Kinetic evidence for five-coordination in AlOH(aq)2+ ion

Trivalent aluminum ions are important in natural bodies of water, but the structure of their coordination shell is a complex unsolved problem. In strong acid (pH < 3.0), Al(III) exists almost entirely as the octahedral Al(H2O)6(3+) ion, whereas in basic conditions (pH > 7), a tetrahedral Al(OH)(4- structure prevails. In the biochemically and geochemically critical pH range of 4.3 to 7.0, the ion structures are less clear. Other hydrolytic species, such as AlOH(aq)2+, exist and are traditionally assumed to be hexacoordinate. We show, however, that the kinetics of proton and water exchange on aqueous Al(III), coupled with Car-Parrinello simulations, support a five-coordinate Al(H2O)4OH2+ ion as the predominant form of AlOH(aq)2+ under ambient conditions. This result contrasts Al(III) with other trivalent metal aqua ions, for which there is no evidence for stable pentacoordinate hydrolysis products.     

磁性海藻酸钠复合凝胶球的制备及对铅离子的吸附性能

  目的  磁性凝胶微球是新型吸附剂，其高效去除污染物的功能和重复利用性能受到热切关注，因此制备1种新型的磁性凝胶球极有必要。  方法  将离子共沉淀法制备的磁性粒子(MNP)用作载体进行硅烷化反应以合成具有氨基末端的磁性纳米颗粒(AM)。静电作用将海藻酸钠(SA)包覆在磁性颗粒表面，制备了1种富含氨基、羟基和羧基多官能团的新型磁性复合凝胶球(SA@AM)。利用傅立叶变换红外光谱(FTIR)、元素分析仪、X射线衍射仪(XRD)、扫描/透射电子显微镜(SEM/TEM)、振动样品磁力计(VSM)表征产物，并开展产物对重金属离子吸附性能研究。  结果  成功制备的目标功能复合凝胶球(SA@AM)呈顺磁性磁铁矿晶型，SA@AM凝胶球的尺寸为1.5~2.0 mm；MNP、AM、SA@AM的磁化值分别为13.8、13.4和6.85 A·m2·kg?1。吸附实验显示:SA@AM对重金属铅离子(Pb2+)表现出高效吸附能力，对Pb2+的最大吸附量为105.82 mg·g?1，吸附机理更符合Langmuir等温吸附模型。重复吸附-解吸实验表明:SA@AM对Pb2+的去除率≥76%。  结论  新型海藻酸钠磁性复合凝胶球对重金属Pb2+有着优异的吸附能力，同时磁性凝胶球有着良好的再生性能。图10表1参25     

芹菜源生物炭对重金属离子的吸附性能

[目的]寻找高效低成本的吸附重金属污染物的材料。[方法]以农业剩余物芹菜为原料,研究芹菜源生物炭对一些典型重金属离子[Cu2+、Cd2+、Cr(VI)]的吸附性能。[结果]中温(350、500℃)限氧热解制备的芹菜源生物炭对Cu2+的吸附量可超过50 mg/g,对Cd2+、Cr(VI)等重金属离子也表现出良好的吸附性能。Freundlich和Langmuir吸附方程能较好地描述吸附过程。结合红外光谱、扫描电镜与能谱等表征手段,证明芹菜源生物炭对重金属离子的高吸附性能与其表面沉淀作用、表面络合和离子交换反应有关。[结论]芹菜源生物炭对重金属离子有较强的吸附性能,应用前景广阔。     

Ordering of V2+, Mn2+, and Fe3+ Ions in Zoisite, Ca2Al3Si3O12(OH)

The presence of very small amounts of Mn(2+), V(2+), and Fe(3+) ions in zoisite can be easily detected by the electron paramagnetic resonance technique at room temperature. The Mn(2+) and Fe(3+) ions are completely ordered and are probably located in the Ca(1)- and Al(II)-sites, respectively, whereas the V(2+) ions probably occupy both Ca(1)- and Ca(2)-sites, with a preference for the Ca(1)-site.     

