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.     

Synthesis of a stable compound with fivefold bonding between two chromium(I) centers

Although in principle transition metals can form bonds with six shared electron pairs, only quadruply bonded compounds can be isolated as stable species at room temperature. Here we show that the reduction of {Cr(mu-Cl)Ar'}2 [where Ar' indicates C6H3-2,6(C6H3-2,6-Pri2)2 and Pr indicates isopropyl] with a slight excess of potassium graphite has produced a stable compound with fivefold chromium-chromium (Cr-Cr) bonding. The very air- and moisture-sensitive dark red crystals of Ar'CrCrAr' were isolated with greater than 40% yield. X-ray diffraction revealed a Cr-Cr bond length of 1.8351(4) angstroms (where the number in parentheses indicates the standard deviation) and a planar transbent core geometry. These data, the structure's temperature-independent paramagnetism, and computational studies support the sharing of five electron pairs in five bonding molecular orbitals between two 3d5 chromium(I) ions.     

Imaging doped holes in a cuprate superconductor with high-resolution Compton scattering

The high-temperature superconducting cuprate La(2-x)Sr(x)CuO(4) (LSCO) shows several phases ranging from antiferromagnetic insulator to metal with increasing hole doping. To understand how the nature of the hole state evolves with doping, we have carried out high-resolution Compton scattering measurements at room temperature together with first-principles electronic structure computations on a series of LSCO single crystals in which the hole doping level varies from the underdoped (UD) to the overdoped (OD) regime. Holes in the UD system are found to primarily populate the O 2p(x)/p(y) orbitals. In contrast, the character of holes in the OD system is very different in that these holes mostly enter Cu d orbitals. High-resolution Compton scattering provides a bulk-sensitive method for imaging the orbital character of dopants in complex materials.     

Intra- and intermolecular band dispersion in an organic crystal

The high crystallinity of many inorganic materials allows their band structures to be determined through angle-resolved photoemission spectroscopy (ARPES). Similar studies of conjugated organic molecules of interest in optoelectronics are often hampered by difficulties in growing well-ordered and well-oriented crystals or films. We have grown crystalline films of uniaxially oriented sexiphenyl molecules and obtained ARPES data. Supported by density-functional calculations, we show that, in the direction parallel to the principal molecular axis, a quasi-one-dimensional band structure of a system of well-defined finite size develops out of individual molecular orbitals. In contrast, perpendicular to the molecules, the band structure reflects the periodicity of the molecular crystal, and continuous bands with a large dispersion were observed.     

玉米FAD2基因的生物信息学分析

脂肪酸脱氢酶（Fatty acid desaturase, FAD2）是产生不饱和脂肪酸的关键酶，在植物对多种逆境胁迫的响应中发挥重要作用。研究通过生物信息学方法对C\-4作物玉米的FAD2基因及其蛋白的结构和功能作以预测和分析。分析结果表明，ZmFAD2基因含有FA-desaturase结构域，表明ZmFAD2蛋白具有脂肪酸去饱和酶的功能。ZmFAD2是定位于内质网的亲水性蛋白，系统进化树表明其与同为C\-4植物的高粱和谷子亲缘关系最近。启动子顺式作用元件以及表达特性分析均表明ZmFAD2参与多种逆境胁迫的响应。研究结果为FAD2基因功能的进一步研究奠定了基础，同时为通过分子育种提高作物在逆境胁迫下的抗性提供了理论依据。     

