金刚烷单季铵盐阳离子表面活性剂的合成

引言金刚烷(Adamantane)化学名为三环[3,3,1,13,7]癸烷,分子式为C10H16,是一种高度对称的笼状烃,整个环系具有周正对称、高度稳定的结构特征[1]。金刚烷分子中1,3,5,7位上四个桥头     

沸石催化合成金刚烷

采用不同类型的沸石催化剂研究了金刚烷的合成，并考察了不同条件对反应的影响。研究表明，Ｎｉ（３％～５％）／ＵＳＹ型催化剂具有较高活性和良好的金刚烷选择性；最佳反应条件为：温度２５０℃，催化剂添加量２５％～２８％，时间２～３ｈ，氢气压力１．０～１．５ＭＰａ；通入微量无水ＨＣｌ气体，金刚烷收率显著提高。     

Catalysts Containing the Adamantane Scaffold

The bulky, but symmetrically beautiful, adamantane ring system is now pervasive throughout physical, medicinal and synthetic chemistry, since it was first discovered in 1924 and coined “dekaterpene”. This fascinating name lived up to its natural product roots when adamantane was isolated from crude oil in 1933, but it was not until 1957 in a landmark contribution by Paul von Ragué Schleyer that adamantane was made readily accessible through synthesis. Beyond the legacy to physical and medicinal chemistry, the adamantane moiety has been quintessential in the development of some of the most important catalysts to date. Considering adamantane's impact on catalyst development past, present and future, this subject is for the first time reviewed herein.

     

介孔HM沸石催化金刚烷的制备

采用酸-碱相结合的处理方法对含有模板剂四乙基氢氧化铵的低硅/铝摩尔比丝光沸石(HM)进行改性处理,制备了一系列介孔HM沸石;采用XRD、N₂吸附-脱附、NH₃-TPD和SEM手段表征所制备的介孔HM沸石催化剂的物化性质,并在100 mL间歇式不锈钢高压反应釜中考察了其在桥式四氢双环戊二烯(endo-TCD)异构化制备金刚烷反应中的催化性能。结果表明,先采用6 mol/L HCl溶液对低硅/铝摩尔比 (n(Si)/n(Al)=9) HM进行酸处理,使其硅/铝摩尔比提高到30.1,进而采用不同浓度的NaOH溶液进行碱处理,可以在HM沸石中成功引入介孔,并且能保持较为完整的晶体形貌。当碱处理液浓度为0.2 mol/L时,所得HM-6H-0.2沸石由于其适宜的酸性质和良好的扩散性能,endo-TCD转化率和金刚烷产率达到最高。采用HM-6H-0.2为催化剂,在较适宜的操作条件下,即m(HM-6H-0.2)/m(endo-TCD) = 0.6、反应温度260℃、反应时间6 h时, endo-TCD转化率达到98.5%,金刚烷产率为33.7%,且催化剂重复使用5次后,金刚烷产率仍可达到28.5%。     

PW/USY复合型催化剂上金刚烷的合成

在100 mL间歇式不锈钢高压反应釜中,考察了超稳Y沸石负载磷钨酸(PW)用于桥式四氢双环戊二烯(endo-TCD)异构化合成金刚烷反应中的催化性能,并用X射线衍射、氨程序升温脱附和FT-IR等表征方法对催化剂进行表征.结果表明,当PW负载量为10%时PW/USY酸量最大,催化剂的酸性质和孔结构是影响催化性能的重要因素.在适宜的操作条件下即10%PW/USY催化剂焙烧温度450℃、反应温度260℃、n(环己烷)/n(endo-TCD)=5、w(cat.)/w(endo-TCD)=0.2、初压0.8 MPa、反应时间6 h,endo-TCD的转化率达到99.5%,金刚烷的收率达到28.3%.     

