Taming superacids: stabilization of the fullerene cations HC60+ and C60.+

A new superacid, H(CB11H6X6) (where X = chlorine or bromine), whose conjugate base is the exceptionally inert CB11H6X6- carborane anion, separates Bronsted acidity from oxidizing capacity and anion nucleophilicity in a manner not previously achieved. Reaction of this superacid with C60 gives HC60+ as a stable ion in solution and in the solid state. In a separate experiment, an oxidant was developed such that the long-sought C60.+ ion can be synthesized in solution. The preparation of these two fullerene carbocations is a notable departure from the prevalent chemistry of C60, which is dominated by the formation of anions or the addition of nucleophiles. The H(CB11H6X6) superacid overcomes the major limitations of presently known superacids and has potentially wide application.     

The transition state of the f + h2 reaction

The transition state region of the F + H(2) reaction has been studied by photoelectron spectroscopy of FH(2)(-). New para and normal FH(2)(-)photoelectron spectra have been measured in refined experiments and are compared here with exact three-dimensional quantum reactive scattering simulations that use an accurate new ab initio potential energy surface for F + H(2). The detailed agreement that is obtained between this fully ab initio theory and experiment is unprecedented for the F + H(2) reaction and suggests that the transition state region of the F + H(2) potential energy surface has finally been understood quantitatively.     

葡萄糖溶液流变特性研究

[目的]研究不同温度和浓度对葡萄糖溶液黏度的影响。[方法]基于文献报道的建模方法,研究不同温度和浓度对葡萄糖溶液黏度的影响。[结果]建立了温度浓度-黏度数学模型μ=μ0exp[(-282 400/T2+1 999/T-2.874)m]。通过外推法发现m→0时理论水黏度μ0≠μ水,借助于1HNMR测量溶液中水分子氢键缔合程度,发现葡萄糖溶液黏度受温度和浓度的影响主要取决于葡萄糖分子和水分子间作用力的相对强弱。结合特定温度下的水黏度常数,确定温度浓度-黏度数学模型中存在μ0=0.410 7μ水+0.518 8的偏差,进一步将葡萄糖溶液黏度与温度和浓度变化的连续方程修正为μ={0.736exp[6.74(273/T)2-4.8(273/T)-1.94]+0.518 8}exp[(-282 400/T2+1 999/T-2.874)m]。[结论]研究结果可为结晶葡萄糖的制备加工提供理论依据。     

Efficient multistep photoinitiated electron transfer in a molecular pentad

A synthetic five-part molecular device has been prepared that uses a multistep electron transfer strategy similar to that of photosynthetic organisms to capture light energy and convert it to chemical potential in the form of long-lived charge separation. It consists of two covalently linked porphyrin moieties, one containing a zinc ion (P(Zn)) and the other present as the free base (P). The metailated porphyrin bears a carotenoid polyene (C) and the other a diquinone species (Q(A)-Q(B)). Excitation of the free-base porphyrin in a chloroform solution of the pentad yields an initial charge-separated state, C-P(Zn)-P(.+).-Q(A)(-)-Q(B), with a quantum yield of 0.85. Subsequent electron transfer steps lead to a final charge-separated state, C(.+)-P(Zn)-P-Q(A)-Q(B)(.-), which is formed with an overall quantum yield of 0.83 and has a lifetime of 55 microseconds. Irradiation of the free-base form of the pentad, C-P-P-Q(A)-Q(B), gives a similar charge-separated state with a lower quantum yield (0.15 in dichloromethane), although the lifetime is increased to approximately 340 microseconds. The artificial photosynthetic system preserves a significant fraction ( approximately 1.0 electron volt) of the initial excitation energy (1.9 electron volts) in the long-lived, charge-separated state.     

An Accurate Quantum Monte Carlo Calculation of the Barrier Height for the Reaction H + H2 rarr H2 + H

An improved quantum Monte Carlo method has been used to calculate the classical barrier height for the hydrogen exchange reaction H + H(2) --> H(2) + H with accuracies greater than previously attained. The method is exact in that, except for the easily estimated Monte Carlo statistical or sampling error, it requires no mathematical approximations or physical approximations beyond those of the Schr?dinger equation. The minimum in the barrier, occurring for the collinear nuclear configuration with the protons separated by 1.757 bohrs, was found to be 9.61 +/- 0.01 kilocalories per mole above H + H(2).     