猪白介素家族重要基因的克隆、表达及其结构与功能预测分析

 【目的】克隆、表达和预测分析猪白介素家族重要成员的结构与功能。【方法】以猪白介素基因家族为对象，通过对猪PBMC刺激诱导，提取RNA，采用RT-PCR技术克隆IL-4、IL-6、IL-18等重要功能基因，并进行原核表达和结构与功能分析。【结果】成功地克隆和表达了IL-4、IL-6和IL-18基因，序列分析发现，克隆的基因与NCBI/GenBank上登载的参考序列的同源性分别为99.25%、99.21%和100％，与其它各物种的基因及其编码蛋白间具有较大的种属差异性；在大肠杆菌中表达的IL-4和IL-6重组蛋白具有较高的生物活性；结构预测表明，这些蛋白分子均含有较多的磷酸化修饰、糖基化修饰（除IL-6）、蛋白激酶以及信号传导结合位点，其中IL-4、IL-6蛋白分子的螺旋化程度较高，均在60%左右，水溶性较低，但这3种蛋白的立体空间结构均为致密的球状，说明该结构特征是其多种生物学功能发挥的基础。【结论】本研究成功地克隆、表达和分析了猪白介素家族的IL-4、IL-6和IL-18等重要分子的结构与功能，为其进一步的生物学功能研究及其应用奠定了基础。     

南方水稻黑条矮缩病毒安徽分离物S5片段的克隆及S5-2基因的原核表达

【目的】探讨南方水稻黑条矮缩病毒(Southern rice black-streaked dwarf virus,SRBSDV)安徽分离物(SRBSDVAn Hui-HN2)的遗传特性,并获得原核表达的P5-2蛋白。【方法】RT-PCR扩增SRBSDV S5片段,克隆、测序并进行序列分析。将S5-2基因插入原核表达载体,重组载体转化大肠埃希菌并用IPTG诱导,Ni2+-NTA亲和柱纯化融合蛋白,SDS-PAGE分析P5-2蛋白的表达情况。【结果】SRBSDV-An Hui-HN2 S5片段全长3 167 bp,包含S5-2基因全长612 bp,编码204个氨基酸。序列比对结果显示,SRBSDV-An Hui-HN2 S5片段与其他SRBSDV分离物S5片段的序列相似性极高,达99.0%~99.7%,而与斐济病毒属(Fijivirus)其他成员S5片段的序列相似性较低,仅为38.0%~71.3%;构建的S5片段系统发育树表明SRBSDV和RBSDV聚成1个分支,其中6个SRBSDV分离物聚成1个亚分支。原核表达获得相对分子质量约为47 000的重组蛋白,Western blot分析显示,GST单抗能够与重组融合蛋白发生特异性反应。【结论】SRBSDV各分离物之间亲缘关系非常近,而与Fijivirus其他成员亲缘关系较远,原核表达获得的融合蛋白为靶标蛋白。     

Interpenetrating As20 fullerene and Ni12 icosahedra in the onion-skin [As@Ni12@As20]3- ion

The [As@Ni12@As20]3- ion was prepared from As7(3-) and Ni(COD)2 in ethylenediamine solutions and isolated as the Bu4P+ salt (As, arsenic; Ni, nickel; COD, cyclooctadiene; Bu, butyl; P, phosphorus). The anion contains an icosahedral [Ni12(mu12-As)]3- fragment that resides at the center of an As20 dodecahedral (fullerene) cage to give an onion-skin-like [As@Ni12@As20]3- cluster with Ih point symmetry. The icosahedron and pentagonal dodecahedron are reciprocal platonic solids, and the 32 surface atoms form a dimpled geodesic sphere composed of 60 triangular faces. In the gas phase, the [As@Ni12@As20]3- ion sequentially loses all 21 As atoms to form a series of Ni12As(21-x) clusters where 0 相似文献   

海带吸附铜、镍离子的研究

[目的]研究海带吸附铜、镍离子过程中的影响因素。[方法]在100ml铜/镍离子溶液中加入0.2g海带粉,所有试验的振荡速度均设为120r/min,用原子分光光度计测定过滤后溶液中的铜、镍离子浓度。[结果]海带吸附铜、镍离子的最佳pH值为4.0。海带对镍离子的吸附平衡时间为60min,对铜离子的吸附平衡时间为90min,吸附等温线均符合Freundlich模型。在pH值为3.0时,海带对铜离子的吸附效率达80%以上。前30min海带对2种离子的吸附速度较快,而后30min吸附速度相对较慢。在同一温度下,相同质量的海带粉对铜离子的吸附量大,对镍离子的吸附量小。海带对铜离子的吸附指数介于0.3～0.5,对镍离子的吸附指数介于0.4～0.6。[结论]该研究为利用生物吸附剂处理工业废水奠定了理论基础。     

