四氟乙烯齐聚体的反应 四氟乙烯四、五聚体和芳香胺的反应

前已报道四氟乙烯四聚体(全氟-3,4-甲基己烯-3)(1)、五聚体(全氟-3,4-二甲基-4-乙基己烯-2)(2)和脂肪烷氧以及脂肪胺的亲核反应.本文报道化合物1,2和芳香胺如苯胺、β-萘胺的反应.由于烯烃1、2双键处于分子中间,因而当亲核试剂进攻时,双键容易发生重排,生成的末端基烯烃更具反应性,故导致一取代、二取代、三取代以及环化降解等复杂产物.     

PHOTOCHEMISTRY OF QUINOLYLMETHYLISOTHIORONIUM SALTS. GUANINE SELECTIVE DNA PHOTOCLEAVAGE REAGENTS

Quinolylmethylisothioronium salts (1a and 4a) cleave DNA upon irradiation. The cleavage is more than 10-fold enhanced by piperidine treatment and subsequently shows a high preference for guanines. Photolysis of 1a, 2a and 4a in water at lambda greater than 300 nm resulted in photoheterolysis. Irradiation of 1a in 2-propanol gave only products from photohomolysis, irradiation of 1a in methanol and 2a and 4a in 2-propanol resulted in products from both photoheterolysis and photohomolysis. Quantum yields for the disappearance of 1a in water and 2-propanol were determined. The presence or absence of oxygen had no effect in water, whereas oxidation products were observed upon irradiation in methanol and 2-propanol in the presence of oxygen. The guanine specific DNA photoreaction is proposed to take place by alkylation at N7 via the quinolylmethyl carbocation and thus to represent a photoalkylation.     

Hydrogen-bond-assisted control of H versus J aggregation mode of porphyrins stacks in an organogel system

To obtain insights into a correlation relationship between the structure and the aggregation mode in an organogel system, we synthesized gelators 2a-4a bearing a porphyrin moiety as a one-dimensional aggregation unit and amide groups as peripheral hydrogen-bonding sites. Gelators 3a and 3b bearing the amide groups at the 4-position of the meso-phenyl groups are classified as versatile gelators, gelating 10 and 14 solvents, respectively, among 23 solvents tested herein. In contrast, gelators 2a and 4a bearing the amide groups at the 3,5-positions and 3-position, respectively, are classified as poor gelators. Examination by spectroscopic methods (UV-vis, ATR-FTIR, XRD, etc.) revealed that in the organogel phase porphyrins in 3a adopt the H aggregation mode whereas those in 2a and 4a adopt the J aggregation mode. X-ray analysis of the single crystals established that in fact 3b features a columnar stack of porphyrin moieties that can be classified as the H-aggregate, whereas 2a results in a two-dimensional a-b plane, in which porphyrin moieties are arranged in the J-aggregate. Very interestingly, the difference in the H versus J aggregation mode is well-reflected by the difference in the macroscopic aggregate morphology observed by SEM: 3a + cyclohexane gel results in a one-dimensionally aggregated fibrillar structure, whereas 2a + cyclohexane gel results in a two-dimensional sheetlike structure. These findings indicate that the H versus J aggregation mode of porphyrin stacks can be controlled by the peripheral hydrogen-bonding interactions and the microscopic hydrogen-bonding network structure is well-reflected by the macroscopic SEM-observed structure.     

Direct drug metabolism monitoring in a live single hepatic cell by video mass spectrometry

The metabolism of anti-breast cancer drug, tamoxifen, in a single human hepatocellular carcinoma cell, HepG2, was directly monitored by a video-mass spectroscope. The cytoplasm, a vacuole or nucleus of the cell was directly sucked by a nano-spray tip under a video-microscope, and then was introduced into a mass spectrometer. Unchanged drug molecules were found in cytoplasm and a vacuole, but the metabolites were only found in the cytoplasm. This direct detection of drug metabolites in a live single cell is useful for speedy drug metabolism monitoring.     

