Unexpected Isolation of 4‐Isothiocyanatomethylene‐4H‐pyridine‐1‐carboxylic Acid Ethyl Ester as Potential Template in Organic Synthesis

The synthesis of 4‐isothiocyanatomethyl‐pyridine 4 in 36% yield by Hasegawa and Kotani (Japanese patent 49088878, 1974) has spurred us to investigate this preparation in detail. In addition to this compound, 4‐isothiocyanatomethylene‐4H‐pyridine‐1‐carboxylic acid ethyl ester 3 can be isolated. The synthesis of both compounds 3 and 4 were optimized to 75% and 50% yield respectively. Reaction of compound 3 with methylamine gave thiourea derivatives 5, the same product obtained on reacting 4‐isothiocyanatomethyl‐pyridine 4 with methylamine. We succeed in adjusting the reaction conditions to obtain high yield either from compound 3 or isothiocyanate derivatives 4.     

Catalyst free,regioselective one-pot three-component synthesis of thiazol-2-imine derivatives in ionic liquid

A one-pot three-component approach for the synthesis of thiazol-2-imines has been described by the reaction of amine, phenyl isothiocyanate and β-nitroacrylate in [Hbim]BF₄ ionic liquid. The method is applicable for aromatic, benzylic, aliphatic and cyclic amines. Reusable reaction media, regioselectivity, mild reaction condition, catalyst free and high yield of products are the salient features of this protocol.     

Synthesis of Potential Antimicrobial Agents from Maltose. III. Introduction of an Amino Group Into the 3′-Position of 1,6-Anhydro-Disaccharides

Abstract

Regioselective cleavage of 1,6-anhydro-maltose (1) with periodate and the subsequent recyclization with nitromethane gave 1,6-anhydro-3′-deoxy-3′-nitro-disaccharides (3). Three diastereomers, prepared by benzylidenation of 3, were separated by column chromatography. Each of 4′,6′-O-benzylidene derivatives successively underwent debenzylidenation, reduction of the nitro group, and peracetylation to give 3′-acetamido-3′-deoxy-disaccharide derivatives (7, 8, and 9). The configurations of the 3-amino sugar moietres in 7 (D-gluco), 8 (D-manno) and 9 (D-galacto) were determined on the basis of the ¹H NMR data. The main product (7) was further modified to the 6-deoxy-6-nitro derivative.     

用毛细管电泳-激光诱导荧光-增强型电荷耦合检测器测定痕量氨基酸

本文对用毛细管电泳－激光诱导荧光－增强型电荷耦合检测器测定氨基酸衍生物进行了研究。考察了荧光黄异疏氰酸酯衍生氨基酸的各种条件。在优化条件下，10－8～10－6mol／L浓度范围内精氨酸与其衍生物的荧光强度呈良好的线性关系，最小可衍生化的精氨酸浓度为5×10－10mol／L。     

微流控芯片毛细管电泳激光诱导荧光检测法测定片剂中盐酸美西律的含量

建立了微流控芯片毛细管电泳激光诱导荧光检测法测定片剂中盐酸美西律含量的方法,对衍生条件和电泳条件进行了系统的考察。盐酸美西律经异硫氰酸荧光素(FITC)40℃衍生6h,以20 mmol/L硼砂为电泳缓冲溶液,进样30s后,分离电压2000V,可在1 min内完成一次检测。方法的检出限为0.022 mg/L、线性范围0.108～1.079 mg/L、相关系数0.994,加标回收率为99.7%～102.3%,方法适用于盐酸美西律的检测和质量控制。     

荧光标记的叶酸修饰壳聚糖纳米载体研制

制备荧光标记的叶酸偶联壳聚糖纳米粒,为抗肿瘤药物给药系统提供载体材料。通过叶酸活性酯与壳聚糖上的氨基反应,使叶酸与壳聚糖偶联。将异硫氰基荧光素与叶酸偶联壳聚糖进行化学嫁接,以离子交联法制成具有荧光的叶酸偶联壳聚糖纳米粒,并与肝癌HepG2细胞进行体外细胞实验。实验结果表明:叶酸活性酯用量和反应温度及试剂滴加速度是影响偶联比的主要因素;在叶酸活性酯与壳聚糖用量质量比为1:1,反应温度为30℃,滴加速度为2mL/min,反应时间为12h的条件下可得到偶联稳定的叶酸偶联壳聚糖;所制得的纳米粒粒径为290nm,形态规则,细胞荧光效果明显;此方法能用于制备荧光标记的叶酸修饰壳聚糖纳米粒载体。     

Sequencing of phosphopeptides sulfonated by 4-sulfophenyl isothiocyanate using post-source decay matrix-assisted laser desorption/ionization time-of-flight mass spectrometry

Phosphorylation/dephosphorylation is probably the most common and important reversible post-translational modification of proteins. Analyzing the functional effects of phosphorylation is helpful for understanding the biological functions of proteins. Identification of the phosphorylation sites of phosphorylated protein is a prerequisite for research on phosphorylation. In this work, an effective and simple method of identification of protein phosphorylation sites has been developed. Phosphopeptides were selectively enriched with immobilized metal affinity chromatography (IMAC) and subsequently chemically modified by 4-sulfophenyl isothiocyanate, and then the chemically modified phosphopeptides were sequenced with post-source decay (PSD) matrix-assisted laser desorption/ionization (MALDI) time-of-flight mass spectrometry for detecting phosphorylation sites. The charge of derivatization by 4-sulfophenyl isothiocyanate introduces a negative sulfonic acid group at the N-terminus of a peptide, and enables the selective detection of only a single series of C-terminal y-type ions. This chemically assisted method greatly simplifies the extremely complex pattern of PSD fragment ions and makes the PSD spectra more easier to be interpreted. The phosphorylation sites of a synthesized model phosphopeptide and human c-myc protein have been successfully identified by this method.     

Structural analysis of tris(tetra-n-butylammonium) hexakisisothiocyanatoyttrate(III)

The structural analysis of [(n-C₄H₉)₄N]₃[Y(NCS)₆] (I) using single-crystal diffraction data and full-matrix least squares refinement has been carried out. The hexaisothiocyanate complex crystallizes in the centrosymmetric triclinic space group P (No. 2) with unit cell constants of a = 12.431(1), b = 12.866(1), c = 22.750(2) Å, = 90.78(1), = 92.05(1), = 96.67(1)°, and Z = 2. The molecular unit consists of three separate cationic tetra-n-butylammonium groups and an independent hexakisisothiocyanatoyttrate anionic group in which the six thiocyanate ligands are octahedrally coordinated through the N atom to the Y central ion. Selected bond distances and angles are presented as well as the synthesis and peripheral studies of (I).