基于多重氢键组装的双杯冠合成及对铯离子的络合

合成了一种基于多重氧键组装形成的新型双杯冠化合物,利用核磁共振氢谱(1H NMR)和碳谱(13C NMR)以及高分辨质谱(ESI-HRMS)对组装前体分子结构进行了表征.通过一维和二维核磁共振氢谱(2D NOESY)研究了该双杯冠的的自组装结构,并采用核磁共振和紫外-可见光谱的方法测定了其对铯离子的络合.实验表明,通过氢键组装形成的双杯冠化合物,由于阻止了单杯冠分子内组装而限制了冠醚环构象改变,其萃取率由单杯冠的82％提高到96％.     

两亲性冠醚化合物的合成及其在离子通道膜中的应用

采用对羟基苯甲酸甲酯、4-羧基苯并-15-冠醚-5等物质为原料制备了具有自组装功能的两亲性冠醚化合物 2-羟甲基-[1,4,7,10,13-苯并15冠5]-3,4,5-三[4-(10-十二烷基-1-羰基)苄氧基]苯甲酸,采用 FT-IR,1H NMR,MS,DSC 以及POM 等方法对其化学结构和结晶性能进行表征.利用...     

14-冠-4冠醚衍生物与Li(I)的络合过程理论研究

臂式冠醚由于其侧臂基团可以不同程度改变冠醚的供电子能力、冠醚环的构象、亲水性等,从而使其与金属离子的络合性能发生变化。以二苯并14-冠-4冠醚(DB14C4)为基础,选取羟基(-OH)、氨基(-NH_2)、羟甲基(-CH_2OH)、氨甲基(-CH_2NH_2)四种侧臂基团,基于密度泛函理论(DFT),在水溶剂模型下,研究了不同侧臂基团对DB14C4与Li(I)络合过程的影响.从结构优化、前线轨道(HOMO、LUMO)及静电势(ESP)、独立梯度函数(IGM)方面进行了分析.结果表明,羟甲基的引入可改善冠醚的配位能力,为高选择性冠醚的设计提供理论支持.     

氨基与冠醚双官能团四苯乙烯衍生物自组装及其聚集诱导荧光研究

冠醚和二级铵盐结构的分子经常被用来构建超分子自组装体,报道了一种不对称的四苯乙烯衍生物单体,其分别与二苯并-24-冠-8(DB24C8)和二级铵盐结构单元通过点击化学反应连接,通过核磁共振氢谱、碳谱和质谱得到结构表征.通过核磁滴定显示出冠醚和二级铵盐结构在酸性条件下能够形成超分子组装体,并初步研究了其在乙腈/水溶液中的聚集诱导荧光性能.     

质子化4,4’-联吡啶盐与二苯并-24-冠-8的包合行为

通过1H NMR, ESI-MS, 紫外-可见光谱等分析手段研究了两个新的质子化联吡啶盐客体与冠醚二苯并-24-冠-8在溶液中和气态下的包合行为. 研究结果表明, 质子化的联吡啶盐与冠醚主要形成1∶1的超分子包合物, 且存在夹心式的几何结构, 双质子化的联吡啶盐比单质子化的联吡啶盐具有更强的结合冠醚的能力, 其缔合常数分别为200, 116 L•mol－1.     

基于杯芳烃主体的分子自组装研究进展

分子自组装是超分子化学最重要的研究内容之一. 杯芳烃作为继冠醚、环糊精之后的第三代人工合成受体分子已在分子自组装研究方面取得了重要进展并显示了广泛的应用前景. 主要综述杯芳烃衍生物通过氢键、金属诱导配位、π-π作用、疏水作用等非共价键弱相互作用力在溶液状态、固态和界面的分子自组装方面的研究进展.     

锂盐阴离子和不同侧基的15-冠-5系冠醚对锂盐/冠醚固态配合物远红外位移的影响

按文献的方法研究了锂盐阴离子和不同侧基的15-冠-5系冠醚对四种锂盐/冠醚固态配合物远红外位移的影响.     

基于二苯并24-冠-8桥联双柱[5]芳烃的线性和网状超分子聚合物

设计合成了一种二苯并24-冠-8桥联双柱[5]芳烃杂交主体1.利用含有2个5-(1,2,3-1H-三氮唑基)戊腈(TAPN)中性键合位点的双主题客体2与主体1中的柱[5]芳烃空腔的强络合构筑了AA/BB型的线性超分子聚合物.进而利用桥链冠醚部分与双主题二级铵盐客体3主客体包结自组装制备了三组分网状的超分子聚合物.通过对线性和网状聚合物进行~1H NMR、黏度、DOSY、SEM等表征,结果表明超分子自组装体的形成呈现浓度依赖性,其线型超分子聚合物在氯仿/丙酮中(V∶V=4∶1)的溶剂中临界聚集浓度(CPC)为28mmol/L.此研究设计了一种利用多次主客体相互作用构建高分子量聚合物的方法,为超分子聚合物的发展开辟了一条新的途径.     

