Crystallographic and spectroscopic characterization of a nonheme Fe(IV)-O complex

Following the heme paradigm, it is often proposed that dioxygen activation by nonheme monoiron enzymes involves an iron(IV)=oxo intermediate that is responsible for the substrate oxidation step. Such a transient species has now been obtained from a synthetic complex with a nonheme macrocyclic ligand and characterized spectroscopically. Its high-resolution crystal structure reveals an iron-oxygen bond length of 1.646(3) angstroms, demonstrating that a terminal iron(IV)=oxo unit can exist in a nonporphyrin ligand environment and lending credence to proposed mechanisms of nonheme iron catalysis.     

An Inorganic Double Helix: Hydrothermal Synthesis, Structure, and Magnetism of Chiral [(CH3)2NH2]K4[V10O10(H2O)2(OH)4(PO4)7]{middle dot}4H2O

Very complicated inorganic solids can be self-assembled from structurally simple precursors as illustrated by the hydrothermal synthesis of the vanadium phosphate, [(CH(3))(2)NH(2)]K(4)[V(10)O(10)(H(2)O)(2)(OH)(4)(PO(4))(7)].4H(2)O, 1, which contains chiral double helices formed from interpenetrating spirals of vanadium oxo pentamers bonded together by P(5+). These double helices are in turn intertwined with each other in a manner that generates unusual tunnels and cavities that are filled with (CH(3))(2)NH(2)(+) and K(+) cations, respectively. The unit cell contents of dark blue phosphate 1, which crystallizes in the enantiomorphic space group P4(3) with lattice constants a = 12.130 and c = 30.555 angstroms, are chiral; only one enantiomorph is present in a given crystal. Magnetization measurements show that 1 is paramagnetic with ten unpaired electrons per formula unit at higher temperatures and that antiferromagnetic interactions develop at lower temperatures.     

Structural basis of biological N2O generation by bacterial nitric oxide reductase

Nitric oxide reductase (NOR) is an iron-containing enzyme that catalyzes the reduction of nitric oxide (NO) to generate a major greenhouse gas, nitrous oxide (N(2)O). Here, we report the crystal structure of NOR from Pseudomonas aeruginosa at 2.7 angstrom resolution. The structure reveals details of the catalytic binuclear center. The non-heme iron (Fe(B)) is coordinated by three His and one Glu ligands, but a His-Tyr covalent linkage common in cytochrome oxidases (COX) is absent. This structural characteristic is crucial for NOR reaction. Although the overall structure of NOR is closely related to COX, neither the D- nor K-proton pathway, which connect the COX active center to the intracellular space, was observed. Protons required for the NOR reaction are probably provided from the extracellular side.     

The Exclusion of D2O from the Hydration Sphere of FeSO4{middle dot} 7H2O Oxidized by Thiobacillus ferrooxidans

Infrared spectra demonstrate that neither FeSO(4) . 7H(2)O nor its bacterial or abiotic hydrated oxidation products incorporate deuterium in acid D(2)O solutions. Deuterium exchange occurred as bridging OD when bacterially oxidized iron was precipitated from D(2)O solutions as ferric hydroxysulfates. The exclusion of deuterium depended upon the stabilization of aquated Fe(II) and Fe(III) complexes by sulfate ions in outer-sphere coordination and is consistent with the requirement and postulated role of sulfate in iron oxidation by Thiobacillus ferrooxidans.     

Structure of the hydrated alpha-Al(2)O(3) (0001) surface

The physical and chemical properties of the hydrated alpha-Al(2)O(3) (0001) surface are important for understanding the reactivity of natural and synthetic aluminum-containing oxides. The structure of this surface was determined in the presence of water vapor at 300 kelvin by crystal truncation rod diffraction at a third-generation synchrotron x-ray source. The fully hydrated surface is oxygen terminated, with a 53% contracted double Al layer directly below. The structure is an intermediate between alpha-Al(2)O(3) and gamma-Al(OH)(3), a fully hydroxylated form of alumina. A semiordered oxygen layer about 2.3 angstroms above the terminal oxygen layer is interpreted as adsorbed water. The clean alpha-Al(2)O(3) (0001) surface, in contrast, is Al terminated and significantly relaxed relative to the bulk structure. These differences explain the different reactivities of the clean and hydroxylated surfaces.     

