Starting from the racemic 3-benzofuranyl- and 3-benzo[b]thiophenyl-3-hydroxypropanoic acid ethyl esters as substrates, various multistep enzymatic procedures were developed for the efficient synthesis of the corresponding highly enantiomerically enriched (R)- and (S)-3-heteroaryl-3-hydroxypropanoic acids. 相似文献
A molecule undergoing reaction may form a short-lived intermediate. Under certain conditions, the rate at which the reaction proceeds toward the product state via the intermediate may exceed that of a simple, direct path. The competition of two alternative reactive pathways is analyzed here in terms of a stochastic model. The approach allows one to diagnose this competition as a function of the energy of the intermediate relative to the barrier heights of the potential surface and values of the reactive vibrational modes. The result has applications to a variety of problems in chemical physics, ranging from the "lock-and-key" mechanism for the enzymatic activity to control of temporal evolution of complex systems by optimal laser fields. 相似文献
ESR spectra characteristic of peroxy radicals appeared rapidly in all of eleven hydrogen-containing polymers examined when treated with dilute fluorine. These radicals presumably result from the reaction of hydrocarbon and fluorocarbon radicals, existing at undetectably low steady-state concentrations, with the oxygen impurity content of commercial fluorine. In poly(vinylidene fluoride) films of thickness 11 and 58 μm the radical contents were nearly proportional to surface area rather than volume, in agreement with earlier reports of a shallow depth of penetration. Some polymers exhibited also or exclusively a broad spectral component, varying in character with the polymer; examples are polystyrene, polyethylene, poly (vinyl chloride), poly(vinylidene chloride), polyoctafluoropentadiene, polyhexafluoropropene, and a fluorinated graphite. The broad spectral component did not react with ordinary radical scavengers such as propylene and oxygen, and is probably not due to a fluorocarbon radical but to unknown transition metal fluorides. 相似文献
In this label-free surface-enhanced Raman scattering (SERS) study of genomic DNA, we demonstrate that the cancer-specific DNA methylation pattern translates into specific spectral differences. Thus, DNA extracted from an acute myeloid leukemia (AML) cell line presented a decreased intensity of the 1005 cm−1 band of 5-methylcytosine compared to normal DNA, in line with the well-described hypomethylation of cancer DNA. The unique methylation pattern of cancer DNA also influences the DNA adsorption geometry, resulting in higher adenine SERS intensities for cancer DNA. The possibility of detecting cancer DNA based on its SERS spectrum was validated on peripheral blood genomic DNA samples from n = 17 AML patients and n = 17 control samples, yielding an overall classification of 82% based on the 1005 cm−1 band of 5-methylcytosine. By demonstrating the potential of SERS in assessing the methylation status in the case of real-life DNA samples, the study paves the way for novel methods of diagnosing cancer.
We prove unboundedness and boundedness of the unsmeared and smeared chiral vertex operators, respectively. We use elementary
methods in bosonic Fock space, only. Possible applications to conformal two-dimensional quantum field theory, perturbation
thereof, and to the perturbative construction of the sine-Gordon model by the Epstein-Glaser method are discussed. From another
point of view the results of this paper can be looked at as a first step towards a Hilbert space interpretation of vertex
operator algebras.
Received: 16 October 1997 / Accepted: 7 July 1998 相似文献
The VIP collaboration is performing high sensitivity tests of the Pauli Exclusion Principle for electrons in the extremely low cosmic background environment of the underground Gran Sasso National Laboratory INFN (Italy). In particular, the VIP-2 Open Systems experiment was conceived to put strong constraints on those Pauli Exclusion Principle violation models which respect the so-called Messiah–Greenberg superselection rule. The experimental technique consists of introducing a direct current in a copper conductor, and searching for the X-rays emission coming from a forbidden atomic transition from the L shell to the K shell of copper when the K shell is already occupied by two electrons. The analysis of the first three months of collected data (in 2018) is presented. The obtained result represents the best bound on the Pauli Exclusion Principle violation probability which fulfills the Messiah–Greenberg rule. 相似文献
A high-performance thin-layer chromatographic method combined with image processing of scanned chromatograms was developed for the determination of some food dyes (tartrazine, azorubine and Sunset Yellow) in different products. Porous silica gel with 3-aminopropyl functional groups attached to the matrix was used as stationary phase and a mixture of isopropanol, diethyl ether and ammonia (2:2:1, v/v/v) formed the mobile phase. Quantitative evaluation was performed using special-purpose software. The linearity of the analytical procedure was sustained by the numerical parameters such as correlation coefficient (0.9952-0.9980) and standard error of determination (0.03-0.20). The limits of detection were found to be within the range of 5.21-9.34 ng/spot, and the limits of quantification between 10.21 and 18.09 ng/spot. Recovery studies performed on two levels of concentration gave values between 96.39 and 102.76%. These results show that the regression approach provides rigorous and realistic detection and quantification limits and as a consequence can be routinely applied to other analytical systems. This method does not require expensive analytical instruments compared with classical densitometry and provides a reliable quantitative evaluation with minimum of time. 相似文献
We consider a few algorithmic problems regarding the hairpin completion. The first problem we consider is the membership problem of the hairpin and iterated hairpin completion of a language. We propose an O(nf(n)) and O(n2f(n)) time recognition algorithm for the hairpin completion and iterated hairpin completion, respectively, of a language recognizable in O(f(n)) time. We show that the n factor is not needed in the case of hairpin completion of regular and context-free languages. The n2 factor is not needed in the case of iterated hairpin completion of context-free languages, but it is reduced to n in the case of iterated hairpin completion of regular languages. We then define the hairpin completion distance between two words and present a cubic time algorithm for computing this distance. A linear time algorithm for deciding whether or not the hairpin completion distance with respect to a given word is connected is also discussed. Finally, we give a short list of open problems which appear attractive to us. 相似文献
We prove that every bounded, linear, 2-local Hilbert space representation of a von Neumann algebra is a representation. In contrast, 1-local representations may fail to be multiplicative, even at the 2 by 2 matrix algebra level.
A capillary electrophoretic protocol for the separation and quantification of the most important species potentially liberated during the cyanidation of gold sulfide‐rich ores was accomplished in this study. The separation of 11 ions: S2O32–, Cu(CN)32–, Fe(CN)64–, Fe(CN)63–, SCN–, Au(CN)2–, Ag(CN)2–, SO42–, OCN–, SO32–, and HS– was achieved using an indirect UV detection method. The robustness of the analytical protocol was tested by analyzing ions speciation during the cyanidation of two gold sulfide‐rich ores. The 1‐h cyanidation of the two ores released up to six complexes into solution: S2O32–, Cu(CN)32–, SCN–, Fe(CN)64–, OCN–, and SO42–. The mineralogy of the ore was found to influence directly the nature and the amount of the dissolved species. Conserving the cyanidation solution for 72 h after sampling resulted in 96% total sulfur recovery. These results allow us to conclude that the analytical protocol developed in this study can become very useful for the optimization of precious‐metals cyanidation plants. 相似文献