Determination of 30 Free Fatty Acids in Two Famous Tibetan Medicines by HPLC with Fluorescence Detection and Mass Spectrometric Identification

A simple and sensitive high-performance liquid chromatographic (HPLC) method with fluorescence detection and mass spectrometric identification has been developed for analysis of 30 long-chain and short-chain free fatty acids (FFAs). The fatty acids were derivatized to their esters with 1-[2-(p-toluenesulfonate)ethyl]-2-phenylimidazole-[4,5-f]-9,10-phenanthrene (TSPP) in N,N-dimethylformamide (DMF) at 90 °C with anhydrous K₂CO₃ as catalyst. A mixture of C₁–C₃₀ fatty acids was completely separated within 60 min by gradient elution on a reversed-phase C₈ column. Qualitative identification of the acids was performed by atmospheric-pressure chemical ionization mass spectrometry (APCI–MS) in positive-ion mode. The fluorescence excitation and emission wavelengths were 260 and 380 nm, respectively. Quantitative determination of the 30 acids in two Tibetan medicines Gentiana straminea and G. dahurica was performed. The results indicated that the medicines contained many FFAs. Linear correlation coefficients for the FFA derivatives were >0.9991. Relative standard deviations (RSDs, n = 6) for the fatty acid derivatives were <3%. Detection limits (at a signal-to-noise ratio of 3:1) were 3.1–38 fmol. When the fatty acid derivatives were determined in the two real samples results were satisfactory and the sensitivity and reproducibility of the method were good.     

Solid-phase synthesis of oligosaccharides and on-resin quantitative monitoring using gated decoupling (13)C NMR

A general strategy for solid-phase oligosaccharide synthesis capable of nondestructive quantitative monitoring has been developed. The synthesis was carried out on TentaGel using thioglycosides as glycosylating agents and dimethylthiomethylsulfonium triflate as the activator. An acylsulfonamide linker was introduced to cleave the oligosaccharide from the resin. The solid-phase reactions were monitored quantitatively by using the inverse gated decoupling technique of (13)C NMR, where two (13)C-enriched markers were used to monitor the reactions: one was (13)C-enriched glycine incorporated as a part of the linker and as an internal standard, and the other was a (13)C-enriched acetyl group used as a protecting group of the glycosylation reagent. A representative synthesis of sialyl Lewis X branched tetrasaccharide was demonstrated.     

Triethylsilane as a mild and efficient reducing agent for the preparation of alkanethiol-capped gold nanoparticles

The reaction of HAuCl(4).4H(2)O and n-C(12)H(25)SH with 1 equiv. of Et(3)SiH in an organic solvent affords spherical gold nanoparticles (AuNPs) with narrow dispersity.     

Spongolactams, farnesyl transferase inhibitors from a marine sponge: isolation through an LC/MS-guided assay, structures, and semisyntheses

Novel nitrogenous diterpenoids, spongolactams A-C (1-3), were isolated as trace components of an Okinawan marine sponge, Spongia sp., by an LC/MS-guided assay for farnesyl transferase (FTase) inhibitors. Their structures were elucidated by spectroscopic analyses. To evaluate their structures and biological activity, the metabolites were semisynthesized from the known furanoditerpene 5, obtained from the same sponge. Three related compounds 4, 13, and 16 were also semisynthesized. The IC50 values against FTase for 1-3 were 23, 130, and >260 microM, respectively, while the IC50 values against a human tumor cell line were 2.0, 3.5, and 20 microM, respectively. The structure-activity relationships within the six compounds suggest some positive correlation between FTase inhibitory and cytotoxic activities.     

Catalytic activity of silica gels bound manganese(III)-porphyrin on oxidative reaction of adrenaline

To develop a solid catalysis on oxidative reaction of adrenaline (Ad), supports bound metal-tetrakis(4-carboxyphenyl)porphine (M-TCPP) were investigated. Silica gels bound Mn-TCPP were proved to has a superior activity in the oxidation of Ad and be able to serve as a useful oxidase model for Ad.     

Distinguishing isomeric pyridylaminated high-mannose (Man7) oligosaccharides based on energy-resolved mass spectra

Analysis of posttranslational modifications of proteins is an important issue for understanding the relationship between protein structure and function. Micro-scale analytical methods capable of elucidating glycan structures are therefore gaining attention in connection with proteomics research. Recent efforts directed toward this goal have successfully distinguished and in some cases identified glycan structures based on collision-induced dissociation (CID) analysis. Despite these advancements, the identification of isomeric glycans such as high-mannose-type oligosaccharides, Man(7)GlcNAc(2), that are closely related structurally, is not yet possible. Using energy-resolved mass spectrometry (ERMS), we found that these isomers could be distinguished by comparing the intensities of certain fragment ions. ERMS is useful because the data obtained can be treated quantitatively. Furthermore, it was found that discrimination can be easily achieved by analyzing only the energy-resolved mass spectra of the sodiated isomeric compounds at the stage of MS(2). Thus, the importance and usefulness of ERMS, which provide the factor of activation energy under CID, in analyzing isomeric molecules are clearly shown.     

