(Polyfluoro)silane-mediated generation of azomethine ylides from imines and their cycloaddition leading to N-heterocycles

The novel generation and cycloaddition of azomethine ylides from an α-(trimethylsilyl)imine using (polyfluoro)silanes is described. The method was successfully applied to an efficient one-pot process. Namely, an azaallyl anion, generated by abstraction of the hydrogen α to an imino nitrogen, was treated with a di- or trifluorosilane to give an azomethine ylide intermediate below room temperature. The generated 1,3-dipole was smoothly trapped with dipolarophiles to afford nitrogen-containing five-membered heterocycles in good yields.     

Controlling the radiation degradation of carboxymethylcellulose solution

In this study, the effects of an irradiation on the viscosity of the carboxymethylcellulose (CMC) solution were investigated, and the methods to control the degradation of the CMC caused by an irradiation were developed. The viscosity of the CMC solution was decreased with an increase in the irradiation dose, but the extent of the degradation by an irradiation was found to decrease with an increase in the CMC concentration in the solution. The dependency of the irradiation sources showed that an electron beam radiation had degraded the CMC less severely than a gamma ray radiation. An addition of vitamin C as a radical scavenger to the solution was shown to be effective in preventing the decrease of the viscosity of the solution. Also, in the case of an irradiation at −70 °C, the decrease of its viscosity was efficiently inhibited. The degradation of CMC in the solution was confirmed by the molecular weight distribution.     

Microfabricated electroosmotic pump for capillary-based sequential injection analysis

A microfabricated electroosmotic pump with an integrated serpentine isolation channel was developed on a glass chip and applied to a capillary-based sequential injection analysis (SIA) system for an enzyme inhibition assay. The pump chip contains an anode reservoir, an ion-exchange membrane electric field decoupler (EFD) that also serves as a cathode reservoir, parallel pump channels and an isolation channel. A two-step etching process was adopted to etch the pump channels to a depth of 20 μm and the isolation channel to a depth of 90 μm. The pump flow rate was very stable: the relative standard deviation (RSD) of the pump rate was 1.9% for propulsion and 2.3% for aspiration. The pump chip was successfully applied to a capillary-based sequential injection analysis system with a confocal fluorescence detector. For repetitive analysis of a 13 μM fluorescein solution, an RSD of 0.6% was attained, which demonstrated the flow stability of the EOF pump. The system was then applied to an enzyme inhibition assay, the diethylenetriaminepentaacetic acid (DTPA) inhibition of the β-galactosidase-catalyzed hydrolysis of fluorescein di(β-d-galactopyranoside). Reproducible results (RSD<3.0%) were obtained.     

Protrusion and deformation of an elastic particle at an advancing front interface

The response of an elastic particle to an extensional field close to an advancing liquid–gas interface in a capillary was examined both from an experimental and theoretical viewpoint. Experimental evidence is given on both the protrusion and deformation of an elastic particle at an advancing front interface. To interpret our experimental results, we followed and extended Hoffman's approach to the case of deformable particles. A hybrid approach was followed where the height of the bump was calculated theoretically as an equilibrium between capillary and drag forces for a given deformation of the particle, whereas the latter was supplied by an independent experimental measurement. For an elastic particle, the height of the bump goes through a maximum and further on decay almost linearly when plotted against the dimensionless parameter introduced by Hoffman. The difference between the theoretical prediction and the experimental data is discussed in relation to the asymmetry of the bump profiles observed in the experiment that could be responsible for a larger contribution of capillary forces from those calculated. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 1362–1374, 2003     

Concise Construction of the ACDE Ring System of Calyciphylline A Type Alkaloids by a [5+2] Cycloaddition

A concise route for construction of the ACDE ring skeleton in calyciphylline A type alkaloids was developed using an intramolecular [5+2] cycloaddition reaction of an oxidopyrylium species bearing a tetrasubstituted olefin. Key to the success of this reaction was the combination of acid and base, which accelerated the construction of this skeleton containing a spiro ring and vicinal quaternary carbon centers. The resultant tricyclic ADE ring compound was converted to an ACDE ring model through C−H oxidation and an aza-Wittig reaction.     

