Direct phase determination from neutron diffraction data of the structure of melampodin

The structure of a large complex molecule, C(21)H(24)O(9), has been solved directly from neutron diffraction data by using sigma-2 and tangent refinement methods. As a consequence, the neutron diffraction technique must be reevaluated as a possible primary tool for crystal structure determination.     

Structural aspects of reversible molecular oxygen uptake

The system IrX(CO)[P(C(6)H(5))(3)](2) in benzene solution adds mo lecular oxygen reversibly if X is chlorine and irreversibly if X is iodine. The crystal structure of the complex IrIO(2)(CO)[P(C(6)H(5))(3)](2) * CH(2)Cl(2) is reported here and compared with a previous study of the structure of IrClO(2)(CO)[P(C(6)H(5))(3)](2). The O-O bond length is 1.47 +/- 0.02 angstroms in the irreversibly oxygenated iodo-compound and 1.30 +/- 0.03 angstroms in the reversibly oxygenated chloro compound.     

Selective bond dissociation and rearrangement with optimally tailored, strong-field laser pulses

We used strong-field laser pulses that were tailored with closed-loop optimal control to govern specified chemical dissociation and reactivity channels in a series of organic molecules. Selective cleavage and rearrangement of chemical bonds having dissociation energies up to approximately 100 kilocalories per mole (about 4 electron volts) are reported for polyatomic molecules, including (CH3)2CO (acetone), CH3COCF3 (trifluoroacetone), and C6H5COCH3 (acetophenone). Control over the formation of CH(3)CO from (CH3)2CO, CF3 (or CH3) from CH3COCF3, and C6H5CH3 (toluene) from C6H5COCH3 was observed with high selectivity. Strong-field control appears to have generic applicability for manipulating molecular reactivity because the tailored intense laser fields (about 10(13) watts per square centimeter) can dynamically Stark shift many excited states into resonance, and consequently, the method is not confined by resonant spectral restrictions found in the perturbative (weak-field) regime.     

Argonne intense pulsed neutron source used to solve the molecular structure of a novel organometallic complex

The single-crystal structure of Mn(CO)(3)(C(7)H(11)) is the first to be solved by direct methods based on time-of-flight neutron diffraction data obtained at the Argonne Intense Pulsed Neutron Source. The molecule contains an unusual three-center, two-electron manganese-hydrogen-carbon interaction.     

Ultrafast x-ray diffraction of transient molecular structures in solution

We report direct structural evidence of the bridged radical (CH2ICH2.) in a polar solution, obtained using time-resolved liquid-phase x-ray diffraction. This transient intermediate has long been hypothesized to explain stereo-chemical control in many association and/or dissociation reactions involving haloalkanes. Ultrashort optical pulses were used to dissociate an iodine atom from the haloethane molecule (C2H4I2) dissolved in methanol, and the diffraction of picosecond x-ray pulses from a synchrotron supports the following structural dynamics, with approximately 0.01 angstrom spatial resolution and approximately 100 picosecond time resolution: The loss of one iodine atom from C2H4I2 leads to the C-I-C triangular geometry of CH2ICH2.. This transient C2H4I then binds to an iodine atom to form a new species, the C2H4I-I isomer, which eventually decays into C2H4 + I2. Solvent dynamics were also extracted from the data, revealing a change in the solvent cage geometry, heating, and thermal expansion.     

Free Radicals and Reactive Molecules in Clathrate Cavities

Reactive molecules and free radicals, when located in the cavities of the water clathrate lattice, can be prevented from recombining at temperatures almost up to the decomposition point of the lattice. The active species are produced by selective photochemical dissociation of the guest molecules in the clathrate compounds. Data taken from water clathrates of H(2)S, CH(3)SH, and C(2)H(5)SH suggest that S(2), CH(3)S and C(2)H(5)S can be preserved in this way.     

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.     