Adamantyl Substitution Strategy for Realizing Solution‐Processable Thermally Stable Deep‐Blue Thermally Activated Delayed Fluorescence Materials

Highly efficient solution‐processable emitters, especially deep‐blue emitters, are greatly desired to develop low‐cost and low‐energy‐consumption organic light‐emitting diodes (OLEDs). A recently developed class of potentially metal‐free emitters, thermally activated delayed fluorescence (TADF) materials, are promising candidates, but solution‐processable TADF materials with efficient blue emissions are not well investigated. In this study, first the requirements for the design of efficient deep‐blue TADF materials are clarified, on the basis of which, adamantyl‐substituted TADF molecules are developed. The substitution not only endows high solubility and excellent thermal stability but also has a critical impact on the molecular orbitals, by pushing up the lowest unoccupied molecular orbital energy and triplet energy of the molecules. In the application to OLEDs, an external quantum efficiency (EQE) of 22.1% with blue emission having Commission Internationale de l'Eclairage (CIE) coordinates of (0.15, 0.19) is realized. A much deeper blue emission with CIE (0.15, 0.13) is also achieved, with an EQE of 11.2%. These efficiencies are the best yet among solution‐processed TADF OLEDs of CIE y < 0.20 and y < 0.15, as far as known. This work demonstrates the validity of adamantyl substitution and paves a pathway for straightforward realization of solution‐processable efficient deep‐blue TADF emitters.     

利用超分子作用提高竹红菌乙素的水溶性：金刚烷修饰的竹红菌乙素的合成及其环糊精聚合物包结物的光动力活性研究

本文设计合成了金刚烷修饰的竹红菌乙素衍生物，利用环糊精聚合物与金刚烷基团间的包结作用制备了基于竹红菌乙素的水溶性光敏体系，并通过顺磁共振技术研究了该光敏体系的活性氧产生能力．     

Host-Guest Complexation Studied by Fluorescence Correlation Spectroscopy: Adamantane�CCyclodextrin Inclusion

The host-guest complexation between an Alexa 488 labelled adamantane derivative and β-cyclodextrin is studied by Fluorescence Correlation Spectroscopy (FCS). A 1:1 complex stoichiometry and a high association equilibrium constant of K = 5.2 × 10⁴ M⁻¹ are obtained in aqueous solution at 25 °C and pH = 6. The necessary experimental conditions are discussed. FCS proves to be an excellent method for the determination of stoichiometry and association equilibrium constant of this type of complexes, where both host and guest are nonfluorescent and which are therefore not easily amenable to standard fluorescence spectroscopic methods.     

Rhombellanic diamond

Rhombellanes are mathematical structures, proposed in 2017; they may appear both in crystal or quasicrystal networks, also in their homeomorphs, further possible becoming real molecules. The simplest rhombellane is the K_2.3 complete bipartite graph, a tile found in the linear polymeric staffanes. In this paper a new binodal crystal network, called here dia-rbl, is introduced; its repeating unit, ada-rbl, is a 4D structure. The crystal structure is characterized by connectivity and ring sequences and also by the Omega polynomial.     

Diamondoid Amino Acid-Based Peptide Kinase A Inhibitor Analogues

The incorporation of diamondoid amino acids (DAAs) into peptide-like drugs is a general strategy to improve lipophilicity, membrane permeability, and metabolic stability of peptidomimetic pharmaceuticals. We designed and synthesized five novel peptidic DAA-containing kinase inhibitors of protein kinase A using a sophisticated molecular dynamics protocol and solid-phase peptide synthesis. By means of a thermophoresis binding assay, NMR, and crystal structure analysis, we determined the influence of the DAAs on the secondary structure and binding affinity in comparison to the native protein kinase inhibitor, which is purely composed of proteinogenic amino acids. Affinity and binding pose are largely conserved. One variant showed 6.5-fold potency improvement, most likely related to its increased side chain lipophilicity. A second variant exhibited slightly decreased affinity presumably due to loss of hydrogen-bond contacts to surrounding water molecules of the first solvation shell.