Temperature dependence of herbicide adsorption from aqueous solutions on activated carbon fiber and cloth

Diuron and amitrole adsorption from aqueous solution on an activated carbon fiber and an activated carbon cloth were studied as a function of temperature. Diuron adsorption was greater than that of amitrole and increased with rising temperature, whereas amitrole adsorption decreased when the temperature increased. Endothermicity of diuron adsorption was due to an increase in the planarity and diffusion of diuron molecules with higher temperatures. However, the exothermicity found for amitrole was due to the increase in amitrole solubility and in vibrational energy of adsorbed molecules with higher temperature. External mass transfer resistance was also found to play an important role in diuron adsorption on activated carbon cloth.     

Double cyclization of aminophosphonoacetate derived β- hydroxyacids to bicyclic β-lactams

The carbon framework for carbapenems was constructed by an asymmetric aldol condensation and subsequent direct coupling of the resulting β-hydroxy acid equivalent with an aminophosphonoacetate. Cyclization to the monocyclic β-lactam 20 was followed by oxidative elaboration to the penultimate aldehyde 22 which was converted to carbapenem 23 by an intramolecular version of a Horner-Emmons cyclization.     

Channel shape effects on the solution-flow characteristics and the liquid/liquid extraction efficiency in polymer microchannel chips.

A polymer microchannel chip with a symmetrical or unsymmetrical zigzag-side-walled structure was fabricated by an imprinting method, and applied to study shape effects on solution flow characteristics as well as on the liquid/liquid extraction efficiency of an aluminium(III) chelate complex (Al-DHAB: DHAB = o,o'-dihydroxyazobenzene) in a microchannel chip. In an unsymmetrical zigzag-side-walled channel chip (us-channel), an oil/water interface was sinusoidal, while that in a symmetrical zigzag-side-walled channel chip (s-channel) was flat as long as the observation was made under an optical microscope. It was demonstrated that the efficiency of the water-to-oil (1-butanol) extraction of Al-DHAB in the microchannel was governed by the contact time between the two phases. As the most important results, furthermore, the extraction efficiency was higher in the us-channel, as compared with that in the s-channel, owing to the sinusoidal liquid/liquid interfacial structure and, therefore, to the high interfacial area between the two phases.     

Prevention of evaporation of small-volume sample solutions for capillary electrophoresis using a mineral-oil overlay.

The suppression of evaporation of water from small volumes of sample solutions or reagents for capillary electrophoresis by the use of a mineral-oil overlay was investigated in affinophoresis applications, in which the affinity constant of a mutant protein of recombinant human galectin-1 to a lactose affinophore, a triply negative charged ion having a lactoside as an affinity ligand, was determined. When an injection was carried out from a minimum of 20 microL of an aqueous solution beneath the oil overlay, no oil contamination inside the capillary was observed, provided the capillary was cleanly cut so that the end was flat, and the polyimide coating had been removed for a distance of about 2 mm from the end. Affinophoresis was carried out using 20 microL of an affinophore solution covered with an oil overlay. The abnormalities in the electropherograms as the result of the evaporation of the water from the solution during storage prior to use in an automatic operation of a capillary electrophoresis instrument were suppressed, with respect to the formation of a base line gap, an increase in the detection time of a marker ion and an increase in the initial current. A solution in a vial could be used repeatedly for a longer period of time when overlaid with mineral oil than in the absence of an overlay. The use of a mineral-oil overlay is a simple but very efficient technique for solving the problem of the evaporation of water from small volumes of aqueous solutions for use in capillary electrophoresis.     

羟基新戊醛的间接电氧化研究

在离子交换膜电解槽内,将电解溴离子生成的溴单质作为氧化剂,使羟基新戊醛变成羟基新戊酸.研究了反应温度、pH、反应物浓度及阳极电位对电流效率和选择性的影响.结果表明,槽内式间接电氧化法制取羟基新戊酸的电流效率和选择性都较高,电流效率可达91.4%.选择性一般在90%以上.     