盐胁迫下胡杨的离子响应

分析土壤和植物组织中的各种离子关系,发现胡杨对盐分不是简单的抿吸机制;对根系环境中的ＮａＣｌ,胡杨吸收的钠离子显著少于不耐盐的杂种胡杨,而吸收的氯离子却大大超过后者,这与以往报道盐胁迫的胡杨根细胞中形成大量富含氯离子的小液泡是一致的,是一种特殊的区隔化构造,与杂种胡杨相比,胡杨有相对较发达的茎干组织,根和茎干占植株总生物量的比例较大,能吸收和储存有害盐离子而减少其进入叶组织,这是胡杨抗盐性的形态解     

Chemical bond-making, bond-breaking, and electron transfer in solution

A method is described for determining heats of heterolysis, DeltaH(het), from the heats of reaction of resonancestabilized carbenium ions with carbanions in solution. These results can be converted into heats of homolysis, DeltaH(homo), for the same bonds by combining DeltaH(het) values with electron transfer energies, deltaG(ET) (deltaG(ET) approximately deltaH(ET)), obtained from redox potentials of the reacting ions. The results provide a comprehensive tabulation of DeltaH(het), DeltaH(homo), and DeltaG(ET) values for an extended series of organic compounds and are examined in terms of their interrelationships and a number of related properties of the ions and radicals.     

Scale for the phase diagram of quantum chromodynamics

Matter described by quantum chromodynamics (QCD), the theory of strong interactions, may undergo phase transitions when its temperature and the chemical potentials are varied. QCD at finite temperature is studied in the laboratory by colliding heavy ions at varying beam energies. We present a test of QCD in the nonperturbative domain through a comparison of thermodynamic fluctuations predicted in lattice computations with the experimental data of baryon number distributions in high-energy heavy ion collisions. This study provides evidence for thermalization in these collisions and allows us to find the crossover temperature between normal nuclear matter and a deconfined phase called the quark gluon plasma. This value allows us to set a scale for the phase diagram of QCD.     

Reactivity of the gold/water interface during selective oxidation catalysis

The selective oxidation of alcohols in aqueous phase over supported metal catalysts is facilitated by high-pH conditions. We have studied the mechanism of ethanol and glycerol oxidation to acids over various supported gold and platinum catalysts. Labeling experiments with (18)O(2) and H(2)(18)O demonstrate that oxygen atoms originating from hydroxide ions instead of molecular oxygen are incorporated into the alcohol during the oxidation reaction. Density functional theory calculations suggest that the reaction path involves both solution-mediated and metal-catalyzed elementary steps. Molecular oxygen is proposed to participate in the catalytic cycle not by dissociation to atomic oxygen but by regenerating hydroxide ions formed via the catalytic decomposition of a peroxide intermediate.     

Composition and dynamics of plasma in Saturn's magnetosphere

During Cassini's initial orbit, we observed a dynamic magnetosphere composed primarily of a complex mixture of water-derived atomic and molecular ions. We have identified four distinct regions characterized by differences in both bulk plasma properties and ion composition. Protons are the dominant species outside about 9 RS (where RS is the radial distance from the center of Saturn), whereas inside, the plasma consists primarily of a corotating comet-like mix of water-derived ions with approximately 3% N+. Over the A and B rings, we found an ionosphere in which O2+ and O+ are dominant, which suggests the possible existence of a layer of O2 gas similar to the atmospheres of Europa and Ganymede.     

Molecular recognition and metal ion template synthesis

Methods for the design and synthesis of ligands intended to be specific for a metal ion have been a recent chemical development. This article describes how this process can be inverted so that the specifics of the coordination environment around the metal ion can be used as a template in large-scale ligand synthesis. The synthesis of macrobicyclic ligands for ferric ion has been accomplished by using active esters of catechol ligands in which catecholate coordination to iron is a prelude to the organic chemical reactions that link the coordination subunits together into one ligand system surrounding a central metal ion coordination site. The lanthanide(III) ions, which are among the most labile metal ions known, have coordination numbers of 8 or higher, and thus their encapsulation into a macrobicyclic structure is a challenging problem. Lanthanide amine complexes have been used as metal templates in the synthesis of such macrobicyclic lanthanide complexes. There is evidence that such a complex is inert to exchange in aqueous solution.     

New biological paramagnetic center: octahedrally coordinated nickel(III) in the methanogenic bacteria

Methanobacterium bryantii was grown in medium supplemented with nickel-61, an isotope with a nuclear spin of 3/2. The appearance of nuclear hyperfine structure in the electron paramagnetic resonance spectrum of a cell extract identified a previously observed signal as nickel(III) in an environment of octahedral coordination with rhombic distortions.     

Gas-phase ion chromatography: transition metal state selection and carbon cluster formation

Gas-phase ion chromatography can separate ions that have the same mass but differ in isomeric structure or electronic configuration. The main features of this technique are briefly outlined, and applications to a series of problems in transition metal chemistry and carbon cluster chemistry are described. Examples in transition metal chemistry include state-selective reactivity, excited state deactivation, and state-selective ligand binding energies. For clusters, ion chromatography was used to determine the structure of pure carbon cluster ions as a function of size from C(4) to C(84). The results indicate that carbon grows first in linear chains, transforms to monocyclic planar rings at about C(10), and forms new families of planar bi-, tri-, and tetracyclic rings at C(20), C(30), and C(40), respectively. Fullerenes, which mysteriously appear at C(30) and dominate by C(50), are generated by heating the planar ring systems above an isomerization barrier rather than by growth of graphite precursors.     

