受体-给体-受体型双马来酰亚胺衍生物的合成及其荧光行为

对于含有给电子生色团的丙烯酰类单体和含有受电子生色团的乙烯氧基类单体的荧光行为以及光敏和光引发聚合行为 ,我们进行了长期系列的研究 [1～ 4 ] .含有给电子生色团的丙烯酰类单体可表示为A(=) - D(* ) 型单体 ,A(=) 表示受电子丙烯酰双键 ,D(* ) 表示给电子生色团 .反之 ,含有受电子生色团的乙烯氧基类单体可表示为 D(=) - A(* ) 型单体 ,D(=) 表示给电子乙烯氧基双键 ,A(* ) 表示受电子生色团 .在相同浓度下 ,这些单体的荧光强度总是远远低于其聚合物或相应饱和模型化合物的荧光强度 .为了区别于众所周知的浓度自猝灭 ,我们称这种…     

N-(2-乙烯氧乙基)-1,8-萘二甲酰亚胺聚合物与共聚物的荧光行为

<正> 我们曾报道过一系列含有给电子生色基团的丙烯酰类单体如甲基丙烯酸二甲氨基苄酯、N-(N′,N′-二甲氨基苯基)丙烯酰胺类、8-丙烯酰氧喹啉类、N-丙烯酰-N′-苯基哌嗪类、N-丙烯酰-N′-嘧啶哌嗪类、N-甲基丙烯酰氧乙基-N-甲基代苯胺等的合成、聚合、引发行为以及它们的聚合物的荧光行为。这些单体结构的共同点在于其双键为缺电子性而生色基团为给电子性,因而在荧光行为上,由于生成激基复合物或电荷转移而发生荧光     

含有给电子生色团的双马来酰亚胺与脂肪二胺的共聚合及其荧光光谱跟踪

我们曾合成了一系列含有给电子生色团的丙烯酰类单体 ,它的给电子本质主要是由氮原子 ,以Ｎ ,Ｎ 二甲基氨基苯基的形式所贡献[1～ 4] ,即 :Ｎ ( 4 Ｎ′,Ｎ′ 二甲氨基苯基 )马来酰亚胺 ,Ｎ ( 4 Ｎ′ ,Ｎ′ 二甲氨基苯基 )丙烯酰胺 ,Ｎ ( 4 Ｎ′ ,Ｎ′ 二甲氨基苯基 )衣康酰胺 ,甲基丙烯酸 (对 4 Ｎ ,Ｎ 二甲氨基 )苄酯 ,这些单体的荧光发射强度总是远远低于相同浓度聚合物的荧光强度 .为了区别所熟知的荧光浓度自猝灭 ,我们称这种现象为结构自猝灭效应 (ＳＳＱＥ) [1～ 5] .具有ＳＳＱＥ的丙烯酰类单体可表示为Ａ( =) Ｄ( ) 型化合物 …     

3-甲基丙烯酰胺基-9-乙基咔唑的合成、聚合及其光化学行为研究

含供电子芳杂环的丙烯酰类功能性单体的合成、聚合及光化学行为一直吸引着人们的兴趣 .原因之一是由于这类单体可用一般的自由基引发剂引发聚合 ,其聚合物表现出包括荧光及光引发行为的光化学性质甚被瞩目[1,2 ] .在以往的工作中发现 ,这类给电子性生色团的丙烯酰类单体在相同生色团浓度下的荧光强度明显低于其聚合物或饱和模型化合物 ,即表现出荧光结构自猝灭效应(ＳＳＱＥ) [3～ 5] .咔唑是一个强给电子性芳香杂环化合物 .虽然文献中已有关于含咔唑生色团的丙烯酰类单体报道 ,但很少涉及其荧光或光敏性质 .近来 ,我们合成了多个含有咔唑生…     

含荧光生色基团烯类单体及其聚合物的光化学行为

近年来关于电荷转移现象的研究因理论及应用方面的重要性而备受瞩目。缺电子性丙烯酰类单体可以和给电子性化合物形成激态电葆转移复合物进而引发光聚合。我们合成了一系列同一分子中既含有给电子性荧光生色团又含缺电子性双键的烯类单体,发现这类单体在相同生色团浓度下的荧光强度均无穷氏人相应的聚合物的荧光强度。我们将这咎现象称为荧光结构自猝灭效应（ＳＳＱＥ）,以区别于众所周知的浓度自猝灭现象。对于电子状态与之相反的     