Modeling of interface phenomena in liquid under vibration, using the chemical model

An analysis of interface phenomena in a liquid under a vibration field is presented, based on the chemical model of vibration in a liquid. The objects studied are a bubble, a solid surface, and a linear macromolecule, in a vibrated liquid. It is concluded that many sonochemical phenomena can be realized in some different (two or more) mechanisms, and mutually stimulate. Inharmonic effects and the influence of distant neighbors are analyzed.     

Modeling of the pseudo-colloids migration for multi-member decay chains with a arbitrary flux boundary condition in a fractured porous medium

A deep geologic disposal is the prime option for the long-term isolation of high-level radioactive waste (HLW) in many countries. For deeply located repositories, a radionuclide released from a failed waste container moves through the engineered and natural barriers before it reaches a biosphere. The pseudo-colloid which a radionuclide is adsorbed on a moving natural humic or fulvic colloid can be generated in a fractured porous medium. The size of a colloid is in general in the order of a hundred nanometer so that its migration velocity in a fracture is higher than that of a radionuclide due to the hydrochromatic effect. A large colloid cannot diffuse easily into a surrounding rock. Also, there are many kinds of actinides and these actinides have decay chains. In this analysis, the canonical form solution is derived for a pseudo-colloid and a solute in a fracture and a surrounding rock with a realistic inlet boundary condition with multi-member decay chains. It is used the Fortran based a computational code which uses a special subroutine for the inversion of Laplace transform. Consequently, the role of the pseudo-colloid in the fractured porous medium is important and also their decay chains aren’t neglected in the performance assessment of the HLW.     

Droplet formation in a thin layer of a two-component solution under the thermal action of laser radiation

Droplet growth in thin layers of water-alcohol solutions under the effect of a concentration-induced capillary flow, which is governed by a laser electromagnetic radiation, is investigated. It is established that an increase in water concentration in a solution accelerates the droplet growth. In low-concentrated solutions, a droplet may reach a quasi-steady state, in which its diameter is no larger than the diameter of the light beam projection onto the layer. A rise in the radiation power above an optimal magnitude decelerates the droplet growth. In low-concentrated solutions, this deceleration results from a decrease in the flow that feeds the droplet, while in high-concentrated solutions, it is due to a droplet constriction and an increase in its curvature radius.     

Photochromism of mixed crystals containing bisthienyl-, bisthiazolyl-, and bisoxazolylethene derivatives

Single crystals composed of two or three different kinds of diarylethenes, having similar geometrical structures but different colors in the closed-ring isomers, 1,2-bis(2-methyl-5-phenyl-3-thienyl)perfluorocyclopentene (1a), 1,2-bis(5-methyl-2-phenyl- 4-thiazolyl)perfluorocyclopentene (2a), and 1,2-bis(5-methyl-2-phenyl-4-oxazolyl)perfluorocyclopentene (3a) have been prepared in an attempt to form single crystals which exhibit different colors, depending on illumination wavelengths. When 1a and 2a are mixed in ethanol and the content of 2a in the feed is higher than that of 1a, only a needle-shaped crystal is obtained. The crystal shape is similar to that of 2a. On the other hand, high content of 1a in the feed leads to formation of a block-shaped crystal, of which the shape is similar to that of 1a. At a feed ratio of 1:1 for 1a and 2a, two types of crystals such as needle- and block-shapes are obtained from the same batch. Mixed crystals composed of three kinds of derivatives 1a/2a/3a have also been prepared. A crystal composed of the three derivatives in the molar ratio of 32 (1a):53 (2a):15 (3a) was obtained. X-ray analysis proved that 1a and 3a are packed in the crystal lattice of 2a. The mixed crystal 1a/2a/3a changed color from colorless to yellow, red, and blue upon irradiation with light of appropriate wavelengths.     