A late-transition metal oxo complex: K7Na9[O=PtIV(H2O)L2], L = [PW9O34]9-

Terminal mono-oxo complexes of the late transition metal elements have long been considered too unstable to synthesize because of repulsion between the oxygen electrons and the mostly filled metal d orbitals. A platinum(IV)-oxo compound flanked by two polytungstate ligands, K7Na9[O=Pt(H2O)L2], L = [PW9O34(9-)], has now been prepared and isolated at room temperature as air-stable brown crystals. X-ray and neutron diffraction at 30 kelvin revealed a very short [1.720(18) angstrom] Pt-O bond and no evidence of a hydrogen atom at the terminal oxygen, ruling out a better precedented Pt-OH complex. Density functional theory and spectroscopic data account for the stability of the Pt(IV)-oxo unit by electron withdrawal into delocalized orbitals of the polytungstates.     

A-Axis--Oriented YBa2Cu3O7/PrBa2Cu3O7 Superlattices

A modulated structure has been fabricated from high transition temperature superconductors where the individual CuO(2) planes are composed of alternating superconducting and insulating strips. This structure is made by growing a-axis-oriented YBa(2)Cu(3)O(7)/PrBa(2)Cu(3)O(7) superlattices by 90 degrees off-axis sputtering on (100)SrTiO(3) and (100)LaAlO(3) substrates. Superlattice modulation is observed to a modulation wavelength of 24 angstroms (12 angstroms-YBa(2)Cu(3)O(7)/12 angstroms-PrBa(2)Cu(3)O(7)), both by x-ray diffraction and by cross-sectional transmission electron microscopy. Rutherford backscattering spectroscopy indicates a high degree of crystalline perfection with a channeling minimum yield of 3 percent. Quasi-one-dimensional conductivity should be obtainable in these structures.     

Tuhualite crystal structure

As judged by crystal structure analysis, the crystallochemical formula of tuhualite is (Na,K)(2)(VI) (Fe(+3))(2)(VI) (Fe(+2))(2)(VI) Si(12)O(30) . H(2)O, with four such formulas in the unit cell. The structure is characterized by six-repeat double chains of silicon tetrahedrons and chains of edge-sharing, alternating iron tetrahedrons and octahedrons. Chains of each kind are connected by corner sharing to four chains of the other type. The iron cations appear to be anomalously ordered with Fe(+2) in tetrahedral and Fe(+3) in octahedral sites.     

H_2O_2清洗对蔬菜中农药去除效果及机制的研究

为了提高蔬菜在清洗过程中的农药去除率,利用低浓度的H_2O_2清洗不同类型的蔬菜。结果表明,在酸性(p H=4.0)条件下,含铁量较高的蔬菜能较明显提高H_2O_2氧化去除敌敌畏的效率。通过叔丁醇试验发现,敌敌畏去除率的提高主要原因可能是由于蔬菜基质自身的Fe~(2+)或Fe~(3+)催化H_2O_2有效地产生了高活性的羟基自由基。试验进一步探讨了H_2O_2清洗几种典型的有机磷、有机氯和氨基甲酸酯类农药的降解,结果表明该体系针对不同类型的农药都具有降解效率。     

A thiolate-ligated nonheme oxoiron(IV) complex relevant to cytochrome P450

Thiolate-ligated oxoiron(IV) centers are postulated to be the key oxidants in the catalytic cycles of oxygen-activating cytochrome P450 and related enzymes. Despite considerable synthetic efforts, chemists have not succeeded in preparing an appropriate model complex. Here we report the synthesis and spectroscopic characterization of [FeIV(O)(TMCS)]+ where TMCS is a pentadentate ligand that provides a square pyramidal N4(SR)apical, where SR is thiolate, ligand environment about the iron center, which is similar to that of cytochrome P450. The rigidity of the ligand framework stabilizes the thiolate in an oxidizing environment. Reactivity studies suggest that thiolate coordination favors hydrogen-atom abstraction chemistry over oxygen-atom transfer pathways in the presence of reducing substrates.     

Fe3 O4／TiO2复合物的制备

[目的]以钛铁矿为原料,制备包覆性Fe_3O_4/TiO_2磁性光催化剂。[方法]研究不同温度、反应时间、钛铁矿颗粒大小、是否冷凝回流等条件下钛铁矿的溶解情况以及TiO_2、Fe_3O_4/TiO_2的产率和催化效果,并采用X射线粉末衍射仪(XRD)、红外光谱(FT-IR)、扫描电镜(SEM)、透射电镜(TEM)等对催化剂产物进行表征,且验证催化剂的磁性能。[结果]该方法可以制备出磁性良好、包覆效果好、较纯净的Fe_3O_4/TiO_2包覆性光催化材料。[结论]制备出的Fe_3O_4/TiO_2复合物保持了Fe_3O_4的磁性,是一种性能优良的包覆性光催化材料。     

Ammonioborite: new borate polyion and its structure

The mineral ammonioborite is monoclinic with unit cell dimensions (in angstroms): a = 25.27, b = 9.65, and c = 11.56; beta = 94 degrees 17', and the space group is C 2/c. Analysis of the crystal structure revealed the crystallo-chemical formula (NH(4))(3)B(15)O(20)(OH)(8).4H(2)O, with four such formula units in the unit cell. The basic structural unit is the double ring consisting of one BO(4) tetrahedron and four BO(3) triangles: in ammonioborite three of these units are connected to give trimeric ions [B(15)O(20)(OH)(8)](3-).     

