Synthesis of four diastereomeric 3,5-dialkoxy-2,4-dimethylalkanals by a simple extension of the non-aldol aldol process to bis(propionates)

[formula: see text] The synthesis of all four diastereomers of bis(propionates), 3,5-dialkoxy-2,4-dimethylalkanals, by non-aldol aldol chemistry is described. The epoxy alcohols (3, 4) were converted into the mesylates (9, 11) which were cleanly rearranged to the desired 3,5-bis(oxygenated)-2,4-dimethylalkanals (10, 12) in high yield. The epoxy mesylates (13, 16) gave the desired products (14, 17) in good yield on treatment with TMSOTf and a hindered base.     

The photoelectron spectrum of HCP and comments on the first photoelectron band of HCN

The photoelectron spectrum of HCP has been obtained, Ionization potentials are found at 10.79 ± 0.01 eV (X² Π) and 12.86 ± 0.01 eV (A ² Σ). By comparison with HCP, a new interpretation of the first photoelectron band of HCN has been proposed which involves a Renner-Teller interaction in the Σ⁺ vibronic states of the molecular ion.     

Nafion化学修饰圆盘预富集-石墨炉 原子吸收联用法对牛血超氧化物歧化酶中铜、锌分布状态的研究

本文研究了Nafion化学修饰钨丝圆盘预富集-石墨炉原子吸收(GFAAS)方法测定牛血超氧化物歧化酶(SOD)中游离态Cu～(2+)及Zn～(2+)的方法,并用GFAAS法直接测定SOD中铜、锌的总量,证实了牛血SOD中金属辅基铜、锌原子个数比为1:1,初步探讨了一定浓度的牛血SOD中Cu～(2+)、Zn～(2+)的表观离解平衡常数。为提高SOD的活性和稳定性的研究,提供了一种有效的方法。     

Survival paths for reaction dynamics in fluctuating environments

We study rate processes in general Gaussian fluctuating environments using a path integral formalism. We derive a variational equation for the dominant survival path when the fluctuations relax exponentially or according to a stretched exponential law. In the case of a slowly varying barrier, the equilibrium regression approximation which is used by Frauenfelder and coworkers emerges. In this approximation, the survival path follows the ordinary law of relaxation to equilibrium. If the rate coefficients vary rapidly with environmental variables, however, the dominant survival paths exhibit more complex behaviour. Many phenomena analogous to geometrical optics occur. These include reflection off of rapid variations in rate constant, as well as refraction, giving paths very different from the equilibrium relaxation properties. A model with a piece-wise linear rate exhibits the basic phenomena, and the survival path equation is exactly solved for the general stretched exponential relaxing environment.     

Construction of a 2,6-difunctionalized 2-methyl-2H-1-benzopyran library by using a solid-phase synthesis protocol

[reaction: see text] A library containing 1200 analogues of 2,6-difunctionalized 2-methyl-2H-1-benzopyran was constructed by using a solid-phase synthesis protocol. Polymer-bound 6-amido-, 6-sulfonamido-, and 6-uredo-functionalized 2-hydroxymethyl-2-methylbenzopyrans 10 were prepared as part of a first-generation diversification step by employing reactions of respective acid halides, sulfonyl chlorides, and isocyanates with the amine precursor 7. Transformations of the resin-bound intermediates 10 by reactions with alkyl and acid halides were then used to produce a diverse series of 2,6-difunctionalized 2-methyl-2H-1-benzopyran analogues 12 and 14.     

Enhancement of photocurrent generation by honeycomb structures in organic thin films.

A light-emitting poly (distyryldimethylbenzene-co-triethylene glycol) rod-coil block copolymer was used to fabricate films with three-dimensionally ordered honeycomb structures by the breath-figure method. Photocurrent generation and photovoltaic performance are studied, and the dependence of photocurrent on applied electric field is investigated. Introducing the ordered porous structure significantly improves the photoelectric conversion behavior, because porous structures not only enhance the light-harvesting efficiency but also benefit charge separation and charge transfer. This phenomenon may have great prospects for enhancing the photovoltaic behavior of organic thin-film devices.     

A trinickel dipyridylamido complex with metal-metal bonding interaction: prelude to polynickel molecular wires and devices?

The molecule Ni(3)(dpa)(4)Cl(2) (1) can be oxidized by AgPF(6) to give crystalline Ni(3)(dpa)(4)(PF(6))(3) (2) (dpa is the anion of di(2-pyridyl)amine). This reversible oxidation occurs at a potential of 0.908 V vs Ag/AgCl electrochemically. The X-ray structure of 2 shows that the oxidation causes a major structural change (even though it is reversible), namely, a contraction of the Ni-Ni distances from ca. 2.43 A to 2.284[1] A. In addition, the electronic structure changes so that from four unpaired electrons in 1 there is only one in 2. From these remarkable results, it is inferred that while 1, and all higher homologues with 5, 7, 9,... nickel atoms are poor electronic conductors, the cations obtainable from them may be much better ones. This in turn means that by controlling the oxidation state electrochemically, these molecules may be able to function as nanoscale diodes.     

Characterization of polystyrene and polyisoprene by normal-phase temperature gradient interaction chromatography

Temperature gradient interaction chromatography (TGIC) is applied to the characterization of polyisoprene (PI) and polystyrene (PS) using normal-phase (NP) stationary phase--bare silica or diol bonded silica. Tetrahydrofuran-isooctane mixtures are used as a mobile phase. PI and linear and star shaped PS samples are successfully fractionated in terms of the molecular mass with a high resolution comparable to that of reversed-phase (RP) HPLC. Temperature dependence of the retention shows that the enthalpy of adsorption of PS to the stationary phase is exothermic. In addition, some characteristic features of the NP-TGIC system relative to those of RP-TGIC are presented, which include a high sensitivity on the polar end group and the simultaneous size-exclusion chromatographic and TGIC characterization of PS and PI mixtures.     

Controlled/“Living “Radical Polymerization of(-)-Menthyl Methacrylate

The atom transfer radical polymerization(ARP)of (-)-menthyl methacrylatc((-)-MnMA) mediated by CuCl/bipyridine and ethy1 2-bromopropionate or 1-phenylethyl bromide in THF system has been studied.The dependence of the specific rotation on molecular weight and the CD of Poly((-)-MnMA) thus obatined was investigated.     

A NEW ONE-STEP REDUCTIVE N-ALKYLATION OF AMINO ACIDS AND THEIR ESTERS

The reductive alkylation of amine with carbonyl compounds usingsodium hydrogen telluride has been investigated in recent years.Application of this method to the synthesis of N-alkyl derivativesof biologically important amino acids and their esters is described.