在二氯甲烷溶液里〔Cu(CH_3CN)_4〕〔MF_6〕与碘化四丁铵的反应

在本实验中,研究了［Ｃｕ（ＣＨ３ＣＮ）４］［ＭＦ６］（Ｍ＝Ｍ０或Ｗ）与碘化四丁铵（Ｃ４Ｈ９）４ＮＩ在二氯甲烷（ＣＨ２Ｃｌ２）中的反应。研究结果表明,在ＣＨ２Ｃｌ２里,（Ｃ４Ｈ９）４ＮＩ未能把［Ｃｕ（ＣＨ３ＣＮ）４］［Ｍ０Ｆ６］和［Ｃｕ（ＣＨ３ＣＮ）４］［ＷＦ６］中的Ｍ０Ⅴ和ＷⅤ还原成Ｍ０Ⅳ和ＷⅣ盐。通过分析得知,反应产物是ＣｕＩ和（Ｃ４Ｈ９）４ＮＭＦ６,配位体ＣＨ３ＣＮ被解脱出来,反应中并没有产生Ｉ２。     

杀菌剂离体生物测定的稳定性探讨

研究了药剂稀释方法、药液保存时间、溶解药剂的溶剂对杀菌剂平板法生物测定稳定性的影响.结果表明:药剂以2/3的比例系列稀释时多次测定标准差最小,表现最稳定.戊唑醇溶解于丙酮冰箱保存13 d,对水稻纹枯病菌的活性影响不大,说明这种药剂在溶剂中较稳定.福美双用丙酮溶解后降解速度较快,降解方程为y=0.301 6x+2.167 8,r=0.943 2.戊唑醇溶于丙酮、二甲基甲酰胺、氯仿、二氯甲烷、甲苯等多种溶剂,对水稻纹枯病菌的活性影响不大,多菌灵溶于盐酸、甲酸、乙酸、硫酸后,使水稻纹枯病菌的活性产生较大差异,这可能是多菌灵与这些溶剂形成不同的轭合物后导致活性的变化.     

Decamethyldizincocene, a stable compound of Zn(I) with a Zn-Zn bond

Unlike mercury, which has an extensive +1 oxidation state chemistry, zinc usually adopts the +2 oxidation state. Decamethyldizincocene, Zn2(eta5-C5Me5)2, an organometallic compound of Zn(I) formally derived from the dimetallic [Zn-Zn]2+ unit, has been isolated from the low-temperature (-10 degrees C) reaction of Zn(C5Me5)2 and Zn(C2H5)2 in diethyl ether. X-ray studies show that it contains two eclipsed Zn(eta5-C5Me5) fragments with a Zn-Zn distance (+/- standard deviation) of 2.305(+/-3) angstroms, indicative of a metal-metal bonding interaction.     

Dinitrogen Cleavage by a Three-Coordinate Molybdenum(III) Complex

Cleavage of the relatively inert dinitrogen (N(2)) molecule, with its extremely strong N identical withN triple bond, has represented a major challenge to the development of N(2) chemistry. This report describes the reductive cleavage of N(2) to two nitrido (N(3-)) ligands in its reaction with Mo(NRAr)(3), where R is C(CD(3))(2)CH(3) and Ar is 3,5-C(6)H(3)(CH(3))(2'), a synthetic three-coordinate molybdenum(III) complex of known structure. The formation of an intermediate complex was observed spectroscopically, and its conversion (with N identical withN bond cleavage) to the nitrido molybdenum(VI) product N identical withMo(NRAr)(3) followed first-order kinetics at 30 degrees C. It is proposed that the cleavage reaction proceeds by way of an intermediate complex in which N(2) bridges two molybdenum centers.     

Radical reactions of c60

Photochemically generated benzyl radicals react with C(60) producing radical and nonradical adducts Rn C(60) (R = C(6)H(5)CH(2)) with n = 1 to at least 15. The radical adducts with n = 3 and 5 are stable above 50 degrees C and have been identified by electron spin resonance (ESR) spectroscopy as the allylic R(3)C(60)(.) (3) and cyclopentadienyl R(5)C(60)(.) (5) radicals. The unpaired electrons are highly localized on the C(60) surface. The extraordinary stability of these radicals can be attributed to the steric protection of the surface radical sites by the surrounding benzyl substituents. Photochemically generated methyl radicals also add readily to C(60). Mass spectrometric analyses show the formation of (CH(3))nC(60) with n = 1 to at least 34.     

