Direct detection of single nucleotide polymorphism (SNP) with genomic DNA by the ferrocenylnaphthalene diimide-based electrochemical hybridization assay (FND-EHA).

A ferrocenylnaphthalene diimide-based electrochemical hybridization assay (FND-EHA) was applied to the direct detection of a C-to-G transition in a codon (TCA) for Ser-447 of the human lipoprotein lipase (LPL) gene, which resulted in the termination of the LPL protein there. Either one of two 13-meric oligonucleotide probes, S447 WT and S447X MT, representing sequences complementary to those of the wild type (WT) and mutated (MT) forms, was immobilized on a gold electrode, followed by hybridization with chromosomal DNA extracted from human leukocytes under the condition in which both WT- and MT-type sequences can form a duplex. These two electrodes were soaked in an electrolyte containing FND under a condition [0.1 M HOAc/KOAc (pH 5.6) containing 0.1 KCl and 0.05 mM FND at 40 degrees C], in which only the MT duplex could undergo dissociation. FND was concentrated in proportion to the amount of the duplex formed on the electrode to give rise to a current signal. The electrochemical signal ratios obtained for WT/WT, WT/MT and MT/MT were close to the theoretical 2:1:0 with the S447 WT-modified electrode, and was again close to 0:1:2 with the S447X MT-modified one.     

Si纳米量子点的LPCVD自组织化形成及其生长机理研究

采用低压化学汽相沉积(LPCVD)方法，依靠纯SiH₄气体分子的表面热分解反应， 在由Si—O—Si键和由Si—OH键终端的两种SiO₂表面上，自组织生长了Si纳米量子点. 实 验研究了所形成的Si纳米量子点密度随SiO₂表面的反应活性位置数、沉积温度以及反应气 压的变化关系. 依据LPCVD的表面热力学过程，定性地分析了Si纳米量子点的形成机理.研究结果对具有密度分布均匀和晶粒尺寸可控的Si纳米量子点的自组织生长，以及Si基新型量子电子器 关键词： Si纳米量子点 LPCVD 自组织化形成 生长机理     

Parametric four-wave mixing in the 3d and 4d Rydberg states of NO

2 Σ⁺,H^′ 2Π^±(v^′=2), and 4dσ,πO²Σ⁺,O^′ 2Π^±(v^′=0) Rydberg states of NO molecules are described. The analyses of the two-photon excitation functions and infrared emission spectra revealed that only the ²Π^- component was involved in PFWM. This is in good accordance with the absence of amplified spontaneous emission (ASE) in the ²Σ⁺ and ²Π⁺ components due to their predissociative character. Results provide some support for the mechanism that the generation of the vacuum ultraviolet radiation was brought by PFWM in which ASE served as a third driving wave. Received: 6 January 1998     

Stepwise strain-induced crystallization of soft composites prepared from natural rubber latex and silica generated in situ

Novel biphasic structured in situ silica filled natural rubber composites were focused on their strain-induced crystallization (SIC) behavior from the viewpoint of morphology. The composites were prepared by in situ silica filling in natural rubber (NR) latex using a sol–gel reaction of tetraethoxysilane. Simultaneous time-resolved wide-angle X-ray diffraction and tensile measurements revealed a relationship between the characteristic morphology and tensile stress–strain properties of the composites associating with the SIC. Results showed stepwise SIC behaviors of NR-based composites for the first time. Pure rubber phases in the biphasic structure were found to afford highly oriented amorphous segments and oriented crystallites. The generated crystallites worked as reinforcing fillers together with the in situ silica to result in high tensile stresses of the composites. The observed characteristics are useful for understanding a role of filler network in the reinforcement of rubber.     

One-pot photochemical synthesis of novel thienobis[1]benzothiophene with an angularly-fused structure that promotes unique intermolecular S⋯S contacts in the crystalline state

4,8-Di(thien-3-yl)thieno[2,3-g:5,4-g′]bis[1]benzothiophene (8a), a member of a new class of angularly-fused thienobis[1]benzothiophenes (TBBTs), was synthesized by using a one-pot photocyclization–dehydrogenation reaction of 2,5-bis[2,2-di(thien-3-yl)ethenyl]thiophene (7a). The results of absorption and emission spectroscopy, and cyclic voltammetry studies suggest that the effective conjugation length of 8a is shorter than that of 7a. X-ray crystallographic analysis revealed that the core TBBT framework of 8a is slightly twisted. In the crystalline state, molecules of 8a are arranged in stacked columns that interact with the adjacent stacked columns via S?S contacts. Moreover, a 1:1 charge-transfer complex between 8a and 7,7,8,8-tetracyanoquinodimethane (TCNQ) forms crystals that have an alternating stacked columnar structure with both 8a and TCNQ being aligned in individual ribbon-like motifs. The crystal properties of these substances suggest that the angularly-fused TBBT framework might be a useful platform for the construction of electrically interesting materials.     

