新型苝酰亚胺衍生物的合成及其光学性能

以3,4,9,10-苝四酸二酐为原料,设计并合成了三个新型的苝酰亚胺衍生物———N,N’-二(1-戊基己基)-3,4,9,10-苝四羧酸二酰亚胺,N,N’-二(1-戊基己基)-1,6,7,12-四(对叔丁基苯氧基)-3,4,9,10-苝四羧酸二酰亚胺和N,N’-二(4-六氟异丙醇基苯基)-1,6,7,12-四(对叔丁基苯氧基)-3,4,9,10-苝四羧酸二酰亚胺,其结构经1H NMR和MS表征。用UV-Vis和荧光光谱研究了他们的光学性质。     

含可聚合基团的萘酰亚胺衍生物的合成

以4-溴-1,8-萘酐和4-硝基-1,78-萘酐为起始原料,与各种芳胺经亚胺化,再与脂肪胺经取代反应,最后与丙烯酰氯经酯化得到一系列具有强烈荧光的含丙烯酰氧乙基氨基的1,8-萘酰亚胺衍生物,它们可作为一种聚合荧光色素的单体。     

新型萘酰亚胺衍生物的合成

N-(N’,N’-二甲基氨基乙基)-4-硝基-1,8-萘酰亚胺和2,3-二甲基苯并噻唑碘化盐在痕量水存在下经亲核取代反应合成了一个新型的萘酰亚胺衍生物——N-(N’,N’-二甲基氨基乙基)-4-[2-(2,3-二氢-2,3-二甲基苯并噻唑)氧基]-1,8-萘酰亚胺,其结构经1H NMR,13C NMR和ESI-MS表征。并对反应机理进行了初步研究。     

取代基对苝酰亚胺衍生物气敏传感性能的影响

制备了两类酰胺位置含有吸电子基团的苝酰亚胺衍生物N,N′-双(三氟乙基)-1,7-二溴-3,4,9,10-苝二酰亚胺(PTCDI-3F)和N,N′-双(七氟丁基)-1,7-二溴-3,4,9,10-苝二酰亚胺(PTCDI-7F),并测定了其气敏传感性能.结果表明,两类苝酰亚胺衍生物在水合肼气氛中(10ppm)的灵敏度变化值基本相同、电阻均降低约4个数量级.其原因在于两者具有相同的最低空轨道能级.这表明酰胺位取代基对苝酰亚胺衍生物气敏传感性能的影响较小.     

两种新型丁二炔衍生物的合成

以3,5-二溴-1-｛3-（十二烷氧基）-2-［（十二烷氧基）甲基］丙氧基｝苯和2-甲基-3-丁炔-2-醇为原料,经选择性Sonogashira偶联反应,Sonogashira偶联反应和去硅保护基反应制得中间体--3-乙炔基-5-（3-甲基-3-羟基)-丁炔基-1-（3-十二烷氧基）-2-｛［（十二烷氧基）甲基］丙氧基｝苯（6）; 6经改良的Glaser偶联反应(CuI为催化剂,Et₃N为溶剂)合成了一个新型的丁二炔衍生物（1）。 6与2,2′-［（2,5-二碘-1,4-亚苯基）双（氧基）］双（四氢-2H-吡喃）经Sonogashira偶联,脱 THP保护基和改良的Glaser偶联反应合成了一个新型的丁二炔衍生物（2）。中间体,1和2的结构经¹H NMR, ¹³C NMR和MALDI-TOF-MS表征。     

新型萘酰亚胺衍生物的合成及抗肿瘤活性评价

本文合成了三种新的萘酰亚胺衍生物,并对其体外抗肿瘤活性进行了评价.初步实验结果表明,以芳基修饰氨萘菲特芳环上氨基所得化合物体外活性不如阳性对照氨萘菲特.而利用1,4-丁二醇修饰4-溴-1,8-萘酐芳环上溴原子得到的化合物3与阳性对照及其它两种衍生物相比对肝癌细胞HepG2具有较低的IC_(50)值.     