石榴籽中2个木脂素的分离与鉴定

[目的]为了开发石榴籽的药用价值,分析研究其药用物质的化学成分。[方法]采用硅胶柱层析法从石榴籽中分离得到2个木脂素类化合物,通过结构解析和波谱数据确定其组成。[结果]化合物1为白色无定形粉末,易溶于氯仿,有20个碳,包括12个C,4个CH,2个CH2,2个CH3O,推出化合物分子式为C20H22O6,化合物骨架为二倍体双四氢呋喃类木质素。化合物2为白色无定形粉末,易溶于氯仿,有20个碳,包括7个C,8个CH,3个CH2,2个CH3O,可推出化合物分子式为C20H22O6,其确定为二芳基丁内脂型木脂素。[结论]确定2个化合物分别为连翘脂素和罗汉松脂素,均为首次从该种植物中分离得到。     

Free energy and temperature dependence of electron transfer at the metal-electrolyte interface

The rate constant of the electron-transfer reaction between a gold electrode and an electroactive ferrocene group has been measured at a structurally well-defined metal-electrolyte interface at temperatures from 1 degrees to 47 degrees C and reaction free energies from -1.0 to +0.8 electron volts (eV). The ferrocene group was positioned a fixed distance from the gold surface by the self-assembly of a mixed thiol monolayer of (eta(5)C(5)H(5))Fe(eta(5)C(5)H(4))CO(2)(CH(2))(16)SH and CH(3)(CH(2))(15)SH. Rate constants from 1 per second (s(-1)) to 2 x 10(4) s(-1) in 1 molar HClO(4) are reasonably fit with a reorganization energy of 0.85 eV and a prefactor for electron tunneling of 7 x 10(4) s(-1) eV(-1). Such self-assembled monolayers can be used to systematically probe the dependence of electron-transfer rates on distance, medium, and spacer structure, and to provide an empirical basis for the construction of interfacial devices such as sensors and transducers that utilize macroscopically directional electron-transfer reactions.     

Growth of diamond from atomic hydrogen and a supersonic free jet of methyl radicals

The growth of small ( approximately 10-micrometer) diamond particles (on 0.1-or 0.25-micrometer seed crystals) using an effusive glow discharge nozzle for H.and a separate supersonic pyrolysis jet for .CH(3) is reported. Laser micro-Raman, scanning electron microscopy, and x-ray photoelectron spectroscopy data are presented as evidence that well-crystallized diamond is indeed formed. Resonant multiphoton ionization spectroscopy is used as a diagnostic for the gas-phase chemistry indicating that the radical sources are clean and quantitative and that there is no detectable interconversion of .CH(3) to C(2)H(2) under the conditions of the experiment. Diamond growth is found at substrate temperatures greater than or equal to 650 degrees C with no marked increase in the rate of growth up to 850 degrees C. Acetylene does not give good quality diamond under similar conditions.     

Lanthanide complexes as nuclear magnetic resonance structural probes: paramagnetic anisotropy of shift reagent adducts

Magnetic anisotropy measurements on single crystals of a series of paramagnetic 8-coordinate lanthanide shift reagent adducts of the type Ln[(CH(3))(3)CCOCHCOC(CH(3))(3)(4-CH(3)C(5)H(1)N)(2) have been made for the following lanthanides: praseodymium, neodymium, samarium, europium, terbium, dysprosium, holmium, erbium, thulium, and ytterbium. The susceptibility tensors are highly anisotropic and nonaxial. Dipolar nuclear magnetic resonance shifts evaluated from the solid-state date are in satisfactory agreement with the solution results.     

Synthesis and structure of a terminal uranium nitride complex

The terminal uranium nitride linkage is a fundamental target in the study of f-orbital participation in metal-ligand multiple bonding but has previously eluded characterization in an isolable molecule. Here, we report the preparation of the terminal uranium(V) nitride complex [UN(Tren(TIPS))][Na(12-crown-4)(2)] {in which Tren(TIPS) = [N(CH(2)CH(2)NSiPr(i)(3))(3)](3-) and Pr(i) = CH(CH(3))(2)} by reaction of the uranium(III) complex [U(Tren(TIPS))] with sodium azide followed by abstraction and encapsulation of the sodium cation by the polydentate crown ether 12-crown-4. Single-crystal x-ray diffraction reveals a uranium-terminal nitride bond length of 1.825(15) angstroms (where 15 is the standard uncertainty). The structural assignment is supported by means of (15)N-isotopic labeling, electronic absorption spectroscopy, magnetometry, electronic structure calculations, elemental analyses, and liberation of ammonia after treatment with water.     

