Enzymatic dissymmetrization of meso-2,3-dimethylbutane-1,4-diol and its diacetate. Synthesis of scalemic (–)-lasiol

Acylation of meso-2,3-dimethylbutane-1,4-diol with vinyl acetate in the presence of porcine pancreatic lipase (PPL) leads to the dextrorotatory monoacetate of the above diol with enatiomeric excess (ee) 58—64%. Absolute configuration of this scalemic specimen was determined by its sequential transformation to levorotatory lasiol, a metabolite of the Lasius ants. Partial hydrolysis of the corresponding meso-diacetate, mediated by PPL or by the Pseudomonas sp. lipase affords the monoacetate of opposite configuration with ee 72—86%, a formal intermediate in the synthesis of (3S,4R)-faranal. Other microbial lipases used are distinctive in low chemoselectivity.     

种植沙生植物--沙棘改善内蒙古地区生态环境

结合内蒙古地区现状，对沙棘的生物学和生态学特性、沙棘属植物化学成分和微量元素及种植沙生植物——沙棘的重要性和必要性进行了详细的研究和探讨。研究表明，沙棘属植物具有极强的生态适应性并富含多种营养成分和生物活性物质，并以耐干旱、耐瘠薄、萌蘖及固氮能力强等特点被称为治理非宜林地水土流失、改善生态环境的先锋树种。种植沙棘是治理内蒙古脆弱生态环境最经济、最有效的措施，是贫瘠的不毛之地发展经济、增加收入的经济树种。另外．种植沙棘的技术简便，容易掌握，投资少，见效快。     

Alkyl-Diol Silica (ADS): restricted access precolumn packings for direct injection and coupled-column chromatography of biofluids

The direct and repetitive injection of untreated biological fluids (e.g., hemolyzed blood, plasma, serum, cell culture and tissue homogenates) onto an HPLC-system and the subsequent analysis of low-molecular weight compounds (e.g. drugs, xenobiotics, metabolites) is rendered possible by a coupled-column configuration and special precolumn packings. For this purpose a new family of chemically and enzymatically tailored reversed-phase packing materials have been prepared. The LC-integrated sample clean-up with these restricted access (bimodal) phases is based on the complete nonadsorptive size exclusion of macromolecules (e.g. proteins) and on the simultaneous dynamic partitioning of the target molecules. The bonded phase which exclusively covers the internal pore surface of a glyceryl-modified silica is a butyryl-(C-4), capryloyl-(C-8) or stearoyl-(C-18) moiety. These ligands allow a classical reversed-phase or ion-pair chromatography during the sample work-up step. The capacity of the n-alkyl phase is comparable with conventional silica based RP-materials. The broad hydrophobic retentive capability of these packings allows the extraction of a wide variety of compounds of biomedical interest. The electroneutral and hydrophilic particle exterior (glyceryl-residues) was generated using either soluble or immobilized enzymes (lipase, esterase) which cleave the fatty acid esters exclusively at the outer surface. Unwanted macromolecular components of a sample (e.g. proteins) are quantitatively eluted in the void volume due to the restricted access given by the pore size (6 nm) and the nonadsorptive external diol coverage. The lifetime of a precolumn (25 × 4 mm I.D.) packed with these novel bimodal, i.e. RP-SEC phases exceeds more than 200 injections of 500 l plasma. In addition to the synthesis, this paper describes an application of each of these Alkyl-Diol Silica (ADS) precolumn packings in fully automated coupled-column HPLC systems for the analysis of drugs and endogenous compounds in different biological matrices.Dedicated to Professor Dr. Dr. h.c. mult. J.F.K. Huber on the occasion of his 70th birthday     

内蒙古地区天然植物沙棘果中黄色素的提取工艺及性质研究

以内蒙古地区沙棘果实为原料，研究了提取黄色素的工艺条件，同时对该色素的性质进行了初步探讨。结果表明，以95％的乙醇溶液作浸提剂，提取的黄色素浓度最高，工艺流程简单易行，且无毒，无污染。对提取的黄色素进行的性质试验表明，沙棘黄色素对光、热具有较好的稳定性，适用于酸性或弱碱性的食品中，葡萄糖、氧化剂(H2O2)、还原剂(Na2SO3)等食品添加剂均无明显影响以上结果为这种优良天然色素的开发与应用提供了参考。     

The synthesis of diastereo- and enantiomerically pure beta-aminocyclopropanecarboxylic acids

The synthesis of diastereo- and enantiomerically pure beta-aminocyclopropanecarboxylic acids (beta-ACCs) is described. Starting from pyrrole, (rac)-4 is readily obtained, which was kinetically resolved by enzymatic hydrolysis. Subsequent oxidation of (-)-4 and deformylation gives rise to the cis-beta-ACC derivative (ent)-9, while (+)-10 was converted to the trans-beta-ACC derivative 8. Both 8 and (ent)-9 and their benzyl esters 13 and 16, being conformationally restricted beta-alanine or gamma-aminobutyric acid (GABA) derivatives, represent useful building blocks for peptides containing unnatural amino acids.     

Solid-Phase Synthesis of a Monofunctional trans-a(2)Pt(II) Complex Tethered to a Single-Stranded Oligonucleotide

Cross-linking ability is possible with the oligonucleotide-tethered, monofunctional trans-Pt(II) complex shown. It was synthesized by a novel solid-phase approach comprising conjugation of immobilized tetrathymidylic acid with a trans-a(2)Pt(II) building unit, ammonolysis, and transformation of the resulting complex (R=1-N-cyclohexylmethylthyminate) into the chloro derivative (R=Cl). a=NH(2)CH(3), T=thymine.     

VUV spectroscopy of pure and Tm-doped LicaAlF6 crystals

Nominally pure and Tm³⁺-doped LiCaAlF₆ crystals were grown by the Czochralski technique in a reducing atmosphere. The optical properties of transparent single crystals were studied using absorption and time-resolved luminescence spectroscopy in the VUV spectral range (330-100 nm). The strongest VUV emission peaking at 60 800 cm⁻¹ with a decay time of 5.6 μs (7 μs) at 300 K (7.4 K) was assigned to the spin-forbidden 4f¹¹5d-4f¹² transition of Tm³⁺. The fine structure observed in the VUV emission and corresponding excitation spectra indicate intermediate strength of electron-phonon coupling in this system. The efficient excitation of f-f emissions above 72 000 cm⁻¹, higher than the onset of f-d absorption at 63 000 cm⁻¹, is mainly caused by the F⁻ to Tm³⁺ charge transfer absorption. The nature of various host-related excitation processes in the energy transfer to the Tm³⁺ ions is discussed.