Study of the electrochemical reduction of dioxygen in acetonitrile in the presence of weak acids

The electrochemical reduction of dioxygen has been studied in acetonitrile at glassy-carbon electrodes. The initial step is the reversible one-electron reduction to form superoxide. In the presence of hydrogen-bond donors (water, methanol, 2-propanol), the superoxide forms a complex with the donor resulting in a positive shift in the potential that can be analyzed to obtain formation constants for these complexes. Stronger acids result in protonation of the superoxide followed by reduction to produce HO2-. In the absence of hydrogen-bond donors, the reduction of superoxide occurs at very negative potentials, and this second reduction peak is very much drawn-out along the potential axis, indicating a small value of the transfer coefficient, alpha. The addition of hydrogen-bond donors, HA, brings about a positive shift in this peak, without a noticeable change in shape. The reaction occurring at the second peak is a concerted proton and electron transfer (CPET) in which the electron is transferred to superoxide and a proton is transferred from HA to the superoxide, forming HO2- and A- in a concerted process. An estimation of the standard potential for this reaction shows that the second reduction always occurs at a high driving force, which explains the small value of alpha that is observed. Consistent with a CPET, a kinetic isotope effect, HA versus DA, was detected for the three hydrogen-bond donors. The increasing positive shift of the second peak with increasing water concentration has been interpreted as being a consequence of the change in the formal potential, as water is both a reactant in the process and a participant through the hydrogen-bond stabilization of the anions.     

A novel method that improves sensitivity of protein detection in PAGE and Western blot

We have developed a simple and inexpensive method that improves sensitivity of protein and antigen detection in standard PAGE procedures. Our technique uses a sample microloader device with a funnel‐like structure, filled with a 4% stacking gel. When attach to the top of a polyacrylamide slab gel, the proteins in a sample are concentrated by electrophoresis into a small volume as they emerge from the device's narrow outlet. Our microloader has several advantages over previous devices, including simple assembly, high versatility, and absence of cross‐contamination between lanes. Addition of this device to a slab gel results in a fivefold increase in the sensitivity of antigen detection in a Western blot. As a result, less protein is required for loading and signal detection. Our protocol is a straightforward modification of a standard experimental technique, and is especially useful when only limited sample quantities are available.     

Real-time monitoring of brain energy metabolism in vivo using microelectrochemical sensors: the effects of anesthesia

Rats were implanted in the striatum with a Pt/Ir electrode for measurement of regional cerebral blood flow (rCBF) (H(2) clearance technique), a carbon paste electrode for monitoring tissue oxygen and a glucose biosensor for monitoring extracellular glucose. Changes in all three parameters were recorded in response to the intraperitoneal (i.p.) administration of the anesthetics chloral hydrate (350 mg/kg), sodium pentobarbitone (60 mg/kg) and ketamine (200 mg/kg). An i.p. injection of normal saline, given as a control for the injection of the anesthetics, produced a parallel increase in rCBF and tissue oxygen accompanied by a brief decrease in extracellular glucose. Changes in tissue oxygen reflected the changes in rCBF; there was a decrease in both after sodium pentobarbitone, a decrease followed by a rebound after ketamine and a transient increase after chloral hydrate. All three anesthetics produced a decrease in extracellular glucose. The disparity between the changes in glucose and the changes in rCBF and oxygen suggests that during anesthesia, the reduction in extracellular glucose is not due to a reduction in the direct delivery of glucose from the blood vascular system. These results also indicate that levels of enzymatic substrates and mediators, which are intrinsic to the design and operation of amperometric biosensors, are clearly altered in a complex manner by anesthesia and suggest that caution should be exercised in extrapolating data from acute anesthetized experiments to normal physiology.     