元江普通野生稻金属硫蛋白(YJMT-2)的获得及序列分析

对SMARTTM技术构建的元江普通野生稻叶片cDNA文库克隆进行随机测序,获得了元江普通野生稻金属硫蛋白(YJMT-2)的cDNA序列。该序列全长为558 bp,5′-端非翻译区为84 bp,3′-端非翻译区为247 bp,开放阅读框长度为225 bp(包括一个终止密码子),可编码74个氨基酸,蛋白分子量为7.51 kD,理论等电点(PI)为6.51,其中含12个半胱氨酸(Cys),占了总氨基酸的16.22%,且集中分布在肽链的N端和C端,呈CXC排列方式,具有植物MT-2的典型特征;经Pfam15.0分析证明,其属于金属硫蛋白家族的成员。BlastP同源性分析,该基因与日本粳稻、大麦的同源性较高,分别为98%和65%。首次得到元江普通野生稻金属硫蛋白基因,为其功能研究提供了基础。     

A New High-Temperature Superconductor: Bi2Sr3-x Cax Cu2O8+y

A new superconductor that displays onset behavior near 120 K has been identified as Bi(2)Sr(3-x)Ca(x)Cu(2)O(8+y), with x ranging from about 0.4 to 0.9. Single crystal x-ray diffraction data were used to determine a pseudo-tetragonal structure based on an A-centered orthorhombic subcell with a = 5.399 A, b= 5.414A, and c = 30.904 A. The structure contains copper-oxygen sheets as in La(2)CuO(4) and YBa(2)Cu(3)O(7), but the copper-oxygen chains present in YBa(2)Cu(3)O(7) do not occur in Bi(2)Sr(3-x)Ca(x)Cu(2)O(8+y). The structure is made up of alternating double copper-oxygen sheets and double bismuth-oxygen sheets. There are Ca(2+) and Sr(2+) cations between the adjacent Cu-O sheets; Sr(2+) cations are also found between the Cu-O and Bi-O sheets. Electron microscopy studies show an incommensurate superstructure along the a axis that can be approximated by an increase of a factor of 5 over the subcell dimension. This superstructure is also observed by x-ray diffraction on single crystals, but twinning can make it appear that the superstructure is along both a and b axes. Flux exclusion begins in our samples at about 116 K and is very strong by 95 K. Electrical measurements on a single crystal of Bi(2)Sr(3-x)Ca(x)Cu(2)O(8+y) show a resistivity drop at about 116 K and apparent zero resistivity at 91 K.     

Creep-resistant, Al2O3-forming austenitic stainless steels

A family of inexpensive, Al2O3-forming, high-creep strength austenitic stainless steels has been developed. The alloys are based on Fe-20Ni-14Cr-2.5Al weight percent, with strengthening achieved through nanodispersions of NbC. These alloys offer the potential to substantially increase the operating temperatures of structural components and can be used under the aggressive oxidizing conditions encountered in energy-conversion systems. Protective Al2O3 scale formation was achieved with smaller amounts of aluminum in austenitic alloys than previously used, provided that the titanium and vanadium alloying additions frequently used for strengthening were eliminated. The smaller amounts of aluminum permitted stabilization of the austenitic matrix structure and made it possible to obtain excellent creep resistance. Creep-rupture lifetime exceeding 2000 hours at 750 degrees C and 100 megapascals in air, and resistance to oxidation in air with 10% water vapor at 650 degrees and 800 degrees C, were demonstrated.     

