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101.
Prof. Dr. Jie-Ping Wan Zhi Tu Yuyun Wang 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(28):6907-6910
A transient and recyclable C−H iodination has been designed for the synthesis of isoflavonoids through the domino reactions of o-hydroxyphenyl enaminones and aryl boronic acids in the presence of catalytic KI and Pd catalyst. Instead of the conventional cross-coupling strategy employing pre-halogenated substrates, this method transforms raw C−H bond by means of a transient C−H halogenation to smoothly relay the subsequent C-arylation. Consequently, such a method avoids the pre-functionalization for C−halogen bond installation as well as the generation of stoichiometric halogen-containing waste following the cross-coupled product, disclosing an intriguing new coupling protocol to forge the C−C bond in the virgin area between classical C−X (X=halogen) bond cross coupling and the C−H activation. 相似文献
102.
We demonstrate that base and sugar protons within a DNA oligomer can be assigned unambiguously following site-specific 15N,13C isotope incorporation at levels as low as 1% enrichment. This simple and cost-effective methodology is demonstrated on the d(GGGTTCAGG) DNA sequence, which forms a dimeric G-quadruplex containing G.G.G.G tetrads sandwiched between G.(C-A) triads. 相似文献
103.
We present a simple model to rationalize the effects of environment on the reaction barrier frequencies derived from free energy profiles. These frequencies are relevant in deviations of a rate constant from its transition state theory value and in determining which environmental dynamics participate in the reaction. In particular, this simple model can be used to understand the changes in the reaction barrier frequencies of an enzymatic catalyzed reaction and the corresponding uncatalyzed process in aqueous solution, a change which has implications for dynamical environmental effects on the enzymatic reaction. Two possible cases are analyzed, in which the polarity (charge separation/localization) of the reacting system increases or decreases as the reaction advances. A simple modeling of the environment′s effects allows the explanation of an unusual “inverse” effect on the reaction frequencies, that is, a free energy barrier lowering accompanied by an increase of the reaction frequency, a behavior observed in some enzymes. The model predictions are successfully compared with results from full simulations for four different enzyme reactions. 相似文献
104.
Serganov A Yuan YR Pikovskaya O Polonskaia A Malinina L Phan AT Hobartner C Micura R Breaker RR Patel DJ 《Chemistry & biology》2004,11(12):1729-1741
Metabolite-sensing mRNAs, or "riboswitches," specifically interact with small ligands and direct expression of the genes involved in their metabolism. Riboswitches contain sensing "aptamer" modules, capable of ligand-induced structural changes, and downstream regions, harboring expression-controlling elements. We report the crystal structures of the add A-riboswitch and xpt G-riboswitch aptamer modules that distinguish between bound adenine and guanine with exquisite specificity and modulate expression of two different sets of genes. The riboswitches form tuning fork-like architectures, in which the prongs are held in parallel through hairpin loop interactions, and the internal bubble zippers up to form the purine binding pocket. The bound purines are held by hydrogen bonding interactions involving conserved nucleotides along their entire periphery. Recognition specificity is associated with Watson-Crick pairing of the encapsulated adenine and guanine ligands with uridine and cytosine, respectively. 相似文献
105.
A non-aqueous reversed phase HPLC was developed for determining alpha-tocopherol in Sea buckthorn oil capsule without the need for saponification. A reversed phase column (Alltima C(18), 4.6 x 250 mm, 5 microm) was used with a mobile phase of methanol-acetonitrile (95 : 5, v/v) and flow rate of 1 ml/min. The contents in capsule were extracted with n-hexane. Detection wavelength was set at 292 nm. Each analysis requires no longer than 20 min. The linearity range for alpha-tocopherol was 9.4-47.0 microg/ml. The detection limit was 0.94 microg/ml. The mean recovery was 95.82 (RSD 2.3%). This method is suitable for quantitative analysis of alpha-tocopherol in Sea buckthorn oil or its Traditional Chinese Medicinal preparation. 相似文献
106.
Tu SL Gunn A Toney MD Britt RD Lagarias JC 《Journal of the American Chemical Society》2004,126(28):8682-8693
Cyanobacterial phycocyanobilin:ferredoxin oxidoreductase (PcyA) catalyzes the four electron reduction of biliverdin IXalpha (BV) to phycocyanobilin, a key step in the biosynthesis of the linear tetrapyrrole (bilin) prosthetic groups of cyanobacterial phytochromes and the light-harvesting phycobiliproteins. Using an anaerobic assay protocol, optically detected bilin-protein intermediates, produced during the PcyA catalytic cycle, were shown to correlate well with the appearance and decay of an isotropic g approximately 2 EPR signal measured at low temperature. Absorption spectral simulations of biliverdin XIIIalpha reduction support a mechanism involving direct electron transfers from ferredoxin to protonated bilin:PcyA complexes. 相似文献
107.
叙述了CAHN-2000磁天平(美国)调试过程中如何解决液氮温区的测试,自制了磁天平与计算机的接口,编写了数据采集、处理和控制等高原 软件,节省了几万美元,部分指标超过原配套水平,三年来仪器在对国同外开放过程中,液氮温区的工作一直正常,实测了上千个样品,提供的数据已撰写数十篇文章在国内外刊物上发表。由此说明,要充分发挥进口仪器的使用效率,必须对仪器的工作原理、结构特点有透乇的了解,同时要有相当的自 相似文献
108.
George Ting-Kuo Fey Hui-Jyuan Tu Kai-Pin Huang Yi-Chuan Lin Hsien-Ming Kao Shih-Hung Chan 《Journal of Solid State Electrochemistry》2012,16(5):1857-1862
Carbon-coated LiFePO4 cathode materials were prepared by a solid-state method incorporating different sizes of polystyrene (PS) spheres as carbon sources. In scanning electron microscope images, small PS spheres appear more effective at preventing aggregation of LiFePO4 particles. From transmission electron microscopy images, it was found that the LiFePO4 particles were completely uniformly coated with 5-nm carbon layer when the carbon source was 0.22 μm PS spheres. When the size of PS sphere was increased to 2.75 μm, a network of carbon was formed and wrapped around the LiFePO4 to create a conductive web. Raman spectroscopy and four-point probe conductivity measurement showed that using larger sizes of PS spheres as carbon sources leads to greater conductivity of LiFePO4/C. The LiFePO4 precursor sintered with 0.22 μm PS spheres delivered an initial discharge capacity of 145 mAh g?1 at a 0.2 C rate, but it only sustained 289 cycles at 80% capacity. When the diameter of PS spheres was increased to 2.75 μm, the discharge capacity of LiFePO4/C decreased, but the cycle life reached 755 cycles, the highest number in this work probably due to the network formation of carbon wrapping around LiFePO4 particles. 相似文献
109.
新型的一次性化学离子敏钾、钠测试卡片,是基于离子选择电极(ISE)原理设计制作的一种电化学传感器~[1]。它由测量电池装置、敏感膜、接触衬底(石墨)和盐桥等构件组装而成。采用两点电位测量法。具有一次性使用、简便、快速、精确度高、成本低等优点,对样品不必作预处理,避免了交叉污染,克服了ISE重现性差、固有漂移等缺点,发挥了ISE选择性好、准确度高等优点。根据临床应用和抽样测试结果,钾、钠测试卡片的精密度±SD:钾1.0;钠2.0,C.V%:钾3.0%;钠2.0%;响应时间为30s;漂移:钾0.3mV/min;钠0.5mV/min;回收率为99.5%,均符合临床应用的基本要求。 相似文献
110.