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.     

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.     

早稻高产施用氮肥技术研究

[目的]为建立优质稻栽培技术体系提供理论依据。[方法]以水稻品种赣早籼46号为材料,研究不同施肥方式(T1:化肥一次性全层施用。T2:化肥80%全层施用+20%穗肥。T3:有机无机复合肥一次性全层施用。T4:有机无机复合肥80%全层施用+20%穗肥。T5:习惯施肥(CK)。T6:不施N(CK0))对土壤和淹水层NH4-N含量、水稻产量、叶绿素含量和N肥当季利用率的影响。[结果]分蘖始期各处理表土层NH4-N含量为:T5>T1>T3>T2>T4>T6;孕穗末期各处理下层土壤NH4-N含量为:T1>T3>T4=T5>T2>T6;分蘖始期,处理T5淹水层NH4-N含量最高;各处理水稻叶绿素含量为:T2>T4>T1>T3>T5>T6;处理T1的N肥当季利用率最高,达到63.34%;处理T3的水稻产量最高。[结论]全层施肥可提高N肥当季利用率。     

不同营养源对人工湿地基质生物膜培养液pH值的影响

采用恒温摇床培养方法,研究了不同营养源(处理1:尿素+乙酸钠;处理2:亚硝酸钠+乙酸钠;处理3:硝酸钾+乙酸钠;处理4:碳酸氢铵;处理5:硫酸铵+碳酸氢钠;处理6:磷酸二氢钾+碳酸氢钠)对复合垂直流人工湿地基质生物膜培养液pH值的影响,探讨了pH值变化过程中生物膜脱氢酶活性和多糖含量的变化规律.结果表明,处理1、4以及5中培养液pH值先下降然后再上升,但下降和上升的幅度不同.处理2、3以及6中培养液pH值添加碳源前在7.30～7.40之间缓慢变化,添加碳源后均上升至9.00左右.在培养液pH值变化的过程中,生物膜脱氢酶活性和多糖含量也发生改变.处理1、2、3中生物膜脱氢酶活性均在pH值上升的过程中达到最高值,而处理4、5、6中脱氢酶活性随pH值的变化呈下降趋势.对于所设6个处理,除处理4中多糖含量在整个试验过程中基本不变外,其余5个处理中多糖含量均在pH值上升过程中一直增加.     

一类高阶非线性泛函微分方程解的振动性

获得了一类高阶非线性泛函微分方程x^（n）（t）＋p（t）f（x（t）,x（t1（t））,x（r2（t））,…,x（rm（t）））g（x^（n-1）（t））=0解的新振动性条件,其中n是偶数,p∈C（[t0,＋∞],R0）,f∈C（Rm＋1,R）,g∈C（R,R）,g〉0且ui〉0（i=1,…,m＋1）时,f（u1,…,um＋1）〉0;当ui〈0（i=1,…,m＋1）时,f（u1,…,um＋1）〈0．     

Binuclear ion containing nitrogen as a bridging group

A binuclear ion ([NH(3))5RuN(2)Ru(NH(3))(5)](5)+ is formed by the direct reaction of N(2) with an aqueous solution of (NH(3))(5)RuOH(2)(2+) at room temperature. The binuclear ion is also formed by the reversible reaction of (NH(3))5RuOH(2)(2+) with (NH(3))(5)RuN(2)(2+). Solid [(NH(3))(5)RuN(2)Ru(NH(3))(5)] (BF(4))(4) has been prepared, and its ultraviolet and infrared spectra are reported.     

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.     

不同氮形态对杉木叶绿素荧光参数和叶绿体超微结构的影响

以1个月生杉木实生苗为试验材料,分析了硝态N、铵态N和铵硝混合（NH₄⁺∶NO₃^-=3∶1）态N对杉木生长、叶绿素荧光参数和叶绿体超微结构的影响。结果表明:1）不同处理下植株根系和地上部生物量大小表现为铵硝混合处理＞全硝处理＞全铵处理,但不同处理间杉木植株生物量不存在显著差异（P＞0.05）。2）铵硝混合处理下可变荧光强度（F_v）和最大荧光强度（F_m）显著高于全硝和全铵处理,而非化学荧光猝灭系数（nPq）显著低于全铵处理。3）铵硝混合处理下PSⅡ最大光化学效率（F_v/F_m）、PSⅡ潜在活性（F_o/F_v）、光化学猝灭系数（q_p）和PSⅡ实际光化学效率值（QY）均显著高于全硝处理,但与铵硝混合处理间不存在显著差异（P＞0.05）。4）叶绿体超微结构结果表明,全硝处理下部分叶绿体膨大隆起,基粒片层排列松散,且数量明显少于全铵和铵硝混合处理,全铵处理显著增加了叶绿体中淀粉粒的数量,而铵硝混合处理中淀粉粒则完全消失,但显著增加了嗜锇颗粒的数量。综上所述,铵硝混合处理一方面能通过增强PSⅡ反应中心电子传递效率和光能的利用能力,促进光合同化产物的积累;另一方面通过抑制淀粉粒的形成,减轻淀粉粒对光合作用的抑制,同时促进光合同化产物的输出,促进杉木幼苗的生长。     