负载型纳米零价铁对硝基苯的还原及铁形态变化

以短孔道有序介孔氧化硅材料Zr-Ce-SBA-15为载体,采用等体积浸渍-气相还原法制备铁硅摩尔比为0.15的纳米零价铁复合材料NZVI/Zr-Ce-SBA-15。以硝基苯(NB)为目标污染物考察复合材料对环状硝基化合物的还原性能,并对复合材料中铁粒子的存在形态进行分析。结果表明,复合材料比未负载纳米零价铁对NB具有更好的还原性能。NB溶液初始浓度为20 mg/L,复合材料投加量为1 g/L,反应12 h时溶液中NB的去除率可达93.6%,苯胺为最终还原产物。反应前材料中的铁以α-Fe0的形式存在,反应后大部分以非晶态铁氧化物的形式附着在材料的铁颗粒表面。     

回归最优设计法在水培白菜肥料效应中的应用

利用“416-A”回归最优设计研究Ca(NO3)2·4H2O、KNO3、NH4H2PO4、MgSO4·7H2O对水培白菜的产量效应。数学模拟建立了四种肥料与白菜产量的回归方程:y=97.808-4.337x1 3.445x2-2.690x3 8.299x4-6.894x1x2 17.331x1x3-7.389x1x4-3.191x2x3 6.364x2x4 0.063x3x4-9.629x12-17.150x22-17.915x32-24.066x42。经检验回归关系显著,并对回归系数进行了检验。从回归方程可得:MgSO4·7H2O对产量以直接作用为主,其次为Ca(NO3)2·4H2O、KNO3和NH4H2PO4。Ca(NO3)2·4H2O与其它三种肥料均有交互作用,其中与NH4H2PO4交互作用达极显著水平。从产量效应回归关系优选出配方浓度为:Ca(NO3)2·4H2O:971mg/L;KNO3:931mg/L;NH4H2PO4:204mg/L;MgSO4·7H2O:581mg/L。采用回归最优设计结合水培研究肥料效应精确可行。     

Laser manipulation of atoms and particles

A variety of powerful techniques to control the position and velocity of neutral particles has been developed. As examples of this new ability, lasers have been used to construct a variety of traps, to cool atoms to temperatures below 3 x 10(-6) kelvin, and to create atomic fountains that may give us a hundredfold increase in the accuracy of atomic clocks. Bacteria can be held with laser traps while they are being viewed in an optical microscope, and organelles within a cell can be manipulated without puncturing the cell wall. Single molecules of DNA can now be stretched out and pinned down in a water solution with optical traps. These new capabilities may soon be applied to a wide variety of scientific questions as diverse as precision measurements of fundamental symmetries in physics and the study of biochemistry on a single molecule basis.     

Superconductivity and the quantization of energy

Ideas about quantized energy levels originated in atomic physics, but research in superconductivity has led to unparalleled precision in the measurement of energy levels. A comparison of levels produced by two Josephson junctions shows that they differ by no more than 3 parts in 10(19) at an energy of 0.0003 electron volt. The fact that the myriad of interactions of 10(12) particles in a macroscopic body, a Josephson junction, can produce sharply defined energy levels suggests a dynamical state effectively divorced from the complexities of its environment. The existence of this state, the macroscopic quantum state of superconductors, is well established, but its isolation from intrinsic perturbations has recently been shown to be extraordinary. These new results, with an improved precision of about ten orders of magnitude, are discussed in the context of highly accurate results from quantum electrodynamics, atomic spectroscopy, and the standards of metrology. Further refinements in precision may be achievable at higher energy levels, about 12 electron volts, as they become available from a new series array of 18,992 Josephson junctions.     

基于数值模拟的厚黄土煤炭开采区冒裂带高度研究

陕北黄土高原煤矿区覆盖着厚黄土层且水资源短缺,为了指导其安全生产和水资源保护,以黄陵二号矿为例,应用多种方法研究冒裂带发育高度,以期得出较优的预测方法,并得出黄陵矿区适合的裂采比.研究主要利用有限差分软件(FLAC3D)进行数值模拟,由于厚黄土自重影响基岩开采沉陷,计算中使用了厚黄土有效载荷对应的等效开采宽度.研究还应用了经验公式计算法和实际钻探测量法,对比实际钻探测量数据,数值模拟结果与其较为一致,而经验公式计算结果则小得多.因此在黄陵厚黄土层煤矿区,经验公式并不适用,而数值模拟则较为准确.通过综合分析计算结果,得出黄陵二号矿适合的裂采比为28,并应用裂采比对黄陵二号矿首采区顶板突水危险性进行了分区预测,为其水害的预防和控制提供了参考.     

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.     

一类带临界指数的凹凸非线性椭圆方程第二个正解的存在性

主要研究了一类凹凸非线性椭圆方程-Δu=up+λuq x∈Ω u>0 a.e.x∈Ω u∈H1(Ω)(1)第二个正解的存在性,其中N≥3,p=N+2/N-2,0相似文献   

Fractional statistics: quantum possibilities in two dimensions

A standard notion of quantum mechanics is that all particles, elementary or composite, must fall into one of two fundamental categories: fermions or bosons. However, it has recently been discovered that there can be quantum particles which are neither fermions nor bosons. Such particles (anyons) can only occur in two spatial dimensions-yet this does not rule out their existence, for they are found as elementary excitations in confined, quasi-two-dimensional condensed-matter systems and may occur in other systems as well. An overview of the argument for the existence of anyons is presented, along with a discussion of their role in condensed-matter physics.     

