有机质等配体与金属离子在矿物表面共吸附有关的研究热点和方向。     

Intercalated clay catalysts

Recent advances in the intercalation of metal complex cations in smectite clay minerals are leading to the development of new classes of selective heterogeneous catalysts. The selectivity of both metal-catalyzed and proton-catalyzed chemical conversions in clay intercalates can often be regulated by controlling surface chemical equilibria, interlamellar swelling, or reactant pair proximity in the interlayer regions. Also, the intercalation of polynuclear hydroxy metal cations and metal cluster cations in smectites affords new pillared clay catalysts with pore sizes that can be made larger than those of conventional zeolite catalysts.     

Light-directed, spatially addressable parallel chemical synthesis

Solid-phase chemistry, photolabile protecting groups, and photolithography have been combined to achieve light-directed, spatially addressable parallel chemical synthesis to yield a highly diverse set of chemical products. Binary masking, one of many possible combinatorial synthesis strategies, yields 2n compounds in n chemical steps. An array of 1024 peptides was synthesized in ten steps, and its interaction with a monoclonal antibody was assayed by epifluorescence microscopy. High-density arrays formed by light-directed synthesis are potentially rich sources of chemical diversity for discovering new ligands that bind to biological receptors and for elucidating principles governing molecular interactions. The generality of this approach is illustrated by the light-directed synthesis of a dinucleotide. Spatially directed synthesis of complex compounds could also be used for microfabrication of devices.     

Metal oxide chemistry in solution: the early transition metal polyoxoanions

Many of the early transition elements form large polynuclear metal-oxygen anions containing up to 200 atoms or more. Although these polyoxoanions have been investigated for more than a century, detailed studies of structure and reactivity were not possible until the development of modern x-ray crystallographic and nuclear magnetic resonance spectroscopic techniques. Systematic studies of small polyoxoanions in inert, aprotic solvents have clarified many of the principles governing their structure and reactivity, and also have made possible the preparation of entirely new types of covalent derivatives such as CH(2)Mo(4)O(15)H(3-), C(5)H(5)TiMo(5)O(18)(3-), and (OC)(3)Mn(Nb(2)W(4)O(19))(3-). Since most early transition metal polyoxoanions have structures based on close-packed oxygen arrays containing interstitial metal centers, their chemistry offers a rare opportunity to study chemical transformations in detail on well-defined metal oxide surfaces.     

Crystallographic evidence for a free silylium ion

Evidence for a three-coordinate silyl cation is provided by the crystal structure of [(Mes)3Si][H-CB11Me5Br6].C6H6 (where Mes is 2,4,6-trimethylphenyl). Free (Mes)3Si+ cations are well separated from the carborane anions and benzene solvate molecules. Ortho-methyl groups of the mesityl substituents shield the silicon atom from the close approach of nucleophiles, while remaining innocent as significant ligands themselves. The silicon center is three-coordinate and planar. The downfield 29Si nuclear magnetic resonance chemical shift in the solid state (226.7 parts per million) is almost identical to that in benzene solution and in "gas phase" calculations, indicating that three-coordination can be preserved in all phases.     

Type I and type II GABAA-benzodiazepine receptors produced in transfected cells

GABAA (gamma-aminobutyric acid A)-benzodiazepine receptors expressed in mammalian cells and assembled from one of three different alpha subunit variants (alpha 1, alpha 2, or alpha 3) in combination with a beta 1 and a gamma 2 subunit display the pharmacological properties of either type I or type II receptor subtypes. These receptors contain high-affinity binding sites for benzodiazepines. However, CL 218 872, 2-oxoquazepam, and methyl beta-carboline-3-carboxylate (beta-CCM) show a temperature-modulated selectivity for alpha 1 subunit-containing receptors. There were no significant differences in the binding of clonazepam, diazepam, Ro 15-1788, or dimethoxy-4-ethyl-beta-carboline-3-carboxylate (DMCM) to all three recombinant receptors. Receptors containing the alpha 3 subunit show greater GABA potentiation of benzodiazepine binding than receptors containing the alpha 1 or alpha 2 subunit, indicating that there are subtypes within the type II class. Thus, diversity in benzodiazepine pharmacology is generated by heterogeneity of the alpha subunit of the GABAA receptor.     

Sequence-specific peptide cleavage catalyzed by an antibody

Monoclonal antibodies have been induced that are capable of catalyzing specific hydrolysis of the Gly-Phe bond of peptide substrates at neutral pH with a metal complex cofactor. The antibodies were produced by immunizing with a Co(III) triethylenetetramine (trien)-peptide hapten. These antibodies as a group are capable of binding trien complexes of not only Co(III) but also of numerous other metals. Six peptides were examined as possible substrates with the antibodies and various metal complexes. Two of these peptides were cleaved by several of the antibodies. One antibody was studied in detail, and cleavage was observed for the substrates with the trien complexes of Zn(II), Ga(III), Fe(III), In(III), Cu(II), Ni(II), Lu(III), Mg(II), or Mn(II) as cofactors. A turnover number of 6 x 10(-4) per second was observed for these substrates. These results demonstrate the feasibility of the use of cofactor-assisted catalysis in an antibody binding site to accomplish difficult chemical transformations.     

Low-temperature synthesis of zintl compounds with a single-source molecular precursor

Thermolysis of the heterobimetallic phosphinidene complex [Sb(PCy)3]2- Li6.6HNMe2 (Cy = C6H11) at 303 to 313 kelvin gives Zintl compounds containing (Sb7)3- anions. The complex thus constitutes a stable molecular single-source precursor to Zintl compounds and provides a potential low-temperature route to photoactive alkali metal antimonates. The new chemical reaction involved, which is driven thermodynamically by the formation of P-P bonds, has implications in the low-temperature synthesis of other technologically important materials (such as gallium arsenide).     

土壤样品中重金属化学形态模型的发展与应用

土壤中重金属的化学形态与其生物有效性和环境迁移性密切相关。相比于实验室分析手段,化学模型计算具有能揭示化学形态分布全景指纹和具有预测能力的优势。文章综述了天然环境样品中元素化学形态模型的发展、经验性和机理性模型的特征、离子在天然有机质(以NICA-Donnan模型为例)和金属氧化物(以CD-MUSIC模型为例)吸附的先进表面络合模型、建立环境样品机理性模型面临的挑战。重点就天然有机质、金属氧化物和"活性"重金属总量等模型输入值的确定方法作了介绍,并结合镉和砷分别作为金属阳离子和含氧阴离子的典型代表,具体阐述了模型在土壤中重金属元素化学形态分布上的应用。总结了机理性化学形态模型在天然环境样品应用的发展现状,并对模型应用面临的问题和后期的发展做出了展望。     

A microscopic basis for the global appearance of energy landscapes

It is shown that the appearance of a multidimensional potential energy surface, or potential energy landscape, can be related to the form of the interatomic or intermolecular potential. Catastrophe theory enables us to describe how the geometry of the surface changes with parameters in the potential, and provides universal scaling relations that explain, for example, the asymmetric reaction profiles observed for systems bound by long-range forces. The principal result is an unexpected connection between barrier heights, path lengths, and vibrational frequencies, with applications to a wide variety of problems in chemical physics, ranging from Hammond's postulate in organic chemistry, to the relaxation dynamics of complex systems such as glasses and biomolecules.