二甲基亚砜对乙酸气相色谱保留时间的影响及其机理

通过气相色谱、红外光谱分析和量子化学计算,探究溶于二甲基亚砜（DMSO）中乙酸保留时间发生波动的原因。 结果显示,乙酸保留时间变化与DMSO体积等量递增呈线性关系,R²=0.99301;根据红外光谱分析得出,DMSO和乙酸之间生成了氢键,以DMSO-乙酸分子的形式通过色谱柱;根据Gaussian09程序计算结果,DMSO电子密度大的部分给予电子,与乙酸之间形成了氢键,而DMSO电子密度小的部分容易获得电子与具有强偶极矩的色谱柱固定液聚乙二醇产生作用力,吸附在固定液上。因此,在上述一系列复杂的分子间作用力的共同影响下,乙酸保留时间发生了波动,且随着溶剂DMSO体积比增加,乙酸保留时间不断延长。     

加强实验教学环境内涵建设 提高环境育人质量

在实验室里的实验教学过程涉及到教书育人、管理育人、服务育人和环境育人。一个良好的实验环境不仅能够对学生起到潜移默化的教育作用,而且对教书育人、管理育人和服务育人工作的开展和实施也能起到推动和促进作用。本文主要介绍厦门大学化学国家级实验教学示范中心"以学生为中心",在强化实验教学环境内涵建设、提高实验环境育人质量方面的一些做法和体会,以期更好地为实验教学"思政"提供可复制、可推广的建设方案。     

Detection of oxygen addition peaks for terpendole E and related indole–diterpene alkaloids in a positive‐mode ESI‐MS

This report describes that a regular positive electrospray ionization mass spectrometry (MS) analysis of terpendoles often causes unexpected oxygen additions to form [M + H + O]⁺ and [M + H + 2O]⁺, which might be a troublesome in the characterization of new natural analogues. The intensities of [M + H + O]⁺ and [M + H + 2O]⁺ among terpendoles were unpredictable and fluctuated largely. Simple electrochemical oxidation in electrospray ionization was insufficient to explain the phenomenon. So we studied factors to form [M + H + O]⁺ and [M + H + 2O]⁺ using terpendole E and natural terpendoles together with some model indole alkaloids. Similar oxygen addition was observed for 1,2,3,4‐tetrahydrocyclopent[b]indole, which is corresponding to the substructure of terpendole E. In tandem MS experiments, a major fragment ion at m/z 130 from protonated terpendole E was assigned to the substructure containing indole. When the [M + H + O]⁺ was selected as a precursor ion, the ion shifted to m/z 146. The same 16 Da shift of fragments was also observed for 1,2,3,4‐tetrahydrocyclopent[b]indole, indicating that the oxygen addition of terpendole E took place at the indole portion. However, the oxygen addition was absent for some terpendoles, even whose structure resembles terpendole E. The breakdown curves characterized the tandem MS features of terpendoles. Preferential dissociation into m/z 130 suggested the protonation tendency at the indole site. Terpendoles that are preferentially protonated at indole tend to form oxygen addition peaks, suggesting that the protonation feature contributes to the oxygen additions in some degrees. © 2014 The Authors. Journal of Mass Spectrometry published by John Wiley & Sons, Ltd.     

Efficient Copper‐Catalyzed Direct Intramolecular Aminotrifluoromethylation of Unactivated Alkenes with Diverse Nitrogen‐Based Nucleophiles

A mild, convenient, and step‐economical intramolecular aminotrifluoromethylation of unactivated alkenes with a variety of electronically distinct, nitrogen‐based nucleophiles in the presence of a simple copper salt catalyst, in the absence of extra ligands, is described. Many different nitrogen‐based nucleophiles (e.g., basic primary aliphatic and aromatic amines, sulfonamides, carbamates, and ureas) can be employed in this new aminotrifluoromethylation reaction. The aminotrifluoromethylation process allows straightforward access to diversely substituted CF₃‐containing pyrrolidines or indolines, in good to excellent yields, through a direct difunctionalization strategy from the respective acyclic starting materials. Mechanistic studies were conducted and a plausible mechanism was proposed.     