外源H2O2处理对马铃薯块茎干腐病的控制及其机理

【目的】研究外源过氧化氢（H2O2）处理对采后马铃薯块茎干腐病的控制效果及作用机理。【方法】在离体条件下通过扫描电镜、透射电镜等方法观察分析外源H2O2对马铃薯干腐病菌(Fusarium sulphureum)生长、菌落形态及其超微结构的影响,并以陇薯3号马铃薯为试材,分别在处理前后接种F. sulphureum,研究外源H2O2对病害的治愈和预防作用。【结果】外源H2O2处理强烈抑制了F. sulphureum的菌丝生长和孢子萌发且表现出明显的浓度效应,显著增大了F. sulphureum的细胞膜透性;扫描电镜观察发现H2O2处理过的F. sulphureum菌落分布不均匀,菌丝缠绕、扭曲在一起,部分菌丝出现断裂、塌陷等现象;透射电镜进一步观察到H2O2处理过的菌丝细胞壁加厚且内部出现空腔。体内试验结果表明,外源H2O2处理对处理前后接种F. sulphureum的马铃薯块茎干腐病均具有一定控制作用。【结论】H2O2不仅对病原物具有直接的抑制作用,还能有效提高马铃薯块茎组织的抗病性,因此H2O2可以作为一种具有潜力的天然防腐剂应用于马铃薯采后病害的控制。     

Crystal Structure of Tl2Ba2Ca2Cu3O10, a 125 K Superconductor

There is now a new series of high-temperature superconductors that may be represented as (A(III)O)(2)A(2)(II)Can-1CunO2+2n where A(III) is Bi or Tl, A(II) is Ba or Sr, and n is the number of Cu-O sheets stacked consecutively. There is a general trend toward higher transition temperatures as n increases. The highest n value for a bulk phase is three and is found when A(III) is Tl. This compound, Tl(2)Ba(2)Ca(2)Cu(3)O(10), has the highest transition temperature( approximately 125 K) of any presently known bulk superconductor. The structure of Tl(2)Ba(2)Ca(2)Cu(3)O(10) has been determined from single-crystal x-ray diffraction data and is tetragonal, with a = 3.85 A and c = 35.9 A. No superstructure is observed, and the material is essentially twin-free. Electron microscopy in the Tl/Ba/Ca/Cu/O system has revealed intergrowths where n = 5; such regions may well be responsible for the superconducting onset behavior observed in this system at about 140 K.     

Structural and Electronic Role of Lead in (PbBi)2Sr2CaCu2O8 Superconductors by STM

The structural and electronic effects of lead substitution in the high-temperature superconducting materials Pb(x)Bi(2-x)Sr(2)CaCu(2)O(8) have been characterized by scanning tunneling microscopy (STM) and scanning tunneling spectroscopy (STS). Large-area STM images of the Bi(Pb)-O layers show that lead substitution distorts and disorders the one-dimensional superlattice found in these materials. Atomic-resolution images indicate that extra oxygen atoms are present in the Bi(Pb)-O layers. STS data show that the electronic structure of the Bi(Pb)-O layers is insensitive to lead substitution within +/-0.5 electron volt of the Fermi level; however, a systematic decrease in the density of states is observed at approximately 1 electron volt above the Fermi level. Because the superconducting transition temperatures are independent of x(Pb) (x 相似文献   

Size-Specific Infrared Spectra of Benzene-(H2O)n Clusters (n = 1 through 7): Evidence for Noncyclic (H2O)n Structures

Resonant ion-dip infrared spectroscopy has been used to record size-specific infrared spectra of C(6)H(6)-(H(2)O)n clusters with n = 1 through 7 in the O-H stretch region. The O-H stretch spectra show a dramatic dependence on cluster size. For the n = 3 to 5 clusters, the transitions can be divided into three types-attributable to free, pi hydrogen-bonded, and single donor water-water O-H stretches-consistent with a C(6)H(6)-(H(2)O)n structure in which benzene is on the surface of a cyclic (H(2)O)n cluster. In n = 6 and 7 clusters, the spectra show distinct new transitions in the 3500 to 3600 wave number region. After comparison of these results with the predictions of ab initio calculations on (H(2)O)n clusters, these new transitions have been assigned to double donor O-H stretches associated with the formation of a more compact, noncyclic structure beginning with (H(2)O)(6). This is the same size cluster for which ab initio calculations predict that a changeover to noncyclic (H(2)O)n structures will occur.     

鸡病原性大肠杆菌（O2）亚单位疫苗的研究

试验提取并纯化了鸡病原性大肠杆菌血清型（Ｏ２）的菌毛，并电镜观察了菌毛及菌毛表达。提取了鸡病原性大肠杆菌血清型（Ｏ２）荚膜多糖及菌体可溶性蛋白质，电镜观察了提取过程中荚膜、细胞壁以及胞内物质等细菌结构变化。将提取的菌毛、荚膜多糖和灭活的菌体作为抗原、蜂胶作佐剂，制成蜂胶疫苗，免疫鸡只，于７周龄进行同尖毒保护试验，从保护指数、细菌分离和病变级数三方面比较了３种疫苗的免疫效果，试验结果表明：荚膜疫苗效