可聚合1,8-萘酰亚胺衍生物掺杂聚硅氧烷复合材料的合成及荧光特性

合成了3种可聚合的1,8-萘酰亚胺衍生物, 并研究了其在二甲基亚砜(DMSO)溶液中的光物理性质. 这些化合物表现出的光物理性质与其电子环境有关. 通过溶胶-凝胶法制备了可聚合1,8-萘酰亚胺衍生物与硅氧烷的共聚物. 尽管3种萘酰亚胺衍生物C-4位的取代基不同, 但在3-氨丙基三乙氧基硅烷(APTES)固凝胶中摩尔分数为0.06%时荧光强度均最大. 利用 ²⁹Si MAS NMR对合成材料进行了表征, 结果表明, 硅氧烷的缩聚程度影响材料的荧光强度, 说明材料中荧光单元的分子运动对材料的荧光性能有重要影响.     

铁磁性高分子——聚丁二炔衍生物的合成与磁性研究

本文报道了三种类型丁二炔的合成:R_1-C≡C-C≡C-R_2,a:R_1=R_2=自由基;b:R_1≠R_2 R_1或R_2为自由基;c:R_1=R_1≠自由基.利用热聚合方法制得三种类型的聚丁二炔,并对它们的磁行为进行了研究,对聚丁二炔衍生物的磁性来源进行了讨论,证明了聚丁二炔衍生物中单独全共轭链自旋体系和单独的自由基侧链自旋体系均不产生铁磁性,其磁性来源于聚丁二炔衍生物中氮氧自由基和共轭主链的共同作用.     

不同氟取代基对苝酰亚胺电子迁移率的影响

利用空间电荷限制电流(SCLC)法测试了二种氟代苝酰亚胺的电子迁移率, 一种是N,N'-二(五氟代苯基)-3,4,9,10-苝四羧基二酰亚胺(1), 另一种是N,N'-二(1,1-二氢十五氟代辛基)-3,4,9,10-苝四羧基二酰亚胺(2). 结果发现, 化合物2的电子迁移率要比1高1～2个数量级. UV-Vis, XRD, SEM和AFM等表征手段证明, 这一现象可以用不同的氟取代基导致不同的聚集态结构来解释: 对于化合物1而言, 苯环平面与苝环平面之间存在大的夹角, 破坏了苝酰亚胺分子的平面性, 再加上刚性的氟代苯环大的空间位阻作用, 化合物1分子无法依靠相邻苝环之间的重叠排列而结晶, 只能无序堆积形成非晶膜; 与之相反, 在化合物2分子中苝环上的端基是柔性的锯齿状氟代烷基链, 空间位阻小, 化合物2分子能通过相邻苝环之间相互接近而形成的π-π偶合作用而结晶, 因此有利于电子在苝酰亚胺分子间的跳跃传输.     

苝酰亚胺衍生物荧光探针的制备及对金属离子的识别

苝酰亚胺衍生物(perlenediimides derivatives,PDIs)作为一类性能优异的新型光电材料,由于其良好的光电性能和强的化学可修饰性,使其在荧光探针方面有着良好的应用前景。以提高苝酰亚胺衍生物溶解性能、改善选择性能为研究切入点,以四氯苝酐为原料,在主链引入供电子基吡啶-2-甲氨基,制备苝酰亚胺衍生物N,N-二(吡啶-2-甲基)-1,6,7,12-四氯-3,4:9,10-苝二酰亚胺(PTCDI-ABD),并对其与Pb~(2+)、Cu~(2+)、Mg~(2+)、Ni~(2+)、Zn~(2+)、K~+、Na~+等金属离子络合后的荧光性能进行详细研究,确定特征金属离子,准确实现金属离子识别。研究证明该化合物分子结构的优化增加了其在空气中的稳定性,与金属离子络合后(即使在较低浓度0.1×10~(-5) mol·L~(-1)),吸收光谱发生蓝移,随着时间的延长,Cu~(2+)的存在导致荧光淬灭。研究显示该化合物是一个很好的Cu~(2+)荧光探针,准确度高、灵敏度强、选择性好、操作简便,容易进行大规模生产和标准化控制。     

