A Chemistry for Incorporation of Selenium into DNA-Encoded Libraries

Conventional direct C−H selenylation suffers from simple selenation with limited atom economy and complicated reaction system. In this work, we designed benzoselenazolone as a novel bifunctional selenide reagent for both off- and on-DNA C−H selenylation under rhodium(III) catalysis. We show that using benzoselenazolone allowed production of a series of selenylation products containing an adjacent aminoacyl group in a fast and efficient way, with high atom economy. The synthetic application of this method was demonstrated by taking advantage of the amide functionality as a nucleophile, directing group, and amide coupling partner. This work shows great potential in facilitating rapid construction of selenium-containing DNA-encoded chemical libraries (SeDELs), and lays the foundation for the development of selenium-containing drugs.     

模板反应及其在含氮大环金属配合物合成中的应用

扼要介绍了模板反应的概念、类型,并举例介绍了在含氮大环金属配合物合成中的应用。     

海洛因对别洛索夫-扎鲍京斯基振荡化学反应的影响及其分析应用

研究了海洛因对Belousov Zhabotinsky(B Z)振荡反应的影响 ,结果表明 :海洛因的加入明显地改变了振荡体系的周期和振幅 ,即对振荡体系产生扰动 ,扰动的浓度范围为 1.8× 10 -8～ 2 .1× 10 -3 mol/L ,且海洛因的浓度分别在 3.8× 10 -6～ 2 .8× 10 -5mol/L和 0 .9× 10 -6～ 2 .9× 10 -5mol/L范围内与振荡周期改变值ΔT和振幅改变值ΔA均呈现良好的线性关系 ,相关系数分别为 0 .9931和 0 .974 6。据此 ,建立了测定海洛因的新方法。     

物理化学中化学势的含义及应用详解

对化学势概念作了比较详细的解读,并结合扩散、相变化、渗透以及化学变化等过程,对化学势判据在这些过程中的应用给出了图文并茂的说明,借此充分阐述了化学势所体现的化学中变化趋势的这一势的含义。     

中美化学教材习题情境创设的比较研究——以“化学反应原理”内容为例

以化学反应原理内容为例,对中国人教版高中化学教材和美国高中化学教材Chemistry:Conceptions and Application习题中的情境创设进行比较研究,发现2者在情境性习题的主题分布与占比、情境素材来源分布、问题与情境的融合度等方面存在明显差异。     

A Chemistry for Incorporation of Selenium into DNA‐Encoded Libraries

Conventional direct C?H selenylation suffers from simple selenation with limited atom economy and complicated reaction system. In this work, we designed benzoselenazolone as a novel bifunctional selenide reagent for both off‐ and on‐DNA C?H selenylation under rhodium(III) catalysis. We show that using benzoselenazolone allowed production of a series of selenylation products containing an adjacent aminoacyl group in a fast and efficient way, with high atom economy. The synthetic application of this method was demonstrated by taking advantage of the amide functionality as a nucleophile, directing group, and amide coupling partner. This work shows great potential in facilitating rapid construction of selenium‐containing DNA‐encoded chemical libraries (SeDELs), and lays the foundation for the development of selenium‐containing drugs.     

过氧草酰类化学发光反应及其在分析化学中的应用

在化学发光试剂中，过氧草酰类试剂是发光量子产率最高的一类试剂，本文对这类试剂的合成、性质、发光机理及其在液相色谱、薄层色谱及流动注射分析等方面的应用进行了评述。引用文献９３篇。     

Reinvestigation on the Reaction of Salicylic Chloride with Salicylic Amide and X-ray Crystal Structure of a New Macrocyclic Polyester

1 INTRODUCTION In the systematic studies on the synthesis, structure and recognition of macrocyclic phospho- ramidate containing biaryl oxadiazole[1, 2], we need to synthesize benzoxazines. Lattmann reported that the salicylic chloride reacts with salicylic amide at 170℃ to give 2-(2-hydroxyphenyl)benzo[1,3]- oxazine-4-one[3]. However, Palazzo got bisamide 1 in 90% yield under similar conditions[4]. Titherley reported that amides of type 1 underwent cycli- zation to benzoxazines if hea…     

物理化学实验改进:修饰的BZ化学振荡反应在食品检测中的应用*

为适应创新应用型人才培养的需要,针对现有物理化学实验教材中的BZ振荡反应实验进行了验证-探索两段式教学尝试。在保留原有验证性实验基础上进行延伸,探索催化剂、反应底物的浓度对碘离子修饰的BZ振荡体系的影响,绘制了罗丹明B的标准曲线,用以检测食品中罗丹明B的含量。相比传统验证性实验,两段式教学模式更易于课上、课下相结合,既能训练学生物理化学基本实验技能,又有利于学生自主创新能力和科研能力的培养。     

Wittig反应在天然产物合成中的应用

综述了近十年来Wittig反应、Wittig－Horner反应及其它类型Wittig反应在天然产物合成中的应用。参考文献33篇。     

离子液体及其在生物催化中的应用

综述了在离子液体中酶及完整细胞的生物催化反应的研究状况, 初步总结了影响离子液体中酶催化反应的因素, 离子液体作为绿色反应介质在生物转化工业中将有广阔的应用前景.     

