X–H rotational-echo double-resonance NMR for torsion angle determination of peptides

C–H and N–H rotational-echo double-resonance (REDOR) NMR is developed for determining torsion angles in peptides. The distance between an X spin such as ¹³C or ¹⁵N and a proton is measured by evolving the proton magnetization under REDOR-recoupled X–H dipolar interaction. The proton of interest is selected through its directly bonded heteronuclear spin Y. The sidechain torsion angle χ₁ is extracted from a ¹³Cβ-detected Hβ–N distance, while the backbone torsion angle φ is extracted from an ¹⁵N-detected H^N–C^′ distance. The approach is demonstrated on three model peptides with known crystal structures to illustrate its utility.     

Sulfation of hesperetin,naringenin and apigenin by the human cytosolic sulfotransferases: a comprehensive analysis

Abstract

Previous studies have revealed sulfation as a major pathway for the metabolism of hesperetin, naringenin and apigenin. The current study was designed to identify the human cytosolic sulfotransferase (SULT) enzyme(s) capable of sulfating these flavonoid compounds. Of the thirteen human SULTs, six (1A1, 1A2, 1A3, 1B2, 1C4, 1E1) displayed significant sulfating activity toward hesperetin, five (1A1, 1A2, 1A3, 1B2, 1C4) displayed sulfating activity towards naringenin, and four (1A1, 1A2, 1A3, 1C4) showed sulfating activity towards apigenin. Of the four human organ specimens tested, liver and intestine cytosols displayed much higher hesperetin-, naringenin- and apigenin-sulfating activity than lung and kidney cytosols. Moreover, sulfation of hesperetin, naringenin and apigenin was shown to take place in HepG2 human hepatoma cells and Caco-2 human colon adenocarcinoma cells under cultured conditions. Taken together, these results provided a biochemical basis underlying the metabolism of hesperetin, naringenin and apigenin through sulfation in humans.

     

Proteomic analysis of mouse liver for the evaluation of effects of Scutellariae radix by liquid chromatography with tandem mass spectrometry

Scutellariae radix or Scutellaria baicalensis is a medicinal plant that contains major flavonoids such as baicalein, baicalin, wogonin and wogonosides. The present work describes the development of an approach using proteomic analysis of mouse liver to study the effects of prolonged exposure to substances present in chemically standardized Scutellariae radix extracts. Histopathological examination of the mouse liver was compared with the proteome data. The botanical extracts were prepared using pressurized liquid extraction (PLE). A method without isotope labeling was developed, using proteolytic digestion with one- and two-dimensional liquid chromatography with tandem mass spectrometry, and was used to characterize the extent of differential protein expression in mouse liver in response to external factors such as extracts from Scutellariae radix. From the histopathological examination and proteome data, significant changes in the mouse livers were not observed for the low-dose group. The Scutellariae radix extracts at high dose were observed to cause damage at the bile duct and expression change of a number of proteins including some involved in catabolism of triglyceride-rich particles, carbohydrate metabolism, regulators of cell signaling processes, and enzymes involved in biotransformation. Thus, proteomic analysis of liver samples from mice treated with botanical extracts is a promising approach to provide information on any potential toxicity effects of the extracts. The present method also provides another means for comparing proteomes in biological samples such as liver lysates from mice subjected to different treatments.     

Determination of Partial Molar Volumes of EPA and DHA Ethyl Esters in Supercritical Carbon Dioxide

The use of supercritical fluids (SCFs) as solvents has been attracting widespread interest in the research and commercial applications. The study of partial molar volumes of solutes at infinite dilution in the near-critical region is of considerable fundamental importance, as these data reflects the interactions occurring between the solute and the solvent. Experimental measurements of partial molar volumes may be divided into two categories: direct and indirect methods. The direct methods…     