A mercury-catalyzed, high-yield system for the oxidation of methane to methanol

A homogeneous system for the selective, catalytic oxidation of methane to methanol via methyl bisulfate is reported. The net reaction catalyzed by mercuric ions, Hg(II), is the oxidation of methane by concentrated sulfuric acid to produce methyl bisulfate, water, and sulfur dioxide. The reaction is efficient. At a methane conversion of 50 percent, 85 percent selectivity to methyl bisulfate ( approximately 43 percent yield; the major side product is carbon dioxide) was achieved at a molar productivity of 10(-7) mole per cubic centimeter per second and Hg(II) turnover frequency of 10(-3) per second. Separate hydrolysis of methyl bisulfate and reoxidation of the sulfur dioxide with air provides a potentially practical scheme for the oxidation of methane to methanol with molecular oxygen. The primary steps of the Hg(II)-catalyzed reaction were individually examined and the essential elements of the mechanism were identified. The Hg(II) ion reacts with methane by an electrophilic displacement mechanism to produce an observable species, CH(3)HgOSO(3)H, 1. Under the reaction conditions, 1 readily decomposes to CH(3)OSO(3)H and the reduced mercurous species, Hg(2)(2+) The catalytic cycle is completed by the reoxidation of Hg(2)(2+) with H(2)SO(4) to regenerate Hg(II) and byproducts SO(2) and H(2)O. Thallium(III), palladium(II), and the cations of platinum and gold also oxidize methane to methyl bisulfate in sulfuric acid.     

降水污染的簇分析

运用簇分析区分不同时间段降水的化学变化,将单个降水事件作为变量来分析,每次降水测量的9项主要离子指定为簇分析的观察值,簇分析完成后,保留6类簇作为描述对象.根据簇中各离子浓度的高低,将各簇概括为:氢离子簇(簇1);无特征离子簇(簇2);氯离子、钠离子簇(簇3);硫酸根、铵根离子簇(簇4);钙、镁离子簇(簇5);硝酸根、钾离子簇(簇6).显然,簇1属酸性降水簇,簇3是海洋型降水簇,簇2、5为中间过渡型,簇4、6为高离子浓度簇,强酸性降水与高离子浓度降水并不属于同一类,降水的酸性与降水中的碱性组分密切相关,降水的酸度仅当NH4+、Ca2+离子浓度尤其是NH4+离子浓度较低时才表现为强酸性.由东北季风气流和锋面系统控制的降水(簇1、2、3)是污染物经较长距离迁移造成的强酸性降水,簇4、簇5、簇6的降水受局地污染源影响,所含的离子浓度较高.     

氯、锌离子对猪精子钙通道和若干酶活调控作用的研究

为了研究了氯离子、锌离子等对猪精子钙通道的调控作用及其机理。将由健康公猪采得的精液经纱布过滤后分为三组,每组6个重复。第一组精液不加任何物质,第二三组精液分别加氯化钠液和硫酸锌液,混匀并静置2.5 h后,观测精子活力和精子、精清中离子含量与酶活。结果表明：（1）在猪精液中分别加适量的氯离子、锌离子,能刺激精清中钙离子向精子中转移,使得精子内钙离子含量显著地(P＜0.05)增加,精清中钙离子有一定程度的(P＞0.05)减少;（2）加锌或加氯离子,精子活力极显著(P＜0.01)地增强;（3）加锌离子组,精子内碱性磷酸酶、碳酸酐酶、腺苷酸环化酶活性极显著地(P＜0.01)提高,cAMP含量极显著地(P＜0.01)增多;精清内碱性磷酸酶、腺苷酸环化酶活性极显著地(P＜0.01)提高,cAMP含量显著地(P＜0.05)增多;（4）加氯离子组,精清内碱性磷酸酶、腺苷酸环化酶活性极显著地(P＜0.01)提高,精清内cAMP含量显著地(P＜0.05)增多;但精子内碳酸酐酶、腺苷酸环化酶活性和cAMP含量都无显著的(P＞0.05)变化。上述结果表明：猪精液加适量锌离子或氯离子,对精子细胞钙通道功能可能都有上调作用,并能提高精液中碱性磷酸酶、腺苷酸环化酶、碳酸酐酶活性,增加精液中cAMP含量,增强精子活力。     

Laser method for synthesis and processing of continuous diamond films on nondiamond substrates