Ultrasonic Assisted Synthesis of Naphthalene Substituted Schiff Base Derivatives and Their Antioxidant Activity Studies

New Schiff base derivatives, 2,2′‐[naphthalene‐2,7‐diylbis(oxy)]bis[N′‐substituted acetohydrazide] ( 4a‐m ) were synthesized by the acid catalyzed condensation of aryl/hetero aromatic aldehydes with 2,2′‐ [naphthalene‐2,7‐diylbis(oxy)]diacetohydrazide ( 3 ) under reflux temperature and ultrasonic irradiation. These Schiff base derivatives were confirmed through spectral characterization using IR, ¹H NMR, ¹³C NMR and mass spectra. All the synthesized compounds were screened for their antioxidant activity using DPPH free radical scavenging method.     

Changes in Electron Structure of the Triple Bond in Substituted Acetylene and Diacetylene Derivatives

The substituent effect is usually considered by means of various Hammett-like substituent constants and is most often related to aromatic systems. Unlike this, we present results of our research on the influence of 27 substituents spanning a wide range of electronic properties, from strongly electron-withdrawing to strongly electron-donating, on the electron structure of X-substituted acetylenes and diacetylenes – thus the systems which until now have practically not been subject of any deeper studies. It is shown that the interaction through triple bond(s) is associated with a significant advantage of resonance effects and that the substituent effect transmitted by the C≡C−C≡C unit is about half of that transmitted by the C≡C unit alone. Substituent X mainly affects the closest carbon atom by means of proximity effect, hence changes of charge on this atom do not follow any substituent constants. The effect on further carbon atoms is much smaller. The presence of the C≡C−C≡C unit withdraws more charge from X than a triple bond alone, and hinders communication between X and the terminal H atom. Comparison of substituent effects to those present in X-substituted benzene derivatives shows that the electronic properties of the terminal hydrogen atom in acetylenes and diacetylenes are most similar to the electronic properties of ortho and para hydrogen atoms in X-substituted benzene derivatives.     

含糖聚合物可控合成研究进展

活性聚合技术的进步,使设计合成结构可控的含糖聚合物成为可能.本文介绍了阴离子聚合、阳离子聚合、原子转移自由基聚合、可逆加成断裂链转移聚合、硝基氧介导聚合、开环聚合和开环易位聚合等一系列可控/"活性"聚合技术在合成含糖聚合物中的应用,并对这一领域所取得的研究进展及现状进行了综述.     

Perfluorophenyl–Phenyl Interactions in the Crystallization and Topochemical Polymerization of Triacetylene Monomers

A series of symmetrically and unsymmetrically substituted octa‐2,4,6‐triyne‐1,8‐diol derivatives with benzoyl, 4‐dodecyloxybenzoyl, as well as perfluorobenzoyl substituents were prepared and investigated with respect to their crystal structures and topochemical polymerizability. Single‐crystal structures for several of these triacetylene monomers have been obtained and proved that the perfluorophenyl–phenyl interactions played a decisive role in the molecular packing. As a consequence of the geometric requirements imposed by the perfluorophenyl–phenyl interactions, packing parameters appropriate for a topochemical triacetylene polymerization in the sense of either a 1,6‐ or a 1,4‐polyaddition along different crystallographic axes were observed in two cases, and UV irradiation led to successful polymerization. Raman as well as solid‐state ¹³C NMR spectra of the obtained polymers revealed that the polymerization had predominantly proceeded in the form of a 1,4‐polyaddition.     

Synthesis and properties of novel functional polymers from tetrachlorinated perylene bisimide

