Spectral shift function and trace formula

The complete proofs of Krein’s theorem on the spectral shift function and the trace formula are given for a pair of self-adjoint operators such that either (i) their difference is trace-class or (ii) the difference of their resolvents is trace-class. The proofs, essentially due to Krein, is based on Herglotz’s theorem on the boundary value of the analytic functions whose imaginary part is non-negative on the upper half plane, and an almost optimal class of functions are obtained for which the trace formula is valid. Also an alternative method based on Weyl-von Neumann’s theorem for self-adjoint operators, avoiding the complex function theory and inspired by Voiculescu’s work, is given for the first case. Furthermore, some applications of the spectral shift function have been discussed.     

Representing workloads in GI/G/1 queues through the preemptive-resume LIFO queue discipline

We give in this paper a detailed sample-average analysis of GI/G/1 queues with the preemptive-resume LIFO (last-in-first-out) queue discipline: we study the long-run state behavior of the system by averaging over arrival epochs, departure epochs, as well as time, and obtain relations that express the resulting averages in terms of basic characteristics within busy cycles. These relations, together with the fact that the preemptive-resume LIFO queue discipline is work-conserving, imply new representations for both actual and virtual delays in standard GI/G/1 queues with the FIFO (first-in-first-out) queue discipline. The arguments by which our results are obtained unveil the underlying structural explanations for many classical and somewhat mysterious results relating to queue lengths and/or delays in standard GI/G/1 queues, including the well-known Bene's formula for the delay distribution in M/G/l. We also discuss how to extend our results to settings more general than GI/G/1.     

Highly regio- and stereocontrolled SN2′ reactions of gem-difluorinated vinyloxiranes with monoalkylcopper reagents

Reaction of gem-difluorinated vinyloxiranes with RCu(X)Li allowed us to introduce the R group regioselectively at the fluorine-attached terminal carbon atom in an S_N2′ manner to afford (E)-allylic alcohols exclusively, while homoallylic alcohols with anti stereochemical relationship were found to be obtained selectively from higher-ordered cuprates derived from CuCl and RMgBr in a ratio of 1:3.     

中药配方颗粒红外光谱法的快速鉴别

采用红外光谱法对中药配方颗粒及其辅料进行了鉴别研究。结果表明：不同生产厂商的配方颗粒中所添加的辅料类型及用量有较大差别；不同种的配方颗粒在辅料含量较低的情况下有较明显的指纹性，而辅料含量较高时，采用差谱技术可以提高谱图的指纹性，达到中药配方颗粒--鉴别的目的。该法简便、快速、可靠，是中药配方颗粒宏观质控的一个强有力的手段。     

Qualitative estimation of the dependence of the number of energetic compounds on their oxygen coefficient

The ratio between the numbers of structural formulas of C,H,N,O-containing energetic compounds belonging to the classes of fuels (low values of the oxygen coefficientA), explosives (mediumA), and oxidants (highA values) was studied by a computer generation procedure. The number of the theoretically possible structural formulas was found to decrease rapidly on going from fuels to explosives and then to oxidants; this observation agrees with the data on the numbers of various energetic compounds currently used and proposed. The strategy of the search for new compounds with the specified properties is described in brief, and its applicability to the search for explosives and oxidants with a small (up to 12) number of atoms in a molecule is evaluated. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 7, pp. 1304–1310, July, 1998.     

A new method for inversion of hydroxyl group of carbocyclic nucleosides

The hydroxyl group of carbocyclic nucleosides was inversed when the compounds were treated with Me_3SiCl,KCN and a catalytic amount of NaI in DMF/CH_3CN.     

Diastereoselective synthesis of the 19-epi-C18-C25 segment of (−)-lasonolide A and an unusual inversion at C19

Diastereoselective construction of the 19-epi-C₁₈-C₂₅ segment of (−)-lasonolide A was achieved using a 5-exo-trigonal mode of radical cyclization for the creation of the contiguous quaternary and tertiary stereogenic centers at C₂₂ and C₂₃ as the key reaction step. During the dehydration stage, it was found that an unusual inversion of configuration took place.     

Absolute stereochemistries and total synthesis of (+)-arisugacins A and B, potent, orally bioactive and selective inhibitors of acetylcholinesterase

In the current studies, we used the Kakisawa-Kashman modification of the Mosher NMR method to determine the complete absolute stereochemistry of arisugacins. We also report the convergent total synthesis of (+)-arisugacins A and B by a sequence including (i) ruthenium complex-catalyzed asymmetric reduction of the cyclohexenone derivative; (ii) stereoselective construction of the arisugacin skeleton by a Knoevenagel-type reaction of an α,β-unsaturated aldehyde derivative with production of a 4-hydroxy-2-pyrone derivative as a key reaction; and (iii) stereoselective dihydroxylation to give the diol derivative, followed by deoxygenation. Accordingly, we defined the absolute structures of arisugacins A and B as 4a-(R),6a-(R),12a-(R), and 12b-(S). Finally, we characterized the bioactivities of the synthetic intermediates to understand the structure-activity relationships of the arisugacins.     

双质谱测定地卟啉取代基组成的解析方法及其应用

根据卟啉标样的双质谱特征，建立一种计算卟啉环上取代基组成的方法。卟啉的平均分子结构简式衡量其取代基的组成，尤其对地质体中相同碳数的卟啉“混合物”大环外取代基的构成十分有效。