Formal Synthesis of Sarain A: Intramolecular Cycloaddition of an Eight‐Membered Cyclic Nitrone to Construct the 2‐Azabicyclo[3.3.1]nonane Framework

An enantioselective route to the tetracyclic skeleton of sarain A has been developed. Asymmetric reduction of an ynone introduced a chiral center which was transferred to the contiguous tertiary stereogenic centers through an Ireland–Claisen rearrangement. The 2‐azabicyclo[3.3.1]nonane framework was constructed by an unprecedented intramolecular cycloaddition of an eight‐membered cyclic nitrone. Using the steric bias of the bicyclic system, the quaternary carbon atom was constructed by a stereoselective aldol reaction. Further ring formations were performed by ring‐closing metathesis for the 13‐membered ring and an iodoamidation reaction for the pyrrolidine ring. The present synthesis has successfully provided an alternative route to the late‐stage intermediate of Overman’s synthesis.     

Extraction of water miscible organic dyes by reverse micelles of alkyl glucosides

The extraction of methyl orange or methylene blue from an aqueous phase to an organic phase of reverse micelles of alkyl glucosides was investigated. Dodecyl glucoside, a biodegradable and biocompatible surfactant, was employed as a kind of alkyl glucosides, since a stable Winsor II system consisting of the water-in-oil type microemulsion and aqueous phases was formed when an organic solution containing dodecyl glucoside was contacted with an aqueous solution. The water content in the reverse micellar organic phase increased with an increase in the concentration of dodecyl glucoside. The extraction ratio of dyes also increased with increasing the concentration of dodecyl glucoside. Furthermore, the extraction ratio of dyes was dramatically dependent upon the pH of an aqueous phase and temperature.     

Development of a fluoride-responsive amide bond cleavage device that is potentially applicable to a traceable linker

A fluoride-responsive (FR) amino acid that induces amide bond cleavage upon the addition of a fluoride was developed, and it was applied to an FR traceable linker. By the use of an alkyne-containing peptide as a model of an alkynylated target protein of a bioactive compound, introduction of the FR traceable linker onto the peptide was achieved. Subsequent fluoride-induced cleavage of the linker followed by labeling of the released peptide derivative was also conducted to examine the potential applicability of the FR traceable linker to the enrichment and labeling of alkynylated target molecules.     

Determination of glucose in wine and fruit juice based on a fibre-optic glucose biosensor and flow-injection analysis

A flow-injection system for the determination of glucose in various samples using a glucose biosensor based on an oxygen optrode with immobilized glucose oxidase (GOD) is described. The consumption of oxygen was determined via dynamic quenching of the fluorescence of an indicator by molecular oxygen. GOD was adsorbed on a sheet of carbon black and cross-linked with glutaraldehyde. Carbon black was used as an optical isolation to protect the optrode from interference from ambient light and sample fluorescence. The system is linear for 0.1–500 mM glucose, with an r.s.d. of 2% at 100 mM (5 measurements). The application of the system to glucose in wine and fruit juice is demonstrated. It was possible to analyse up to 60 samples per hour. The enzyme optrode was stable for more than 400 h in continuous use and was easily maintained.     

Synthetic studies aimed at (-)-cochleamycin A. Evaluation of late-stage macrocyclization alternatives

An efficient route to the fully functionalized ABC ring systems of the unnatural enantiomer of cochleamycin A was developed. L-(-)-Malic and L-(-)-ascorbic acids served well as starting materials for the two building blocks used to construct an (E,Z,E)-1,6,8-nonatriene intermediate. The AB part structure was assembled by way of a stereocontrolled intramolecular Diels-Alder cycloaddition via adoption of an endo transition state. From this vantage point, two general pathways were subsequently explored as to their suitability for elaboration of the CD rings. Initially examined was a protocol involving 10-membered carbocycle construction. When this approach was demonstrated not to be workable, attention was directed to 10-membered macrolactonization as an alternative tactic. Although assembly of the C-ring in this manner was easily achieved, ultimate closure of the six-membered ring to form ring D remains an unsolved problem.     