Stibnite (Sb2S3) Solubility in Sodium Sulfide Solutions

The solubility of stibnite ( Sb(2)S(3)) was measured at 25 degrees C and 1 atmosphere in solutions ranging from 0.45 to 7.16 percent Na(2)S by weight. Sb(2)S(3): Na(2)S mole ratios of saturated solutions range from 0.238 to 0.403. Stibnite solubility increases at an increasing rate with rising Na(2)S concentration. The reaction that best fits the experimental data is 2Sb(2)S(3) + HS- + OH-= Sb(4)S(7)(2-) + H(2)O, for which an equilibrium constant was estimated to be about 5.0.     

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.     

Carbon-13--rich diagenetic carbonates in miocene formations of california and Oregon

Carbon unusually rich in C(13)(deltaC(13) = +5.4 to +19.0 per mil relative to the Peedee belemnite carbonate standard of the University of Chicago) is characteristic of certain diagenetic limestones and dolomites in the Miocene Monterey Shale of California and the Nye Mudstone of Oregon. This heavy carbon may have originated through low-temperature equilibration between CO(3)- - and CO(2) in migrating carbonated waters or between CH(4) and CO(2) in natural gas. Light carbon (deltaC(13) = -5.6 to -18.2 per mil) derived through nonequilibrium oxidation of organic matter also occurs in the carbonate of Monterey Shale in some localities, but at most places it is much less common than heavy carbon.     

舍饲生长期牦牛NH3排放及其对CH4与CO2

为舍饲育肥牦牛高效生态生产、减少有害气体和温室气体排放提供参考,采用大型呼吸测热环控舱(Chamber)模拟舍饲状态,对4头生长期育肥牦牛排放的主要温室气体甲烷(CH4)和二氧化碳(CO2)及有害气体氨气(NH3)进行动态监测.结果表明:牦牛在采食1.5~3 h后CH4排放量达最大值,维持一段时间后,排放量逐渐下降;CO2排放相对平稳;NH3排放无明显规律.CH4、CO2和NH3日平均排放量分别为22.42 g/头、1 023.10 g/头和5.84 g/头,舍内NH3浓度为157.29 mg/m3,超出牦牛耐受氨气浓度.NH3排放不影响CH4和CO2排放规律,但是影响气体总排放量.     

一类等距结点上的双周期整插值问题

给定结点组xk=kπ/σ(σ>0,k∈Z),对于正整数m1相似文献   

Effects of Nitrogen Fertilizer with Nitrification Inhibitor DMPP (3,4-Dimethylpyrazole phosphate) on Nitrate Accumulation and Quality of Cabbage (Brassica campastris L.ssp.pekinesis)

To assess the effects of N fertilizer ammonium sulphate nitrate [(NH4)2SO4 plus NH4NO3;ASN] with the new nitrification inhibitor (NI) 3, 4-dimethylpyrazole phosphate (DMPP)(ASN+DMPP) on yield, nitrate accumulation, and quality of cabbage (Brassica campastrisL. ssp. pekinesis), two field trials were carried out under various soil-climatic conditions in Jinhua City and Xinchang County, Zhejiang Province of China in 2002.Results showed that DMPP could increase the mean yield by + 2.0 t ha-1 in Jinhua, +5.5 t ha-1 in Xinchang, decrease NO3--N content by -9.4% in Jinhua, -7.3% in Xinchang and improve nutritional quality by increasing vitamin C (VC), soluble sugar, K, Fe, Zn contents significantly.     

