着色剂之红曲素和红斑素的对比分析

介绍了红曲素和红斑素的结构、特性和异同点以及红曲色素的组成和分离。红曲色素对人体健康有积极作用,但也可能存在隐患。     

A convenient method to prepare random LA/CL copolymers from poly(L-lactide) and ε-caprolactone

Sequential addition of L-lactide(LA) followed by ε-caprolactone(CL), and simultaneous addition of both monomers, afforded random LA/CL copolymers in the presence of lanthanide aryloxides under mild conditions. Transesterification was proved to play a predominant role in random copolymer formation. Moreover, treatment of poly(L-lactide) with ε-CL led to random copolymer formation, which provides a new strategy not only to prepare random LA/CL copolymers, but also to directly modify PLLA.     

双矿化剂对合成ZSM-5分子筛酸性和织构特征及其甲醇转化制丙烯催化性能的影响

采用静态水热法在F^--OH^-体系中,以四丙基氢氧化铵为模板剂、偏铝酸钠为铝源、正硅酸乙酯为硅源,合成了纳米SiO₂-ZSM-5分子筛,考察了F^-/Al₂O₃物质的量比对所合成的ZSM-5分子筛织构性质和甲醇转化制丙烯催化性能的影响。结果发现,随着初始溶胶F^-/Al₂O₃物质的量比的增大,产物中SiO₂的含量增大,ZSM-5分子筛的相对结晶度有所降低;同时,分子筛的比表面积和孔容减小、酸强度降低、酸量减少。对于甲醇转化制丙烯,最佳F^-/Al₂O₃物质的量比为12;此时,丙烯选择性高于45%,丙烯/乙烯（P/E）比值大于10。反应机理分析表明,过渡态择形选择性是控制烯烃选择性的重要因素。     

CO<Subscript>2</Subscript>-responsive Polymeric Fluorescent Sensor with Ultrafast Response

Abstract Response speed is one of the most important evaluation criteria for CO₂ sensors. In this work, we report an ultrafast CO₂ fluorescent sensor based on poly[oligo(ethylene glycol) methyl ether methacrylate]-b-poly[N,N-diethylaminoethyl methacrylate-r-4-(2-methylacryloyloxyethylamino)-7-nitro-2,1,3-benzoxadiazole] [POEGMA-b-P(DEAEMA-r-NBDMA)], in which DEAEMA units act as the CO₂-responsive segment and 4-nitrobenzo-2-oxa-1,3-diazole (NBD) is the chromophore. The micelles composed of this copolymer could disassemble in 2 s upon CO₂ bubbling, accompanying with enhanced fluorescence emission with bathochromic shift. Furthermore, the quantum yield of the NBD chromophore increases with both the CO₂ aeration time and the NBD content. Thus we attribute the fluorescent enhancement to the inhibition of the photo-induced electron transfer between unprotonated tertiary amine groups and NBD fluorophores. The sensor is durable although it is based on “soft” materials. These micellar sensors could be facilely recycled by alternative CO₂/Ar purging for at least 5 times, indicating good reversibility.     

Catalyst-free and atom-economic synthesis of substituted 1-acetyl and 1-hydroxyl carbazoles

The first-ever Diels-Alder reactions of 3-alkenyl indoles with a conjugated alkynyl ketone are reported. These reactions proceed in an atom-economic manner without a catalyst and give various substituted 1-acetyl carbazoles in moderate to excellent yields. These products can be converted to 1-hydroxyl carbazoles in high yields under mild reaction conditions.     

可见光照射下ATRP法合成高分子量聚丙烯腈

可见光下,以α-溴苄基乙酸乙酯为引发剂,采用ATRP法合成了高分子量聚丙烯腈（PAN, M_n,GPC/2.5=8.6×10⁴ g·mol^-1, M_w/M_n=1.24）,转化率95%;以Ir(ppy)₃为催化剂,PAN-Br为大分子引发剂,与丙烯酸丁酯(BA)聚合,合成了PAN-b-PBA嵌段共聚物,其结构经¹H NMR和GPC确证。研究了Ir(ppy)₃催化聚合体系的动力学行为。结果表明：该体系的聚合行为具有典型的“活性”特征。     

片段法合成抗骨质疏松多肽药物特立帕肽

将特立帕肽序列中的34个氨基酸分成4个片段:1-11、 12-16、 17-24和25-34;以Wang Resin（王树脂）为固相载体制得25-34肽树脂;以CTC Resin（2-氯三苯甲基氯树脂）为固相载体制得1-11、 12-16和17-24等3个片段的全保护肽,然后将3个片段的全保护肽按照肽序依次缩合到25-34的肽树脂上,经三氟乙酸切割并脱除侧链保护基得特立帕肽粗品,再经液相色谱纯化得特立帕肽,纯度大于99%,总收率达33%,其结构经MS(ESI)确证。     

度鲁特韦关键中间体的合成及分子蒸馏提纯工艺

4-甲氧基乙酰乙酸甲酯是合成抗HIV新药度鲁特韦的关键中间体。本文以4-氯乙酰乙酸甲酯与甲醇为起始原料,氢化钠和甲醇钾作为混合碱,合成4 甲氧基乙酰乙酸甲酯,通过分子蒸馏法对其进行提纯获得纯品,总收率88%,纯度99.7%,其结构经¹H NMR和¹³C NMR确证。并对分子蒸馏工艺条件进行了优化。     

基于环己酮氧化脱氢构建碳-碳与碳-杂键

环己酮是一种廉价易得的大宗有机化工产品,被广泛用作有机合成反应的原料和中间体。脱氢芳构化是合成功能化芳烃的有效途径,使用环己酮作为反应底物,经过亲核加成、脱水和催化脱氢可以将非芳香的有机分子转化为芳香化合物。与传统的芳基化反应相比,该策略避免了苛刻的反应条件和含卤化合物的生产,克服了化学和区域选择性难以控制的难题,为功能化芳烃的合成提供了一条温和、环保的途径。本文就近年来以环己酮为原料,进行氧化脱氢、直接构建碳-碳和碳-杂键,及通过碳-杂键的形成合成杂环化合物的研究现状进行介绍。     

Orbitrap高分辨质谱法高通量筛查生化药品、中成药与保健品中非法添加的13种消化类化学药物

建立了生化药品、中成药和保健品中非法添加的13种消化类化学药的超高效液相色谱-Orbitrap高分辨质谱(UHPLC-HRMS)高通量筛查方法。供试品以甲醇-水(50∶50)为提取溶剂,经Hypersil Gold C18(2.1 mm×100 mm,3μm)色谱柱分离,以乙腈-0.1%甲酸水为流动相进行梯度洗脱,单次分析仅需10min。采用正离子检测,Full MS/dd-MS2扫描模式。通过比较供试品与对照品的色谱保留时间、高分辨一级和二级质谱,判断供试品中是否非法添加消化类药物,并对阳性样品进行定量分析。13种化合物的线性范围均为8.0~800μg/L,相关系数(r)均不低于0.998 5,回收率为94.6%~106.2%,相对标准偏差为1.2%~2.9%。该法快速简便、通量高、选择性好、灵敏度高,并已用于生化药品、中成药及保健品非法添加消化类化学药的高通量筛查和测定,在38批中成药中发现5批阳性样品,在43批保健品中发现3批阳性样品。