基于Schiff-Base反应的成环策略及应用

基于Schiff-base反应的大环化合物是近些年来超分子领域研究的热点.这些大环化合物不但在传感器、功能材料等领域发挥着重要的作用,而且在自组装研究领域具有重要的意义.从模板法和非模板法两方面分析了一些具有代表性Schiff-base大环的合成,发现,不但具有合适半径和构型的离子可以作为成环反应的模板,而且强烈的分子内氢键也能有效地驱动成环反应.同时,对于该类大环分子合成所面临的问题及发展方向进行了评述和预测.     

停流—荧光反应速率仪及其应用于测定维生素B1

本文利用国产930型荧光光度计作为检测器,采用自已制作的流通池,配以蠕动泵及记录仪,组装成停流-荧光动力学分析装置,并用以进行了停流荧光反应速率法测定维生素B_1的研究,利用Hg~(2+)离子在碱性介质中将硫胺素(维生素B_1)氧化为硫胺荧的动力学反应,测定了维生素B_1片剂中维生素B_1的含量。结果表明,这套仪器用于动力学分析,操作简便、省时,维生素B_1的测定结果与标准值基本相符,相对标准偏差为1.28％,其准确度和重现性均令人满意。     

物理化学中关于n级反应及其半衰期的讨论

相对于积分法和微分法,由半衰期法确定反应级数的方法具有更高的可靠性和普适性。但教科书上由n级反应推导半衰期的过程却较为模糊。本文通过四种不同的方法详细探讨了n级反应及其半衰期的推导过程,有利于学生加深对n级反应及其半衰期推导过程的认识。     

Tetrazole Photoclick Chemistry: Reinvestigating Its Suitability as a Bioorthogonal Reaction and Potential Applications

The bioorthogonality of tetrazole photoclick chemistry has been reassessed. Upon photolysis of a tetrazole, the highly reactive nitrile imine formed undergoes rapid nucleophilic reaction with a variety of nucleophiles present in a biological system, along with the expected cycloaddition with alkenes. The alternative use of the tetrazole photoclick reaction was thus explored: tetrazoles were incorporated into Bodipy and Acedan dyes, providing novel photo‐crosslinkers with one‐ and two‐photon fluorescence Turn‐ON properties that may be developed into protein‐detecting biosensors. Further introduction of these photo‐activatable, fluorogenic moieties into staurosporine resulted in the corresponding probes capable of photoinduced, no‐wash imaging of endogenous kinase activities in live mammalian cells.     

美国高中化学教科书中氧化还原反应图片设计分析

统计了美国高中化学教科书《化学：概念与应用》中氧化还原反应的知识内容所包含的图片类型，分析研究其作用，同时针对我国化学教科书图片设计提出了建议。     

Dissipative Dynamic Covalent Chemistry (DDCvC) Based on the Transimination Reaction

This work reports that the composition of a dynamic library (DL) of interconverting imines can be controlled over time in a dissipative fashion by the addition of an activated carboxylic acid used as a chemical fuel. When the fuel is added to the DL, which is initially under thermodynamic equilibrium, the composition of the mixture dramatically changes and a new, dissipative (out of equilibrium) state is reached that persists until fuel exhaustion. Thus, a transient dissipative dynamic library (DDL) is generated that, eventually, reverts back to the initial DL when the fuel is consumed, closing a DL→DDL→DL cycle. The larger the amount of added fuel, the longer the time spent by the system in the DDL state. The transimination reaction is shown to be an optimal candidate for the realization of a dissipative dynamic covalent chemistry (DDCvC).     

克拉霉素的电化学反应机理研究与应用

应用线性扫描伏安法、循环伏安法、常规脉冲伏安法等电化学手段并结合紫外吸收光谱研究了药物克拉霉素(clarithromycin, CAM)在pH 1.8～9.2 Britton-Robinson缓冲溶液和0.05 mol•L^－1 NaOH溶液中的电化学行为. 在所研究的pH范围, CAM分别产生P₁, P₂, P₃, P₄四个还原波, 其中P₁, P₂, P₄三个波均为其药效活性基团C-9位羰基的还原所产生. 实验结果表明: 在pH 1.8～5.7的B-R缓冲溶液条件下所获得的P₁波为两电子不可逆弱吸附还原波; 在6.0＜pH＜9.2的B-R缓冲溶液中, CAM产生P₂和P₃两个波, 其中P₂为两电子不可逆还原波, P₃为催化氢波. 在0.05 mol• L^－1 NaOH溶液中, CAM产生的P₄波是一个单电子的不可逆吸附还原波. 根据P₄波的峰电流i_P与CAM浓度的线性关系, 建立了CAM含量测定的新方法.     

双氮桥联1,10-菲咯啉大环与金属离子的配位反应研究

双氮桥联 1 ,1 0 -菲咯啉大环 H2 HAPP(图 1 )是类卟啉大环配体 .1 972年 ,Ogawa等 [1] 首次报道了　Fig.1　 Molecular structure of aza-bridged bis-phenan-throline macrocycle( H2 HAPP)该大环的合成 ,其钴、镍和铜配合物的制备也已见报道 [1～ 7] .研究结果显示 ,H2 HAPP的金属配合物可以作为人工 DNA裂解酶 [8,9] 和催化 CO2 还原的催化剂 [10 ] .由于 H2 HAPP合成产率低 ,难溶于大多数溶剂 ,因而在过去几十年中对于这类大环化合物的研究并未引起人们的广泛注意 .虽然 Ogawa等 [2 ]曾报道 ,在热的 H2 HAPP硝基苯溶液回…