南极菌B-3胞外寡聚糖对黄瓜的诱导抗病作用

[目的]研究南极菌B-3对黄瓜的诱导抗病作用。[方法]以黄瓜幼苗为材料,研究南极菌B-3胞外寡聚糖的分子量、单糖组成,及对黄瓜叶中防御酶的诱导作用与黄瓜白粉病的诱导抗病性。[结果]B-3胞外寡聚糖经高效凝胶渗透色谱测定其分子量为2112D,气相色谱分析由甘露糖和葡萄糖2种单糖组成;0.3%、0.5%和0.8%的B-3胞外多糖分别对黄瓜幼苗喷施不同时间后,黄瓜体内的几丁质酶,β-1,3-葡聚糖酶,苯丙氨酸解氨酶（PAL）,过氧化物酶（POD）的活性均较对照有不同程度的提高,且与0.5%的壳聚糖具有相似的诱导效果;同时,0.5%的B-3多糖能够显著地降低黄瓜白粉病的病情指数,防效达24.49%。[结论]B-3寡聚糖有望开发为新型抗病诱导子。     

Comparative Compressibilities of Silicate Spinels: Anomalous Behavior of (Mg,Fe)2SiO4

Compressibilities of five silicate spinels, including gamma-Mg(2)SiO(4), gamma-Fe(2)SiO(4), Ni(2)SiO(4) and two ferromagnesian compositions, were determined on crystals positioned in the same high-pressure mount. Subjection of all crystals simultaneously to the same pressure revealed differences in compressibility that resulted from compositional differences. Ferromagnesian silicate spinels showed an anomalous 13 percent increase in bulk modulus with increasing iron content, from Mg(2)SiO(4) (184 gigapascals) to Fe(2)SiO(4) (207 gigapascals). This result suggests that ferrous iron and magnesium, which behave similarly under crustal conditions, are chemically more distinct at high pressures characteristic of the transition zone and lower mantle.     

Molecular/Organic ferromagnets

Quantitative bulk ferromagnetic behavior has been established for the molecular/organic solid [Fe(III)(C(5)Me(5))(2)].(+)[TCNE].(-). Above 16 K the dominant magnetic interactions are along a 1-D chain and, near T(c), 3-D bulk effects as evidenced by the value of the critical exponents dominate the susceptibility. The extended McConnell model was developed and provides the synthetic chemist with guidance for making new molecular materials to study cooperative magnetic coupling in systems. Assuming the electron-transfer excitation arises from the POMO, ferromagnetic coupling by the McConnell mechanism requires stable radicals (neutral, cations/anions, or ions with small diamagnetic counterions) with a non-half-filled POMO. The lowest excited state formed via virtual charge transfer (retro or forward) must also have the same spin multiplicity and mix with the ground state. These requirements limit the structure of a radical to D(2d) or C>/=(3) symmetry where symmetry breaking distortions do not occur. Intrinsic doubly and triply degenerate orbitals are not necessary and accidental degeneracies suffice. To achieve bulk ferromagnetism, ferromagnetic coupling must be established throughout the solid and a microscopic model has been discussed. These requirements are met by [Fe(III)(C(5)Me(5))(2)].(+)[TCNE].(-). Additionally this model suggests that the Ni(III) and Cr(III) analogs should be antiferromagnetic and ferrimagnetic, respectively, as preliminary data suggest. Additional studies are necessary to test and further develop the consequences of these concepts. Some molecular/organic solids comprised of linear chains of alternating metallocenium donors (D) and cyanocarbon acceptors (A) with spin state S = 1/2 (...D.(+)A.(-)D.(+)A.(-)...) exhibit cooperative magnetic phenomena, that is, ferro-, antiferro-, ferri-, and metamagnetism. For [Fe(III)(C(5)Me(5))(2)].(+)[TCNE](-). (Me = methyl; TCNE = tetracyanoethylene), bulk ferromagnetic behavior is observed below the Curie temperature of 4.8 K. A model of configuration mixing of the lowest charge-transfer excited state with the ground state was developed to understand the magnetic coupling as a function of electron configuration and direction of charge transfer. This model predicts that ferromagnetic coupling requires stable radicals with a non-half-filled degenerate valence orbital and a charge-transfer excited state with the same spin multiplicity that mixes with the ground state. Ferromagnetic coupling must dominate in all directions to achieve a bulk ferromagnet. Thus, the primary, secondary, and tertiary structures are crucial considerations for the design of molecular/organic ferromagnets.     