两种臂式荧光氮杂冠醚化学传感器

合成了萘基臂式苯并氮杂15-冠-5（3）和5-氯喹啉基臂式苯并氮杂15-冠-5（4）两种荧光化学传感器,由元素分析、NMR等进行了结构表征;在乙醇溶剂中采用紫外光谱和荧光光谱法分别研究了冠醚3和4对金属离子K＋,Ca2＋,Mg2＋,Pb2＋,Co2＋,Ni2＋,Mn2＋,Cu2＋,Zn2＋,Cd2＋和Hg2＋的选择性传...     

基于非共价键作用的二嵌段共聚物/均聚物超分子体系的自组装行为

采用实空间求解的自洽场理论,研究了两亲性二嵌段共聚物(AB)/均聚物(C)超分子体系在溶液中的自组装行为,其中B疏水嵌段的自由末端与C均聚物的一个末端形成可逆的非共价键.在稀溶液中,AB/C超分子聚合物体系通过自组装形成了一系列不同形貌的胶束,如核-壳-冠的三层胶束和蠕虫状胶束等.研究发现,胶束形貌受到非共价键强度和初...     

咔唑衍生物作为引发剂的研究——Ⅱ.N-取代咔唑的合成及其引发甲基丙烯酸甲酯聚合的研究

用不同的方法合成了八种N-取代咔唑。测定了它们的红外光谱和核磁共振波谱。记录了各咔唑衍生物在CCl_4中不同光照时间的紫外-可见光谱。比较了各种咔唑衍生物单组份或与CCl_4组成的双组分体系对甲基丙烯酸甲酯光引发聚合活性。当N-烯丙基咔唑作为引发剂时,它参加了与甲基丙烯酸甲酯的共聚合反应。     

二芳基大环冠醚共轭8-羟基喹啉的合成及光致发光性质

设计并合成了两种新型二芳基大环冠醚共轭8-羟基喹啉衍生物7a和7b及其锌配合物, 通过核磁共振(1H NMR, 13C NMR)、质谱(MS)、红外光谱(FT-IR)和紫外光谱(UV)等对7a和7b进行了结构表征. 初步研究了7a和7b及其锌配合物在溶液中的光致发光性质. 结果表明, 相对于2-甲基-8-羟基喹啉, 化合物7a和7b的荧光光谱向长波方向有明显的移动, 分别在460和467 nm处出现发射峰, 处于蓝光的范围. 配合物8a和8b的荧光发射峰分别为562和665 nm, 属黄光范围, 但荧光强度较弱.     

Synthesis and properties of template-promoted switchable dithienylethenebased macrocycles

Three switchable macrocycles based on photochromic dithienylethene were synthesized under the template of dibenzylammonium hexafluorophosphate. Their structure were well-confirmed by NMR, ESI-MS and X-ray diffraction. Their photochromism indicated that they showed good reversibility in solution. Additionally, the theoretical calculation suggested that photoirradiation can change the cavity of macrocycles.     

新型丁二炔-二酰胺大环化合物的合成及与TTF和DNP在溶液中的络合行为

由三甘醇和四甘醇出发,经炔丙基烷基化、Mitsunobu反应和Eglinton偶联反应3步合成了2个含均苯四甲酸二酰亚胺结构单元以及丁二炔结构单元的大环化合物,关环产率分别为81%和85%.大环化合物及中间体的化学结构经核磁共振氢谱、碳谱、低分辨质谱、高分辨质谱或元素分析等确认.通过氘代丙酮中1HNMR实验以及氯仿中紫外滴定实验研究了这类大环化合物与客体分子四硫富瓦烯(TTF)和1,5-二甲氧基萘(DNP)在溶液中的相互作用,结果发现,大环化合物的核磁化学位移及紫外光谱均发生变化.通过得到的主-客体间的络合常数可知,此类新型大环化合物与TTF和DNP之间有一定的络合作用.     