Deposition of cation-absorptive biocolloids onto a charged surface

Classical theoretical assumptions, which are implausible for describing biological behavior in real systems include uniform fixed charge distribution in colloidal outer membrane layer, uniform dielectric constant throughout the membrane phase, and point charge for ionic sizes. In the present study, absorption of cations by fixed functional groups in the membrane layer, variation in dielectric constant in a system, and effect of ionic sizes are considered to investigate the deposition of biocolloids each covered with an ion-penetrable membrane. The simulated results reveal that a larger numbers of cations involved in the formation of a cations-fixed groups complex, a smaller dielectric constant near a biological uncharged core, a larger dielectric constant of the membrane phase, a smaller cation-absorption equilibrium constant, a smaller concentration of total functional groups in the membrane layer, a thicker membrane, smaller cations, larger anions, and larger functional groups yield a faster rate of deposition.     

Fast choice of separation conditions for analyses by capillary zone electrophoresis using an information system Xemic

An information system Xemic applicable in analytical chemistry is described and its use in capillary electrophoresis for searching suitable separation conditions is demonstrated. This system is capable to provide suitable separation conditions even for analytes for which no electrophoretic experiments have been published so far. The system works with a database of components of anionic character the analyses of which have been performed, published in reviewed scientific journals, and included into a database created by an expert. Moreover, the system learned to search also in abstracts or complete scientific articles to find articles dealing with the determination of a substance in a given sample matrix. When no experiments have been published so far for a defined substance in a specific matrix, Xemic shows the separation conditions for determination of the substance regardless of the matrix. When no response can be found for the analyte of interest at all, the system Xemic works like an expert in the field and searches chemically similar substances and offers a series of substances the physicochemical properties of which are close to the followed analyte with respect to the behavior in the electric field, and shows working conditions for their analysis. Thus, the analyst puts only the order in the form of a given analyte in a given matrix and obtains a recommendation of a separation system that should enable to perform a successful separation. The system is not rigid and enables the operator to change the importance of individual attributes used in similarity search so as to obtain a broader or narrower group of similar components. With a certain probability the analyte of interest can be successfully analyzed under separation conditions that suited for the analysis of the most similar substances in the given matrix.     

Direct determination of traces of Ag, Cd, Pb, Bi, Cr, Mn, Co, Ni, Li, Be, Cu and Sb in environmental waters and geological materials by simultaneous multi-element graphite furnace atomic absorption spectrometry with Zeeman-effect background correction

A method was developed for direct determination of minor and trace amounts of Cr, Mn, Cu, Ni, Co, Li, Pb, Cd, Bi, Sb, Be and Ag in silicate rock, lake and stream sediments using a microwave oven dissolution method and a multi-element graphite furnace atomic absorption spectrometer equipped with a Zeeman-effect background correction device. The measurement technique was also suitable for direct determination of trace and ultra-trace amounts of these elements in drinking and seawater samples. A rock or sediment sample was brought into solution in a Teflon vessel by heating in a microwave oven with a mixture of hydrofluoric acid and aqua regia, followed by a further heating with a mixture of boric acid and ethylenediaminetetraacetic acid. The specified elements were directly determined in a group of four elements in one firing and eight elements in two firings from this solution or from a diluted solution using the optimum operating parameters developed in this work. The method, tested with 23 international reference rocks and sediments and seven international quality control and reference water samples, showed good to excellent agreement with the recommended values.     

Triggering blue-red transition response in polydiacetylene vesicles: an electrochemical surface plasmon resonance method