The crystal structure of [Fe]-hydrogenase reveals the geometry of the active site

Biological formation and consumption of molecular hydrogen (H2) are catalyzed by hydrogenases, of which three phylogenetically unrelated types are known: [NiFe]-hydrogenases, [FeFe]-hydrogenases, and [Fe]-hydrogenase. We present a crystal structure of [Fe]-hydrogenase at 1.75 angstrom resolution, showing a mononuclear iron coordinated by the sulfur of cysteine 176, two carbon monoxide (CO) molecules, and the sp2-hybridized nitrogen of a 2-pyridinol compound with back-bonding properties similar to those of cyanide. The three-dimensional arrangement of the ligands is similar to that of thiolate, CO, and cyanide ligated to the low-spin iron in binuclear [NiFe]- and [FeFe]-hydrogenases, although the enzymes have evolved independently and the CO and cyanide ligands are not found in any other metalloenzyme. The related iron ligation pattern of hydrogenases exemplifies convergent evolution and presumably plays an essential role in H2 activation. This finding may stimulate the ongoing synthesis of catalysts that could substitute for platinum in applications such as fuel cells.     

镍胁迫对玉米苗根系生长及膜保护系统的影响

[目的]研究镍（Ni2＋）胁迫对玉米（Zea mays L.）根系生长及膜保护系统的影响。[方法]以玉米为材料,研究了不同浓度Ni2＋胁迫对玉米幼苗根系生长、根系活力及根系中超氧化物歧化酶（SOD）、过氧化物酶（POD）活性和丙二醛（MDA）含量的影响。[结果]不同浓度Ni2＋处理对玉米幼苗根系具有低浓度的促进效应和高浓度的抑制效应,且随着浓度的增加抑制效应逐渐增强。根系长度、鲜重、根系活力、SOD活性、POD活性、MDA含量在3个处理阶段（10、30、30 d）变化趋于相同;随着玉米幼苗的生长,各项指标变化更加明显。根系活力在Ni2＋浓度为50 mg/kg（土）时最强,随着Ni2＋浓度的升高而逐渐减弱;根系保护酶系统中SOD和POD活性随着Ni2＋浓度的增加而呈现先升高后下降的变化趋势,在Ni2＋浓度为50 mg/kg（土）时出现峰值;根系细胞内MDA含量在低Ni2＋浓度处理下增幅较小,Ni2＋浓度在100～800 mg/kg（土）时增加显著。[结论]Ni2＋浓度低于50 mg/kg（土）时对玉米幼苗期根系的生长有促进作用,而超过该浓度则表现为抑制作用,Ni2＋浓度越高,抑制作用越明显。     

不同种类Ni~(2+)盐浸种对作物种子活力的影响

[目的]为镍肥的进一步开发利用提供基础理论依据。[方法]以春小麦和樱桃番茄为试材,选取均匀一致、饱满的50~100 g种子,分别置于不同浓度、不同种类的Ni2+盐溶液中浸种6~12 h,研究了3种Ni2+盐(氯化镍、硝酸镍、硫酸镍)浸种对作物种子活力的影响。[结果]适量浓度的Ni2+盐浸种可以促进两种作物种子萌发,促进根系和芽生长,幼苗干物质积累增加。春小麦浸种适宜浓度范围为0~2μmol/L,且因Ni2+盐种类而异;樱桃番茄浸种适宜浓度均为0.5μmol/L,其作用效应大小因Ni2+盐种类和作物品种而异。[结论]相同浓度条件下不同Ni2+盐所产生的生物效应差异可能与Ni2+盐中阴阳离子的加和作用有关。     