Infrared observations of the jovian system from voyager 1

The infrared spectroscopy and radiometry investigation has obtained spectra of Jupiter and its satellites between approximately 180 and 2500 cm(-1) with a spectral resolution of 4.3 cm(-1). The Jupiter spectra show clear evidence of H(2), CH(4) C(2)H(2), C(2)H(6), CH(3)D, NH(3), PH(3), H(2)O, and GeH(4). A helium concentration of 0.11 +/- 0.03 by volume is obtained. Meridional temperature cross sections show considerable structure. At high latitudes, the stratosphere is warmer in the north than in the south. The upper troposphere and lower stratosphere are locally cold over the Great Red Spot. Amalthea is warmer than expected. Considerable thermal structure is observed on Io, including a relatively hot region in the vicinity of a volcanic feature.     

Infrared observations of the saturnian system from voyager 1

During the passage of Voyager 1 through the Saturn system, the infrared instrument acquired spectral and radiometric data on Saturn, the rings, and Titan and other satellites. Infrared spectra of Saturn indicate the presence of H(2), CH(4), NH(3), PH(3), C(2)H(2), C(2)H(6), and possibly C(3)H(4) and C(3)H(8). A hydrogen mole fraction of 0.94 is inferred with an uncertainty of a few percent, implying a depletion of helium in the atmosphere of Saturn relative to that of Jupiter. The atmospheric thermal structure of Saturn shows hemisphere asymmetries that are consistent with a response to the seasonally varying insolation. Extensive small-scale latitudinal structure is also observed. On Titan, positive identifications of infrared spectral features are made for CH(4), C(2)H(2), C(2)H(4), C(2)H(6), and HCN; tentative identifications are made for C(3)H(4) and C(3)H(8). The infrared continuum opacity on Titan appears to be quite small between 500 and 600 cm(-1), implying that the solid surface is a major contributor to the observed emission over this spectral range; between 500 and 200 cm(-1) theopacity increases with decreasing wave number, attaining an optical thickness in excess of 2 at 200 cm(-1). Temperatures near the 1-millibar level are independent of longitude and local time but show a decrease of approximately 20 K between the equator and north pole, which suggests a seasonally dependent cyclostrophic zonal flow in the stratosphere of approximately 100 meters per second. Measurements of the C ring of Saturn yield a temperature of 85 +/- 1 K and an infrared optical depth of 0.09 +/- 0.01. Radiometer observations of sunlight transmitted through the ring system indicate an optical depth of 10(-1.3 +/-0.3) for the Cassini division. A phase integral of 1.02 +/- 0.06 is inferred for Rhea, which agrees with values for other icy bodies in the solar system. Rhea eclipse observations indicate the presence of surface materials with both high and low thermal inertias, the former most likely a blocky component and the latter a frost.     

Zn_(1-x)Mg_xO薄膜的溶胶—凝胶法制备与光学性质分析

以二水合乙酸锌和四水合乙酸镁为主要原料,石英玻璃为基片,采用溶胶—凝胶法结合旋涂工艺制备Zn1-xMgxO薄膜(x=0、0.1、0.2、0.3).用XRD和分光光度计分别测量薄膜的晶体结构和透射光谱,并对所得谱线进行分析.XRD分析表明,所制备的薄膜仍保持氧化锌的六角纤锌矿结构,未发现形成MgO杂相;Zn0.7Mg0.3O薄膜沿(002)晶面具有一定的择优取向,Mg2+离子替代Zn2+离子进入ZnO晶格,使晶格常数发生变化;随Mg2+离子掺杂浓度的增加,系列样品(002)晶面衍射峰半高宽增大,平均晶粒尺寸递减,(002)晶面的晶面间距略微减小.透射光谱分析表明,随掺杂浓度增高,薄膜在可见光区域内的透光率增大,光学带隙依次增大.