Nonadiabatic interactions in the Cl + H2 reaction probed by ClH2- and ClD2- photoelectron imaging

The degree of electronic and nuclear coupling in the Cl + H2 reaction has become a vexing problem in chemical dynamics. We report slow electron velocity-map imaging (SEVI) spectra of ClH2- and ClD2-. These spectra probe the reactant valley of the neutral reaction potential energy surface, where nonadiabatic transitions responsible for reactivity of the Cl excited spin-orbit state with H2 would occur. The SEVI spectra reveal progressions in low-frequency Cl.H2 bending and stretching modes, and are compared to simulations with and without nonadiabatic couplings between the Cl spin-orbit states. Although nonadiabatic effects are small, their inclusion improves agreement with experiment. This comparison validates the theoretical treatment, especially of the nonadiabatic effects, in this critical region of the Cl + H2 reaction, and suggests strongly that these effects are minor.     

Diffusion of weak acids across lipid bilayer membranes: effects of chemical reactions in the unstirred layers

Chemical reactions in the aqueous unstirred layers of solution adjacent to a membrane can have dramatic effects on the diffusion of solutes across that membrane. This is demonstrated by the diffusion of labeled salicylate and salicylic acid across a phospholipid bilayer membrane. Two types of chemical reactions are considered. The first is an isotopic exchange reaction between the ionic and nonionic forms of a weak acid, HA + *A(-) [unknown] H*A + A(-). This reaction provides a way of estimating the true membrane permeability to a highly permeant weak acid and also a way of estimating the thickness of the unstirred layers. The second chemical reaction, the dissociation of a weak acid, HA [unknown] H(+) + A(-), can be used to show how the presence or absence of buffers in the unstirred layers controls the net transport of permeant weak acids across a membrane. In principle, the addition of appropriate "antacid" buffers to salicylates can increase their rate of absorption from the stomach.     

Mendelevium: divalency and other chemical properties

Mendelevium (element 101) is the first actinide element found to give a divalent ion stable in solution. Reduction from the 3+ oxidation state was accomplished with Zn dust, Zn-Hg amalgam, Cr(2+), Eu(2+), and V(2+); additionally, measurements of the equilibrium with V(2+) provided an estimate of +0.2 volt for the couple, Md(2+) = Md(3+) + e(-). The chemical behavior of Md(3+) is similar to that of the other trivalent actinides and lanthanides. Oxidation from the trivalent to higher valence states with sodium bismuthate was not detected.     

A solid sulfur cathode for aqueous batteries

Because of its high resistivity and subsequent low electroactivity, sulfur is not normally considered a room-temperature battery cathode. An elemental sulfur cathode has been made with a measured capacity of over 900 ampere.hours per kilogram, more than 90 percent of the theoretical storage capacity of solid sulfur at room temperature, accessed by means of a lightweight, highly conductive, aqueous polysulfide interface through the electrocatalyzed reaction S + H(2)O + 2e(-) --> HS(-) + OH(-). This solid sulfur cathode was first used in a battery with an aluminum anode for an overall discharge reaction 2Al + 3S + 3OH(-) + 3H(2)O --> 2Al(OH)(3) + 3HS(-), giving a cell potential of 1.3 volts. The theoretical specific energy of the aluminum-sulfur battery (based on potassium salts) is 910 watt.hours per kilogram with an experimental specific energy of up to 220 watt.hours per kilogram.     

17—4PHMo钢的热处理与电化学腐蚀关系的研究

本文讨论了17—4PHMo(OCr17Ni4Cu4Mo2Nb)钢在含1.8％H_2SO_4和4.5％NaCl的溶液中电化学腐蚀行为。试验表明:经正常热处理的试样,在含Cl~-和H~+的溶液中能生成稳定的钝化膜,这种钝化膜只有当金属阳极电位高于20毫伏时才能被击穿。同时,由于Epp值相对较正,即使钝化膜被击穿而产生局部的点蚀,也能重新钝化,恢复完整的钝化膜。本文还讨论了钢热处理后的显微组织,也讨论了热处理工艺与电化学性能之间的关系,从而阐明该钢在较高NaCl含量的酸性溶液中不易产生点腐蚀破坏。     

Resonant tunneling in the quantum Hall regime: measurement of fractional charge

In experiments on resonant tunneling through a "quantum antidot" (a potential hill) in the quantum Hall (QH) regime, periodic conductance peaks were observed as a function of both magnetic field and back gate voltage. A combination of the two periods constitutes a measurement of the charge of the tunneling particles and implies that charge deficiency on the antidot is quantized in units of the charge of quasi-particles of the surrounding QH condensate. The experimentally determined value of the electron charge e is 1.57 x 10(-19) coulomb = (0.98 +/- 0.03) e for the states v = 1 and v = 2 of the integer QH effect, and the quasi-particle charge is 5.20 x 10(-20) coulomb = (0.325 +/- 0.01)e for the state v = (1/3) of the fractional QH effect.