Biphenyl‐Derived Phosphepines as Chiral Nucleophilic Catalysts: Enantioselective [4+1] Annulations To Form Functionalized Cyclopentenes

Because of the frequent occurrence of cyclopentane subunits in bioactive compounds, the development of efficient catalytic asymmetric methods for their synthesis is an important objective. Introduced herein is a new family of chiral nucleophilic catalysts, biphenyl‐derived phosphepines, and we apply them to an enantioselective variant of a useful [4+1] annulation. A range of one‐carbon coupling partners can be employed, thereby generating cyclopentenes which bear a fully substituted stereocenter [either all‐carbon or heteroatom‐substituted (sulfur and phosphorus)]. Stereocenters at the other four positions of the cyclopentane ring can also be introduced with good stereoselectivity. An initial mechanistic study indicates that phosphine addition to the electrophilic four‐carbon coupling partner is not the turnover‐limiting step of the catalytic cycle.     

The second law of thermodynamics under unitary evolution and external operations

The von Neumann entropy cannot represent the thermodynamic entropy of equilibrium pure states in isolated quantum systems. The diagonal entropy, which is the Shannon entropy in the energy eigenbasis at each instant of time, is a natural generalization of the von Neumann entropy and applicable to equilibrium pure states. We show that the diagonal entropy is consistent with the second law of thermodynamics upon arbitrary external unitary operations. In terms of the diagonal entropy, thermodynamic irreversibility follows from the facts that quantum trajectories under unitary evolution are restricted by the Hamiltonian dynamics and that the external operation is performed without reference to the microscopic state of the system.     

Beckmann Fission of Some Fused Cyclobutanones: A New Entry into Indole-2-Acetonitriles and Benzo[b]thiophene-2-acetonitrile

Fused cyclobutanone derivatives have been utilized as intermediates in a variety of synthetic schemes.¹⁾ We are investigating the synthesis and ring opening reactions of cyclobutanones fused to indoles, benzo[b]furans, and benzo[b]-thiophenes, in part with the hope of discovering a novel method for introduction of two carbon atoms to such heteroaromatic systems. In this communication the synthesis and Beckmann fission²⁾ of the cyclobutanone derivatives fused to 1-benzoyl-indoles and benzo[b]thiophene are described. This provides a new entry into indole-2-acetonitriles³⁾ and benzo[b]thiophene-2-acetonitrile.⁴⁾     

REACTION OF AROMATIC NITRO COMPOUNDS WITH ELEMENTAL SULFUR IN LIQUID AMMONIA AND AMINES

Abstract

Aromatic nitro compounds were reduced with elemental sulfur in liquid ammonia and in amines, yielding the corresponding anilines. However, introduction of a substituent on the benzene ring or variation of the amine changed somewhat the pattern of this reaction. For example, 4-nitrotoluene (3) and 4-cyanonitrobenzene (6) were found to give not only the corresponding reduced products but also 4,4′-dicyanodiphenyl disulfide (10), formed by replacement of the nitro group, in addition to 4-cyanoaniline (9) in the reaction with elemental sulfur in liquid ammonia. Probable mechanisms of these reactions are discussed in the light of new knowledge on the similar reactions of elemental sulfur.     

Polymer-Complex Mediated Enzyme Electrodes for Amperometric Determination of Glucose

The immobilized enzyme chemically modified solid-state electrodes based on bilayer-film coating for amperometric determination of glucose have been fabricated and their sensor characteristics have been examined. The electrode substrate was coated with two kinds of polymeric films in a bilayer state, that is, System I: first with the cobalt tetrakis(o-aminophenyl)porphyrin polymer (poly-CoTAPP) film and then with an enzyme film consisting of bovine serum albumin and glucose oxidase (GOx), and System II: first with the Ru(NH₃)³⁺ ₆-containing montmorillonite clay film and then with the GOx enzyme film. The glucose concentration could be monitored by measuring the currents corresponding to the O₂ reduction and the H₂O₂ reduction which are electrocatalyzed by the poly-CoTAPP film (System I) and the clay film (System II), respectively. The reproducible relationship between glucose concentration and sensor output was obtained for both systems with a dynamic range of ～ 1-100 mM (for System I as an electrochemical detector for a flow injection analysis) and ～0.4-4 mM (for System II). In addition, the sensors showed long-term stability (more than 1 and 2 months in System I and System II, respectively) and relatively rapid response (response times of System I and System II are ? 5-10 and 40-60 s, respectively).