A Molecular Ferromagnet with a Curie Temperature of 6.2 Kelvin: [Mn(C5(CH3)5)2]+[TCNQ]-

The study of magnetic phase transitions in insulating molecular solids provides new insights into mechanisms of magnetic coupling in the solid state and into critical phenomena associated with these transitions. Only a few such materials are known to display cooperative magnetic properties. The use of high-spin molecular components would enhance intermolecular spin-spin interactions and thus a series of chargetransfer (CT) salts have been synthesized that utilize the spin S = 1 molecular cation, [Mn(C(5)(CH(3))(5))(2)](+) (decamethylmanganocenium). The structure and cooperative magnetic behavior of [Mn(C(5)(CH(3))(5))(2)](+)[TCNQ(-) (decamethylmanganocenium 7,7,8,8-tetracyano-p-quinodimethanide) are reported. This salt is a bulk molecular ferromagnet with the highest critical (Curie) temperature (T(c) = 6.2 K) and coercive field (3.6 x 10(3) gauss), yet reported for such a material.     

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-).     

不同笼养条件下蛋鸡健康与福利的比较研究

研究不同笼养条件下蛋鸡的健康和福利状况。选取位于北京地区的3家商品蛋鸡场,场A、B、C,其饲养密度分别为411、420和450 cm2/只。对夏季不同蛋鸡场内环境参数及空气中NH3、CO2和H2S的质量浓度进行测定,记录蛋鸡的产蛋性能和死亡率,分析异常行为的发生频率。结果表明:场C的即时风速、最大风速和平均风速均显著高于场A和B(P<0.05),场C和A的空气温度、风寒温度、应激温度、露点温度均显著低于场B(P<0.05)。NH3和CO2质量浓度各场均有显著差异(P=0.003和P=0.011),其中均以场C最低,分别为1.00和83.73 mg/m3;H2S质量浓度低于测定下限1.00 mg/m3。观察发现,场C鸡群比场A和B鸡群对外界敏感性强。蛋鸡外观评分各场差异不显著,但蛋鸡步态评分及鸡蛋污损评分各场差异显著(P=0.042和P=0.023),其中步态评分场C显著高于场A和B(P<0.05),鸡蛋污损评分场C显著低于场A和B(P<0.05)。各场中蛋鸡异常行为的发生频率无显著差异。场C入舍母鸡产蛋量显著高于场A和B(P<0.05),平均蛋重、料蛋比、平均产蛋率、高峰期产蛋率、腿病发生率、产蛋疲劳症发生率、死亡率各场均无显著差异,但场C蛋鸡生产周期显著短于场A和B(P<0.05)。3家商品蛋鸡场饲养环境、管理措施等综合因素造成的差异远大于单纯饲养密度造成的差异,为了提高现阶段我国笼养蛋鸡的健康和福利状况,应该更加重视蛋鸡整体养殖环境和管理措施的改善。     

Dianion Stabilization by (M(C5(CH3)5)2)+: Theoretical Evidence for a Localized Ring in (DDQ)2-

Organic dianions have been stabilized by (M(C(5)(CH(3))(5))(2))(+), where M is iron or cobalt. This has allowed the structural and spectroscopic characterization of these dianions. The structure of (M(C(5)(CH(3))(5))(2))(2)(+) (DDQ)(2-), where DDQ is 2,3-dichloro-5,6-dicyanobenzoquinone, has been determined by x-ray crystallography. The structure of (DDQ)(2-)is consistent with ab initio molecular orbital calculations that suggest a localizd as opposed to a delocalized (aromatic) ring structure.     

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.     

Large first hyperpolarizabilities in push-pull polyenes by tuning of the bond length alternation and aromaticity

Conjugated organic compounds with 3-phenyl-5-isoxazolone or N,N'-diethylthiobarbituric acid acceptors have large first molecular hyperpolarizabilities (beta) in comparison with compounds with 4-nitrophenyl acceptors. For example, julolidinyl-(CH=CH)(3)-CH=N,N'- diethylthiobarbituric acid, which has 12 atoms between the donor and acceptor, has a beta(0) of 911 x 10(-30) electrostatic units, whereas (CH(3))(2)NC(6)H(4),-(CH=CH)(4)-C(6)H(4)NO(2), with 16 atoms between its donor and acceptor, has a beta(0) of 133 x 10(-30) electrostatic units. The design strategies demonstrated here have resulted in chromophores that when incorporated into poled-polymer electrooptic modulators exhibited significant enhancements in electrooptic coefficients relative to polymers containing the commonly used dye Disperse Red-1. Poled polymer devices based on these or related chromophores may ultimately lead to high-speed electrooptic switching elements with low drive-power requirements, suitable for telecommunications applications.