Natural products in combinatorial chemistry: an andrographolide-based library

The generation of a natural-product-based library starting from andrographolide is described. Utilizing andrographolide itself in parallel solution-phase synthesis leads to a 360-membered library. The initial transformation of the starting material via ozonolysis is followed by the conversion into a suitable template by introduction of a thiazole moiety. Subsequent decoration at two points of diversity yields the desired natural product derivatives. The selection of actually synthesized compounds is based on a virtually generated library and the assessment of its members with respect to physicochemical parameters, thus ensuring pharmacological relevance of the compounds.     

No Spin-Localization Phase Transition in the Spin-Boson Model without Local Field

We explore the spin-boson model in a special case, i.e., with zero local field. In contrast to previous studies, we find no possibility for quantum phase transition （QPT） happening between the localized and delocalized phases, and the behavior of the model can be fully characterized by the even or odd parity as well as the parity breaking, instead of the QPT, owned by the ground state of the system. The parity breaking mentioned in our case is completely different from the spontaneously broken symmetry relevant to the conventionally defined QPT in previous studies. Our analytical treatment about the eigensolution of the ground state of the model presents for the first time a rigorous proof of no- degeneracy for the ground state of the model, which is independent of the bath type, the degrees of freedom of the bath and the calculation precision. We argue that the QPT mentioned previously appears due to incorrect employment of the ground state of the model and/or unreasonable treatment of the infrared divergence existing in the spectral functions for Ohmic and sub-Ohmic dissipations.     

Capillary zone electrophoresis of lipoarabinomannan by multi-layered concentration

The present article describes a capillary zone electrophoresis method which relies on a multilayered water-alkali solvent stacking with online ionization to enhance detection of mannose, arabinose, and their oligosaccharides, which are used as the migration profile standards but are also the distinctive structural components of lipoarabinomannan. Lipoarabinomannan is detected in patients having tuberculosis. The capillary electrophoresis method with ionization of the whole saccharides without degradation in alkaline solution inside the capillary is based on the structural deprotonation of the molecules under ultrahigh pH conditions. The validation of the capillary electrophoresis parameters revealed that the 15-fold electrolyte–water-injection plug allowed detection of one-third lower concentrations than detected without online concentration. For the first time, the better detectability was seen especially for highly polymerized, but otherwise poorly ionized, arabinooctaose. The applicability of the method for detecting whole large biological saccharide complexes was confirmed by the glycolipid lipoarabinomannan. For the first time also, the migration of the indestructible lipoarabinomannan was detected together with oligosaccharides used representing the capping units, namely mannose, mannobiose, and mannotriose. The myo-inositol-phosphate-lipid unit was seen to migrate separately from the arabinomannan, since it was hydrolyzed from one lipoarabinomannan product under alkaline conditions in capillary electrophoresis.     

甲基酮的二氟同系化-卤化反应:一锅法合成β-卤代-α,α-二氟代酮

以（溴二氟甲基）三甲基硅烷（TMSCF₂Br）为二氟卡宾源,利用其兼具TMS转移特性及自活化特性,仅在催化量的n-Bu₄NBr的催化启动下,直接完成甲基酮的烯醇化-二氟环丙烷化反应以及与卤正离子的开环卤化反应,并使用卤负离子作为卤源,采用其原位氧化形成卤正离子的方法实现了偕二氟环丙烷硅醚的开环-卤化,合成了β-卤代-α,α-二氟代酮类物质.     

Photo-induced metal-free ATRP of MMA with 2,7-bi-(N-penothiazinyl)fluorenone as photocatalyst

In this study, 2,7-bi-(N-penothiazinyl)fluorenone was employed as photocatalyst (PC), ethyl α-bromophenylacetate (EBP) as atom transfer radical polymerization (ATRP) initiator, and photo-induced metal-free ATRP of methyl methacrylate (MMA) was performed at 25°C under blue light irradiation. PMMAs with well-defined architectures and precisely controlled chain lengths were synthsized. The kinetics results confirmed that molecular weights increased linearly with monomer consumption. The molecular weight distributions (M_w/M_n) of the resultant PMMA were narrow. The polymerization was activated and deactivated by periodic light control process. ¹H nuclear magnetic resonance spectrometer (NMR) and gel permeation chromatography (GPC) were used to characterize the obtained PMMAs. The living characters of the polymerization system were further confirmed by chain extension of from the PMMA-Br macroinitiator.     

A divergent synthesis of functionalized unsaturated delta-lactones from alpha-alkenoyl-alpha-carboxyl ketene dithioacetals

A divergent synthesis of functionalized unsaturated delta-lactones 2, 3, 4, and 5 has been developed starting from the readily available alpha-alkenoyl-alpha-carboxyl ketene dithioacetals 1 in high to excellent yields under mild reaction conditions. Thus, 6-substituted 3-(1,3-dithiolan/dithian-2-ylidene)-3H-pyran-2(6H)-ones 2, obtained from a consecutive reduction with NaBH4 and acidic workup of 1 via a novel vinylogous Pummerer cyclization, can be further transformed into alpha-pyranones 3, 4, and 5 upon a sequential isomerization catalyzed by triethylamine (to give 3), followed by dethioacetalization (to give 4) or a formylation with Vilsmeier reagent (to give 5).     

用于干涉型光纤传感器的相位生成载波解调技术

相位生成载波技术是用于光纤传感器中很重要的一种信号解调方法。简要说明了相位生成载波调制的原理和两种基本的调制方法 ,着重介绍了相位生成载波调制信号的解调方法 ,包括 :零差法、伪外差法和合成外差法 ,并对以上各种方法进行了分析比较。对相位生成载波技术在干涉型光纤传感器中的应用作了详细的介绍。针对现在最有希望用于智能结构的光纤布拉格光栅传感器 ,介绍了相位生成载波技术在这方面的应用。     

Production of charged pions, kaons and antikaons in relativistic C + C and C + Au collisions

Production cross-sections of charged pions, kaons and antikaons have been measured in C+C and C+Au collisions at beam energies of 1.0 and 1.8 AGeV for different polar emission angles. The kaon and antikaon energy spectra can be described by Boltzmann distributions whereas the pion spectra exhibit an additional enhancement at low energies. The pion multiplicity per participating nucleon M(π⁺)/<A _part> is a factor of about 3 smaller in C+Au than in C+C collisions at 1.0 AGeV whereas it differs only little for the C and the Au target at a beam energy of 1.8 AGeV. The K⁺ multiplicities per participating nucleon M(K⁺)/ <A _part> are independent of the target size at 1 AGeV and at 1.8 AGeV. The K^- multiplicity per participating nucleon M(K^-)/ <A _part> is reduced by a factor of about 2 in C+Au as compared to C+C collisions at 1.8 AGeV. This effect might be caused by the absorption of antikaons in the heavy target nucleus. Transport model calculations underestimate the K^-/K⁺ ratio for C+C collisions at 1.8 AGeV by a factor of about 4 if in-medium modifications of K-mesons are neglected. Received: 10 December 1999 / Accepted: 14 November 2000     

A Study of the Characteristics of the Wave Packets of a Paul-Trapped Ion

Based on the former studies, the time-dependent characteristics of the wave packets of a Paul-trapped ion are investigated explicitly in cylindrical coordinates by the method of function series expansion (HE). It is shown that the present work relates the quantum motion of a Paul-trapped ion to the orbit of the classical motion and presents a more clear physical picture than the former studies.