Electrochemical surface plasmon resonance (E-SPR) was used to investigate whether the chromic properties of a polydiacetylene (PDA) vesicle films, adsorbed onto an ultra-thin gold electrode, could be triggered by applied potential. This approach constitutes a preliminary model for a novel approach to the use of a triggered chromic transition, as an indicator of biorecognition headgroup binding in these materials. A PDA chromic blue-red transition was identified in E-SPR against the background Deltaepsilon(e) and Deltaepsilon(m). The latter resulted in a ca. 100 mDeg V(-1) shift in the SPR minimum, in the presence of PDA, with the PDA shielding changes in epsilon(e). Electrochemical charge transfer processes in the pre-oxide/oxide anodic region with adsorbed oxygen and hydroxide, involving a change in Au redox state (Au(0)/Au(+)) were visible in the SPR, due to a change in the gold layer thickness and gold oxide layer. However, the cathodic processes, not involving a change in the Au redox state or a increase/decrease in the surface layer dielectric, did not cause a change in the SPR. Based on this, dramatic changes in the optical properties of the adsorbed PDA film could be triggered at an applied cathodic potential, and were identified using SPR. These correlated with a pH-induced chromic transition. Both protonation and ion binding, linked with headgroup environment, were implicated in causing structural transitions in the adsorbed vesicle layer that may also be linked with their bulk optical properties.     

Guiding DC glow discharge in microchannels

This work describes the conditions, in terms of dimensions and geometry, to guide a dc glow discharge preferentially through a microchannel in simple networks. Two- and three-channel microfluidic structures were studied. A preference towards a wider channel, in a two-channel network, was observed when the difference in width was at least 18% and the length was at least 10 mm. In a three-channel structure, a change in glow discharge intensity was observed when the network was downscaled from a pathlength of 2 to 0.5 cm. While the intensity within the path with fewer turns decreased with a reduction in size, the intensity of the path with greater number of turns increased.     

CSTR和批式反应器中酶法拆分萘普生的比较

比较了批式反应器和连续流动搅拌反应器中酶动力学拆分萘普生的不同之处。从宏观反应器平衡角度,推导出了在ＣＳＴＲ中不同于在批式反应器中的酶立体选择性,产物对映体过量值和反应转化率的定量关系式,并通过脂肪酶催化的萘一甲酯的不对称水解反应得到了证实。     

Some practical aspects of free energy calculations from molecular dynamics simulation

In this work, we address two critical aspects of calculation of the free energy differences in molecular systems from molecular simulations. The first aspect involves checking whether the calculated free energy difference depends significantly on the extent of perturbation used for accomplishment of a given transformation. The second aspect of interest is to verify if the sampling errors in calculating the free energy differences between the wild-type molecule and a mutated one in its free state and in a complex are similar, or not, for a finite-length dynamic simulation. The reliability of the free energy estimates obtained from molecular simulations using thermodynamic cycles depends in part on this fact. For investigating these aspects, we use a self-transformation scheme in which a transformation of a part of a molecular system into itself is considered. We perform MD simulations of DNA fragments in which a part of a specific base is subjected to such a self-transformation. Results indicate that the estimated free energy differences do not depend significantly on the extent of perturbation used to achieve the transformation. Interestingly, the variation in the cumulative free energy difference, ΔA, with the coupling parameter, λ, depends significantly on the extent of perturbation. We examine the physical basis of the observed nature of the variation of the accumulated free energy difference, ΔA, against the λ value in the case of a self-transformation. In a thermodynamic cycle, the sampling errors due to the finite-length simulation for the molecular system are found to be similar to each other for the two perturbations (free and in a complex) justifying the use of such approach in calculating ΔΔA in molecular complexes. ©1999 John Wiley & Sons, Inc. J Comput Chem 20: 877–885, 1999     

TDP-mycaminose biosynthetic pathway revised and conversion of desosamine pathway to mycaminose pathway with one gene

Analysis of the tylosin gene cluster in Streptomyces fradiae uncovered an ORF, tyl1a, homologous to a hexose 3,4-isomerase found in Aneurinibacillus thermoaerophilus. Inclusion of the tyl1a gene along with other mycaminose biosynthetic genes (tylB, tylM1, tylM2, tylM3) identified in previous studies in an in vivo expression system successfully reconstituted the mycaminose pathway. Expression of tyl1a alone in the S venezuelae KdesI mutant converted a desosamine pathway to a mycaminose pathway. These results strongly support the role of Tyl1a as a TDP-4-keto-6-deoxy-d-glucose 3,4-isomerase.