Synthesis and characterization of new biodegradable thermosensitive polyphosphazenes with lactic acid ester and methoxyethoxyethoxy side groups

<正>Two novel biodegradable thermosensitive polyphosphazenes with lactic acid ester and methoxyethoxyethoxy side groups were synthesized via the macromolecular substitution reactions of poly(dichlorophosphazene) with the sodium salt of lactic acid ester and sodium methoxyethoxyethoxide.Their structures were confirmed by ~(31)p NMR,~1H NMR,~(13)C NMR,IR,DSC,and elemental analysis.The lower critical solution temperature(LCST) behavior in water and in vitro degradation property of the polymers was investigated.The results indicated that two polymers showed LCST phase transition over a range of concentrations from 0.13 to 15 wt%and pH-sensitive degradation properties.     

Assembly of alpha-helical peptide coatings on hydrophobic surfaces

The adsorption or covalent attachment of biological macromolecules onto polymer materials to improve their biocompatibility has been pursued using a variety of approaches, but key to understanding their efficacy is the verification of the structure and dynamics of the immobilized biomolecules. Here we present data on peptides designed to adsorb from aqueous solutions onto highly porous hydrophobic surfaces with specific helical secondary structures. Small linear peptides composed of alternating leucine and lysine residues were synthesized, and their adsorption onto porous polystyrene surfaces was studied using a combination of solid-state NMR techniques. Using conventional solid-state NMR experiments and newly developed double-quantum techniques, their helical structure was verified. Large-amplitude dynamics on the NMR time scale were not observed, suggesting irreversible adsorption of the peptides. Their association, adsorption, and structure were examined as a function of helix length and sequence periodicity, and it was found that, at higher solution concentrations, peptides as short as seven amino acids adsorb with defined secondary structures. Two-dimensional double-quantum experiments using (13)C-enriched peptide sequences allow high-resolution determination of secondary structure in heterogeneous environments where the peptides are a minor component of the material. These results shed light on how polymeric surfaces may be surface-modified by structured peptides and demonstrate the level of molecular structural and dynamic information solid-state NMR can provide.     

An Explosive Organic／Inorganic Hybrid： Synthesis and Thermal Property of Octa （2,4-dinitrophenyl） silsesquioxane

Octaphenylsilsesquioxane (OPhS) was prepared by a modifying method and a new core-shell nanocomposite, octa(2,4-dinitrophenyt)sitsesquioxane, [(R2PhSiO1.5)8, R=-NO2, ODNPhS], was synthesized by nitration of OPhS in a mixed acid solution of nitric and sulfuric acids at about 60℃. Their molecular structures were determined by DRIFTS, ^1H NMR, ^13C NMR spectra analysis. The thermal analysis shows that ODNPhS is an explosive that detonates at about 420℃.     

Two distinct conformers of the cyclic heptapeptide phakellistatin 2 isolated from the fijian marine sponge stylotellaaurantium

The isolation, structure determination, and solution conformation of two conformers of the cyclic heptapeptide phakellistatin 2 (cyclo-[Phe1-cis-Pro2-Ile3-Ile4-cis-Pro5-Tyr6-cis-Pro7]) isolated from the Fijian marine sponge Stylotella aurantium are reported. The conformers can be isolated separately by HPLC and are stable in methanol solution over a period of weeks as determined by NMR. Their NMR spectra and mass spectral fragmentation patterns differ significantly. Their solution conformations were determined by NOE-restrained molecular dynamics calculations and indicated that the two conformers had different folds, hydrogen bonding patterns, and solvent accessible surfaces. These factors may contribute to the independent stability of the two conformers, and may explain the variable biological activity previously reported for phakellistatin 2.     

Costa型长链烷基钴化合物的合成、表征及其与β-环糊精的作用

烷基钴Costa型化合物是一种以N,N‘－双（2,3－丁二酮－2－亚胺－3肟）丙二胺为平面配体[简称（DO）（DOH)pn]的有机钴化合物,与烷基钴肟和Schiff碱类烷基钴辅酶B12模型化合物比较,它有较好的水溶性,更接近生物体系,因而是一类重要的模型化合物^[1],近来,模拟辅酶B12在与酶相似的疏水环境中的结构和性质的全酶模型已成为研究的热点。     

主链含茜草双酯亚结构单元的聚磷酸酯的合成,降解及释药性能研究

通过茜草双酯与磷酰二氯的溶液缩聚合成了８种主链含茜草双酯亚结构单元的聚磷酸酯，并以元素分析、核磁共振氢谱和红外光谱确证了它们的结构。测定了它们的数均分子量。研究了其体外降解性能，并用高效液相色谱跟踪５－氟尿嘧啶从部分聚合物基质片中的释放行为。