Hetero diacylation of 1,1-diborylalkanes: Practical synthesis of 1,3-diketones

An efficient protocol for the synthesis of asymmetric 1,3-diketones was reported through diacylation of 1,1-diborylalkanes using two different acyl sources. In this transformation, an enolate boron species was initially formed by introducing an acyl group, then it was trapped by another acyl group to form 1,3-diketone. This method not only provided the gateway to obtain a series of 1,3-diketones, but also afforded an operationally simple and efficient access to pyrazoles and isoxazoles.     

Maximum spectrum of continuous wavelet transform and its application in resolving an overlapped signal

To estimate the number of peaks and to find the individual peak positions in an overlapped signal, a new method called maximum spectrum of continuous wavelet transform (MSCWT) was developed by extracting the maximum coefficients of continuous wavelet transform (CWT). The peak position in MSCWT was the same as that in its original signal. In this process, CWT was performed not on a single dilation but on an appreciation dilation range. To obtain such a range, a new criterion was introduced to choose a center dilation, which was used to form the dilation range. If Cdilation denoted the center dilation, the proper dilation range was [Cdilation -6 +/- 2, Cdilation +1 +/- 1]. The Mexican Hat function was an analytical wavelet. Utilizing the information of the peak number and the position detected by MSCWT, a fitting route was performed to recover the original signal. One simulated and four true overlapped signals, including high performance liquid chromatography (HPLC), ultraviolet-visible (UV) spectrum, and differential pulse voltammetric (DPV), were processed, and the results indicated that MSCWT could detect an overlapped peak number and position, and the curve fitting based on information of MSCWT had a higher accuracy. The proposed method was an efficient one in resolving different types of overlapped signals.     

Instrumental neutron activation analysis of hafnium in zirconium metal using internal standardization

Instrumental neutron activation analysis with the internal standard correction was applied to determination Hf in high purity Zr metal. Zirconium, which was a matrix element, was used as an internal standard to compensate for inhomogeneity of the neutron flux through an irradiation capsule and to improve the gamma ray measurement uncertainty. It was found that the linearity of the calibration curves of Hf was improved with using an internal standard. The analytical result of Hf in Zr metal was in good agreement with that obtained by ICP-SFMS. The relative expanded uncertainty (k = 2) was 2.1%, and it was comparable to that of ICP-SFMS.     

A facile synthesis of phytosphingosine from diisopropylidene-D-mannofuranose

In the present study, an efficient method with a high overall yield for preparing phytosphingosine and an analogue was developed. Starting with commercially available 2,3;5,6-di-O-isopropylidene-d-mannofuranose, a variety of lipid moieties were incorporated to obtain phytosphingosine and an analogue. Through an eight-step manipulation, phytosphingosine was obtained with an overall yield of 57%.     

钙离子体系中隐式和显式内随机共振

近年来, 细胞内钙离子信号及其产生机理已成为研究热点之一, 这是因为钙离子信号能控制细胞的生死、 传递细胞间的信息、 提高基因表达的有效性和特殊性[^1~3]. 在钙离子信号传递过程中, 受环境扰动是不可避免的. Shuai等^[4]发现噪音能够控制钙离子通道中钙离子的释放. 在过去的十年中, 无论是物理、 化学还是生物体系^[5~10]的噪音效应已被广泛研究, 其中包括对随机共振(SR)的研究^[5], 经典SR是环境噪音能够放大弱的外加信号. 但随着研究的深入, 发现有无噪音SR^[11]和内SR(ISR) ^[6]. ISR的内信号来自噪音诱导的内信号, 这种SR现象叫隐式内SR(IISR). 而我们则发现了另外一种内SR, 即显式内SR(EISR) ^[12], 它的内信号是体系固有的内信号, 而不是由噪音诱导的. 本文主要研究加入外信号将对IISR和EISR产生的影响.