Peroxidase-like catalytic activity of aqueous- and immobilized-Mn(3+)-octabromo-porphyrins on ion-exchange resin supplied as mimetic of horseradish peroxidase

In order to explore the capability of metal porphyrins as an alternative of horseradish peroxidase (HRP), HRP-like activity of three manganese-porphyrins (Mn-Ps) and three Mn-octabromo-porphyrins (Mn-OBPs) was examined in both aqueous and immobilized states. It was found that Mn(3+)-octabromotetrakis(1-methyl-pyridinium-4yl)porphine (Mn-OBTMPyP) has an activity of at least 90% of HRP in an aqueous solution. Mn-OBTMPyP exhibited a catalytic activity even in the presence of hydrogen peroxide without suicide reaction. In addition, Mn-OBTMPyP was revealed to function as an alternative to HRP in the quantitative determination of serum uric acid. These results are of great interest because they indicate that metal-octabromo-porphyrins possibly include promising candidates of artificial enzyme capable of substituting for HRP.     

Combinatorial library of five-membered iminocyclitol and the inhibitory activities against glyco-enzymes.

BACKGROUND: Oligosaccharide processing enzymes are important classes of catalysts involved in synthesizing specific oligosaccharide structures on proteins and sphingolipids. Development of specific inhibitors of such enzymes is of current interest as these inhibitors may be used to control cellular functions. Five-membered iminocyclitols have been shown to be potent inhibitors of such enzymes. Since a rational design and synthesis of inhibitors is often extremely difficult due to the limited information regarding the structure of the active site, we carried out a combinatorial library approach. RESULTS: To create diversity, we decided to use an aldehyde group of a protected iminocyclitol for reductive amination and the Strecker reaction. After transformation of the nitrile group introduced by the Strecker reaction into an amine and amide and complete deprotection, a small library of five-membered iminocyclitols consisting of 27 compounds was synthesized. A series of compounds obtained by reductive amination was first screened as potential inhibitors of glycosidases and glycosyltransferases. Among them, compounds carrying a C(10)-alkyl group showed marked enhancement of inhibitory activity against alpha-mannosidase at 10 microM concentration when compared with its parent compound and deoxymannojirimycin. Furthermore, compounds having the phenylethyl group showed an extremely strong inhibitory effect against alpha-galactosaminidase at a K(i) value of 29.4 nM. Compounds with an aminomethyl and amide group at the C-1' position of these two molecules showed a decrease in inhibitory activities. CONCLUSIONS: A combinatorial approach based on five-membered iminocyclitols with a galacto-configuration was exploited. The potential usefulness of the library as a source of inhibitors of glycoenzymes is clearly shown in this study.     

钒掺杂介孔二氧化钛的制备及可见光催化性能

以表面活性剂十六烷基三甲基溴化铵(CTAB)为模板, 钛酸四正丁酯为钛源, 偏钒酸铵为掺杂离子前驱体, 通过液晶模板辅助溶胶-凝胶法制备钒掺杂介孔Ti\begin{array}{c}{O_2}_{}\end{array}(VMT), 采用X射线衍射(XRD)、 N₂吸附-脱附分析、 热重-差热分析(TG-DTA)、 X射线光电子能谱(XPS)、 紫外-可见光谱(UV-Vis)和透射电子显微镜(TEM)等对样品结构进行表征, 选择亚甲基蓝为目标降解物, 对VMT的可见光催化性能进行了研究. 结果表明, 钒掺杂减小了介孔TiO₂(MT)的粒径和光生电子-空穴复合率, 增大了比表面积及Ti³⁺和羟基浓度, 导致VMT比纯MT和P25光催化活性高, 并且钒掺杂使MT带隙能降低, 使其具有很高的可见光催化活性. 最佳的光催化条件为: VMT的浓度为0.83 g/L, MB的浓度为1 mg/L.     

青藏高原多年冻土区高寒草甸植物群落主要植物化学元素含量特征

分析了青藏高原北麓河地区29种高寒植物15个元素含量的特征。结果表明,这些植物中元素平均含量>400μg/g的元素有Ca,Mg,Na,K,Fe,10～100μg/g的有Mn,Cr,Zn,Cu,<10μg/g的有Ni,Co,As,Pb,Cd,Hg;种间同种元素的含量变化规律不统一。相关性分析表明,Cu与Cd,Fe与Cd和Hg,Cr与Ni,Co和Mg极显著正相关,Cr和Ca极显著负相关;聚类分析表明,Na,As元素对本区植物聚类的影响最大,莎草科、禾本科、菊科科内植物元素含量相似。