Metal‐Free Oxidative Radical Addition of Carbonyl Compounds to α,α‐Diaryl Allylic Alcohols: Synthesis of Highly Functionalized Ketones

A metal‐free direct alkylation of simple carbonyl compounds (ketones, esters, and amides) with α,α‐diaryl allylic alcohols is described. The protocol provides facile access to highly functionalized dicarbonyl ketones by a radical addition/1,2‐aryl migration cascade. The regioselectivity of the reaction was precisely controlled by the nature of the carbonyl compound.     

Isolation of a Neutral Boron‐Containing Radical Stabilized by a Cyclic (Alkyl)(Amino)Carbene

Utilizing a cyclic (alkyl)(amino)carbene (CAAC) as a ligand, neutral CAAC‐stabilized radicals containing a boryl functionality could be prepared by reduction of the corresponding haloborane adducts. The radical species with a duryl substituent was fully characterized by single‐crystal X‐ray structural analysis, EPR spectroscopy, and DFT calculations. Compared to known neutral boryl radicals, the isolated radical species showed larger spin density on the boron atom. Furthermore, the compound that was isolated is extraordinarily stable to high temperatures under inert conditions, both in solution and in the solid state. Electrochemical investigations of the radical suggest the possibility to generate a stable formal boryl anion species.     

气相色谱-质谱法同时测定水果中9种保鲜剂的残留量

建立了采用气相色谱-质谱(GC-MS)同时测定水果中9种保鲜剂残留量的分析方法。水果样品用正己烷/乙酸乙酯(1/1,v/v)混合提取剂超声提取,经Florisil层析柱净化后用正己烷/乙酸乙酯(1/3,v/v)混合洗脱剂洗脱,以磷酸三苯脂(TPP)为内标物,采用GC-MS的全扫描方式(SCAN)和选择离子监测方式(SIM)对9种保鲜剂进行定性与定量分析。实验结果表明,9种保鲜剂的检出限(LOD)为0.10~2.16μg/kg,在50、100、200μg/kg添加水平下的回收率为75.3%~128%,相对标准偏差为1.57%~11.6%。本分析方法样品前处理简便,净化效果明显,在SIM谱图中分析目标物响应值大、灵敏度高,定量准确可靠,能够满足保鲜剂痕量残留的检测要求。     

A Small-Molecule AIE Chromosome Periphery Probe for Cytogenetic Studies

The chromosome periphery (CP) is a complex network that covers the outer surface of chromosomes. It acts as a carrier of nucleolar components, helps maintain chromosome structure, and plays an important role in mitosis. Current methods for fluorescence imaging of CP largely rely on immunostaining. We herein report a small-molecule fluorescent probe, ID-IQ , which possesses aggregation-induced emission (AIE) property, for CP imaging. By labelling the CP, ID-IQ sharply highlighted the chromosome boundaries, which enabled rapid segmentation of touching and overlapping chromosomes, direct identification of the centromere, and clear visualization of chromosome morphology. ID-IQ staining was also compatible with fluorescence in situ hybridization and could assist the precise location of the gene in designated chromosome. Altogether, this study provides a versatile cytogenetic tool for improved chromosome analysis, which greatly benefits the clinical diagnostic testing and genomic research.     

Estimation of 47Sc and 177Lu production rates from their natural targets in Kyoto University Research Reactor

Journal of Radioanalytical and Nuclear Chemistry - To assess the capability of Kyoto University Research Reactor to supply the domestic needs of medical isotopes, its neutron flux has been fully...     

Production of 99Mo/99mTc by photonuclear reaction using a natMoO3 target

Journal of Radioanalytical and Nuclear Chemistry - Amount estimation of production of 99Mo required for medical applications was carried out by utilizing an electron linear accelerator with...