Asymmetric tetrachlorinated perylene‐3,4,9,10‐tetracarboxylic acid bisimides (4Cl‐PBI) were prepared in one‐pot by a reaction of tetrachlorinated perylene‐3,4,9,10‐tetracarboxylic acid dianhydride with a mixture of 2‐aminoethanol and dodecanamine or 2‐decyltetradecan‐1‐amine. Then, two 4Cl‐PBI methacrylates bearing one (M1) and two (M2) long alkyl tails were prepared, and a series of functional homopolymers were obtained by subjecting conventional radical polymerization and atom transfer radical polymerization. Furthermore, amphiphilic block copolymers pendent with 4Cl‐PBI units, PEO‐PM1 and PEO‐PM2, were prepared using monomethoxyl PEO bromoisobutyrate as a macroinitiator. Size exclusion chromatography, UV–vis spectroscopy, fluorescence spectroscopy, and cyclic voltammetry have been applied to characterize the polymers obtained. Moreover, the Ullmann reactions between the grafted 4Cl‐PBI units were conducted to form large π units, and the PEO‐PM2 block copolymers gave di‐ or tri‐PBI units in about 30%. Also, self‐assembly of the amphiphilic block copolymers PEO‐PM1 and PEO‐PM2 in water was applied to generate spherical nanoparticles of 4Cl‐PBI. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

螺旋状纳米二茂铁苯甲酰胺化合物的合成及晶体结构

以对-二茂铁苯甲酰氯和1,2-二邻-胺基苯氧乙烷为原料,合成了两个新型的含有二茂铁苯基的酰胺化合物,单晶结构显示,二者均为螺旋状分子。化合物3为三斜晶系,p-1空间群,分子中存在两种N-H…O分子内氢键;位于分子端基C46和C8上的氢原子间的达1.62nm,使得分子框架距离达纳米级。化合物4为正交晶系,Pca21空间群,分子中也存在N-H…O分子内氢键,并且二茂铁和与之相连的苯环的二面角在3.8°到20.8°之间的变化范围。     

取代萘并吡喃的合成和晶体结构研究

以芳醛、丙二腈（或氰乙酸酯）、β－萘酚为原料在六氢吡啶存在下以乙醇为 溶剂一锅合成了取代萘并吡喃，产物的结构通过单晶X射线衍射分析确定。     

取代茚基的茂金属Ti、Zr化合物的合成及其催化乙烯聚合活性

茂金属化合物;烯烃聚合;取代茚基的茂金属Ti、Zr化合物的合成及其催化乙烯聚合活性     

苝四羧酸二酰亚胺衍生物的合成及其性能研究

以苝四羧酸二酐为原料,设计并合成了3个苝四羧酸二酰亚胺类化合物[1,7-二溴-3,4,9,10-苝四酸酐(1), N,N′-二(十二烷基)-1,7-二溴-3,4,9,10-苝四羧酸二酰亚胺(2)和N,N′-二(十二烷基)-1,7-二对叔丁基苯氧基-3,4,9,10-苝四羧酸二酰亚胺(3)],其结构经1H NMR和MS表征.用循环伏安法和热分析法研究了2和3的电化学性质和热学性质.结果表明:2和3的氧化电位分别为931.6 mV, 170.1 mV,还原电位分别为-1 028 mV, -1 941 mV;2和3具有高的分解温度(>300 ℃),有良好的热稳定性.     

Enzymatic Precision Polymerization for Synthesis of Glycosaminoglycans and Their Derivatives

Hyaluronidase (HAase)-catalyzed polymerization was performed to provide synthetic hyaluronan (HA), chondroitin (Ch) and their derivatives. The 2-methyl oxazoline derivatives derived from their repeating disaccharides of N-acetylhyalobiuronate ( 1a ) and N-acetylchondrosine ( 3a ) were effectively polymerized by the enzyme, giving rise to synthetic HA and synthetic Ch in good yields through regio-selective and stereo-controlled ring-opening polyaddition. The oxazoline derivatives of 2-ethyl ( 1b , 3b ), 2-n-propyl ( 1c , 3c ), 2-isopropyl ( 1d , 3d ), 2-phenyl ( 1e , 3e ), 2-vinyl ( 1f , 3f ) and 2-isopropenyl ( 1g ) were synthesized and subjected to the enzymatic reaction. Monomers 1b , 1c , 1f , 3b and 3f were polymerized to corresponding polysaccharides 2b , 2c , 2f , 4b and 4f , all of which are unnatural glycosaminoglycans. Compounds 1d , 3c and 3d were also catalyzed by the enzyme, affording oligomers of 2d , 4c and 4d were produced in trace amounts. Monomers 1e , 1g and 3e were not catalyzed by HAase.