A laser method based upon carbon ion implantation and pulsed laser melting of copper has been used to produce continuous diamond thin film. Carbon ions were implanted with ion energies in the range of 60 to 120 keV, and doses of 1.0 x 10(18) to 2.0 x 10(18) ions cm(-2). The ion-implanted specimens were treated with nanosecond excimer laser pulses with the following parameters: energy density, 3.0 to 5.0 J cm(-2); wavelength, 0.308 microm; pulse width, 45 nanoseconds. The specimens were characterized with scanning electron microscopy (SEM), x-ray diffraction, Rutherford backscattering/ion channeling, Auger, and Raman spectroscopy. The macroscopic Raman spectra contained a strong peak at 1332 cm(-1) with full width at half maximum of 5 cm(-1), which is very close to the quality of the spectra obtained from single-crystal diamond. The selected area electron diffraction patterns and imaging confirmed the films to be defect-free single crystal over large areas of up to several square micrometers with no grain boundaries. Low voltage SEM imaging of surface features indicated the film to be continuous with presence of growth steps.     

A discrete self-assembled metal array in artificial DNA

DNA has a structural basis to array functionalized building blocks. Here we report the synthesis of a series of artificial oligonucleotides, d(5'-GH(n)C-3') (n = 1 to 5), with hydroxypyridone nucleobases (H) as flat bidentate ligands. Right-handed double helices of the oligonucleotides, nCu2+.d(5'-GH(n)C-3')2 (n = 1 to 5), were quantitatively formed through copper ion (Cu2+)-mediated alternative base pairing (H-Cu2+-H), where the Cu2+ ions incorporated into each complex were aligned along the helix axes inside the duplexes with the Cu2+-Cu2+ distance of 3.7 +/- 0.1 angstroms. The Cu2+ ions were coupled ferromagnetically with one another through unpaired d electrons to form magnetic chains.     

Synthesis and Characterization of Molybdenum Carbide Clusters MonC4n, (n = 1 to 4)

Laser radiation (XeCl laser, 308-nanometer wavelength) focused into a cell containing Mo(CO)(6) vapor produced ultrafine particles in the extended waist of the laser beam. Negative ion mass spectrometry revealed molybdenum carbide cluster ions with a stoichiometry MonC4n (n = 1 to 4). The MonC4n(-) (n = 2 to 4) ions are completely unreactive with NH(3), H(2)O, and O(2), suggesting structures in which the molybdenum atoms are unavailable for coordination to additional ligands. Collision-induced dissociation studies of these anions show the loss of MoC(4) units as the main fragmentation pathway. This observation, together with the lack of addition reactions, provides a basis for structures in which a planar cluster of two, three, or four molybdenum atoms is surrounded by, and bonded to, carbon dimers.     

低能离子束注入甘草的刺激效应和诱变效应的RAPD分析

利用生物材料专用的低能离子束注入机,分别以低能(30 keV)Ar+0(对照),600×(2.6×1013),900×(2.6×1013)和1 200×(2.6×1013)ions/cm2的剂量注入甘草种子,M1代材料中,900×(2.6×1013)ions/cm2剂量处理对甘草具有明显刺激生长效应,而其他剂量没有这种刺激生长作用。分别把对照和900×(2.6×1013)ions/cm2剂量处理的植株进行了RAPD多态性比较。从200个引物中筛选出24个引物进行扩增,经分析可以认为,离子束注入甘草种子在基因结构上没有太多的变化,甘草的这种刺激生长效应是低能离子束物理刺激的结果。     

Ionosphere of venus: first observations of the dayside ion composition near dawn and dusk

The first in situ measurements of the composition of the ionosphere of Venus are provided by independent Bennett radio-frequency ion mass spectrometers on the Pioneer Venus bits and orbiter spacecraft, exploring the dawn and duskside regions, respectively. An extensive composition of ion species, rich in oxygen, nitrogen, and carbon chemistry is idenitified. The dominant topside ion is O(+), with C(+), N(+), H(+), and He(+) as prominent secondary ions. In the lower ionosphere, the ionzization peak or F(1) layer near 150 kilometers reaches a concentration of about 5 x l0(3) ions per cubic centimeter, and is composed of the dominant molecular ion, O(2)(+), with NO(+), CO(+), and CO(2)(+), constituting less than 10 percent of the total. Below the O(+) peak near 200 kilometers, the ions exhibit scale heights consistent with a neutral gas temperature of about 180 K near the terminator. In the upper ionosphere, scale heights of all species reflect the effects of plasma transport, which lifts the composition upward to the often abrupt ionopause, or thermal ion boundary, which is observed to vary in height between 250 to 1800 kilometers, in response to solar wind dynamics.