聚吡咯衍生物的合成及液晶性能

系统论述了新型导电功能性液晶聚合物3-和N-液晶基元取代聚吡咯的合成和液晶行为。指出通过化学氧化聚合、电化学氧化聚合和脱卤缩合聚合可以获得液晶性聚吡咯衍生物。它们均显示热致液晶行为，且多数呈现近晶液晶相，少数呈现向列液晶相，有些具有2种近晶相，有些具有单变液晶性。N-液晶基元取代聚吡咯比3-位取代聚吡咯具有较高的液晶稳定性。较长的亚甲基间隔和极性的介晶基团能够使N-取代聚吡咯具有较大的液晶微区和稳定的液晶相。N-取代液晶聚吡咯在摩擦力的作用下还可以诱发单轴取向。这种热致液晶性聚吡咯衍生物的研究成功有希望克服聚吡咯难以成型加工的巨大障碍。     

溶液的pH值对纳米CeO2晶粒形貌及形成机制的影响

以亚硝酸铈盐和氨水沉淀法合成了二氧化铈纳米粒子. 通过对溶液pH值的调节制备出了形貌各异的纳米CeO2晶粒. TEM和BET结果表明 酸性条件下, 得到的是球形的纳米CeO2晶粒且其比表面为148.1944 m2·g-1;中性时, CeO2晶粒的形貌为球形和棒状的混合形, 比表面为114.7975 m2·g-1;而碱性环境下, 易得到棒状的、比表面为106.2465 m2·g-1 的CeO2晶体. 另外还对各种形貌产物的形成机制进行了研究.     

A New Reaction-controlled Phase-transfer Catalyst System

A new reaction-controlled phase-transfer catalyst system was designed and synthesized.In this system, heteropolytungstate [C7H7N(CH3)3]9PW9O34 was used for catalytic epoxidation of cyclohexene with H2O2 as the oxidant. The conversion of H2O2 was 100% and the yield of cyclohexene oxide was 87.1% based on cyclohexene. Infrared spectra showed that both fresh catalyst and the recovered catalyst do have completely same absorption peak, indicating the structure of catalyst is very stability and can be recycled.     

电感耦合等离子发射光谱法测定渣油中铁、镍、钙、镁、钠、钒金属元素

用电感耦合等离子发射光谱法（ICP-AES）测定渣油中金属元素铁、镍、钙、镁、钠、钒，考察了不同的酸浓度对分析结果的影响和共存元素间的相互干扰，进行了加标回收率和精密度试验。     

Indium (III) Tribromide : An Excellent Catalyst for Biginelli Reaction

A highly efficient catalyst indium (III) tribromide is used to synthesize 5-alkoxy- carbonyl-4-hydrocarbyl-3,4-dihydropyrimidin-2(1H)-ones by a three-component coupling of β-keto ester, aldehydes and urea through improved Biginelli reaction.     

Determination of binding sites in carboplatin-bound cytochrome c using electrospray ionization mass spectrometry and tandem mass spectrometry

Interaction of carboplatin with cytochrome c (Cyt. c) has been investigated by electrospray ionization mass spectrometry (ESI-MS) and tandem mass spectrometry (MS/MS). ESI-MS studies revealed that the ring-opened adducts of carboplatin with Cyt. c were formed in the stoichiometric ratio of 1:1 and 2:1 at pH 5.0 and 37 degrees C and in the stoichiometric ratio of 1:1 only at pH 7.0 and 37 degrees C. It was also found that Cyt. c could be cleaved by carboplatin at pH 2.5 and 50 degrees C. The cleaved fragments of Cyt. c were determined by ESI-MS and MS/MS analysis to be Glu66 approximately Met80, Ac-Gly01 approximately Met65, Glu66 approximately Glu104, Ac-Gly01 approximately Met80 and Ile81 approximately Glu104. The carboplatin prefers to anchor to Met65 first, then to Met80. To further confirm the binding site of Met, AcMet-Gly was used as the model molecule to investigate its interaction with carboplatin and its hydrolysis reaction. On the basis of species detected during the reaction monitored by ESI-MS, a possible pathway of the cleavage reaction was proposed.