取代芳烃对大型蚤急性毒性的定量构效关系研究

[目的]建立具有良好相关性和稳定性的取代芳烃对大型蚤定量结构-活性关系（QSAR）模型。[方法]采用Gaussian03程序包中密度泛函理论（DFT）B3LYP方法计算取代芳烃的部分结构参数和毒性参数。[结果]-lgEC50的回归方程为-lgEC50=4.496＋1.5×10-2MM＋9.958×EHOMO＋0.677×ΔQR;方程中各自变量的变异膨胀因子（VIF）分别为：1.508、1.364和1.157。取代芳烃对大型蚤急性毒性的主要影响因子为分子量MM、分子最高占有轨道能EHOMO和苯环上净电荷增量ΔQR,且这3个结构参数与-lgEC50正相关,其标准系数分别为0.986、0.289和0.175。分子量越大,分子总能量（能量为负值）越低,化合物越稳定,毒性越大;分子量越大,lgP越大,化合物的脂溶性越大,毒性越大。[结论]该试验建立的模型具有良好的稳定性和很强的预测能力。     

Atomlike, hollow-core-bound molecular orbitals of C60

The atomic electron orbitals that underlie molecular bonding originate from the central Coulomb potential of the atomic core. We used scanning tunneling microscopy and density functional theory to explore the relation between the nearly spherical shape and unoccupied electronic structure of buckminsterfullerene (C60) molecules adsorbed on copper surfaces. Besides the known pi* antibonding molecular orbitals of the carbon-atom framework, above 3.5 electron volts we found atomlike orbitals bound to the core of the hollow C60 cage. These "superatom" states hybridize like the s and p orbitals of hydrogen and alkali atoms into diatomic molecule-like dimers and free-electron bands of one-dimensional wires and two-dimensional quantum wells in C60 aggregates. We attribute the superatom states to the central potential binding an electron to its screening charge, a property expected for hollow-shell molecules derived from layered materials.     

A

A solid state, electronically addressable, bistable [2]catenane-based molecular switching device was fabricated from a single monolayer of the [2]catenane, anchored with phospholipid counterions, and sandwiched between an n-type polycrystalline silicon bottom electrode and a metallic top electrode. The device exhibits hysteretic (bistable) current/voltage characteristics. The switch is opened at +2 volts, closed at -2 volts, and read at approximately 0.1 volt and may be recycled many times under ambient conditions. A mechanochemical mechanism for the action of the switch is presented and shown to be consistent with temperature-dependent measurements of the device operation.     

Toward separation and purification of olefins using dithiolene complexes: an electrochemical approach

The complex Ni[S2C2(CF3)2]2 reacts with light olefins, including ethylene and propylene, selectively and reversibly. The reaction is not poisoned by hydrogen gas, carbon monoxide, acetylene, or hydrogen sulfide, which are commonly present in olefin streams, presumably because olefin binding occurs through the sulfur ligand rather than the metal center. The reversible reaction of olefins with Ni[S2C2(CN)2]2n (n = 0, -1, -2) can be controlled electrochemically, where the oxidation state-dependent binding and release of olefins are fast on the electrochemical time scale. The observed tolerance to poisons and controllable electrochemical reactivity present an alternative approach to the separation of olefins from complex streams.     

A dinuclear Ni(mu-H)Ru complex derived from H2

Models of the active site in [NiFe]hydrogenase enzymes have proven challenging to prepare. We isolated a paramagnetic dinuclear nickel-ruthenium complex with a bridging hydrido ligand from the heterolytic cleavage of H2 by a dinuclear NiRu aqua complex in water under ambient conditions (20 degrees C and 1 atmosphere pressure). The structure of the hexacoordinate Ni(mu-H)Ru complex was unequivocally determined by neutron diffraction analysis, and it comes closest to an effective analog for the core structure of the proposed active form of the enzyme.