含胺基功能性单体的聚合研究——ⅩⅦ.N-(4-二甲氨基苯基)马来酰亚胺的聚合及其光化学行为

关于在同一分子中既含有给电子生色基团又含有受电子碳碳双键基的单体的合成、聚合及它们的光化学行为,我们所报道过的多是一元不饱和羧酸的衍生物。本文报道含有给电子生色基因的1,2-不饱和二元羧酸类单体N-(4-二甲氨基苯基)马来酰亚胺(DMAPMI)的合成、聚合及其光化学行为。     

含吩噻嗪氧化物的N-丙烯酰基吩噻嗪氧化物的合成及其荧光行为

含吩噻嗪氧化物的Ｎ 丙烯酰基吩噻嗪氧化物的合成及其荧光行为刘向前杜福胜李子臣李福绵（北京大学化学与分子工程学院北京１００８７１）关键词Ｎ 丙烯酰基吩噻嗪氧化物，荧光光谱，荧光结构自猝灭我们曾报道过含给电子性生色基团的丙烯酰类单体及其聚合物的荧光行为...     

8-羟基喹啉的丙烯酸酯及其聚合物的荧光光谱研究

在同一分子中既含有电子给体基团,又含有电子受体基团的单体,如甲基丙烯酸二甲氨基苄酯(DMABMA),N-(4-N′,N′-二甲氨基苯基)代丙烯酰胺(DMAPAA)及其聚合物的荧光光谱颇为有趣。     

N-甲基丙烯酰-N′-嘧啶基哌嗪及其聚合物敏化的丙烯腈光聚合

我们曾报道过同一分子中含有给电子生色基团和电子受体基团的一类功能性单体,如甲基丙烯酸-4-N,N-二甲氨基苄酯(DMABMA),N-(4-N′,N′-二甲氨基苯基代丙烯酰胺,N-(4-N′、N′)-二甲氨基苯基代甲基丙烯酰胺(DMAPMA),8-丙烯酰氧喹啉(AQ),N-丙烯酰-N′-苯基哌嗪(APP)的合成、聚合以及单独或与过氧化二酰构成氧化还原体系以引发烯类单体的聚合研究。N-甲基丙烯酰-N′-嘧啶基哌嗪(MPMP)     

几种β-二酮化合物互变异构体的光谱性质研究

合成了5种不同结构的β-二酮化合物,采用电喷雾质谱、紫外光谱、红外光谱和核磁共振法对其结构进行表征,并讨论了它们的酮式-烯醇式互变异构现象.结果表明,β-二酮分子内酮式-烯醇式的互变异构平衡明显受取代基影响,它们的酮式-烯醇式互变异构体含量完全不同.在固态和CDCl3溶液中,其中2种β-二酮化合物(a1,a2)中主要以烯醇形式存在,仅含有少量的酮式结构;而2种α-取代β-二酮(b1,b2)由于烯醇异构体的空间位阻效应,不能以分子内氢键形成烯醇六元环,全部以酮式结构形式存在;另外,由于强吸电子基团-CF3的作用,使得β-二酮(c)全部以烯醇形式存在.     

220-MHz NMR spectra of acrylic monomer–2-substituted 1,3-diolefin alternating copolymers

An investigation by 220-MHz NMR spectroscopy was carried out on the alternating copolymers of acrylic monomer with 2-substituted 1,3-diolefin. The chain structures were determined. The acrylic monomers used were methyl methacrylate (MMA), acrylonitrile (AN), and methacrylonitrile (MAN); isoprene (IP) and chloroprene (CLP) were the 1,3-diolefins. In the MAN–IP alternating copolymer, the 1-position methylene protons of IP showed an AB quartet peak, confirming the α-1 linkage structure. Similarly, in the MMA–CLP and AN–CLP copolymers, the 1-position methylene protons of CLP showed and AB quartet and an ABX pattern, respectively, confirming the α-1 linkage structure in both these cases also. The α-1 linkage structure was also revealed by the decoupling technique in the MAN–CLP alternating copolymer. The AN–IP and MMA–IP alternating copolymers also possess a bond between the α-position of the acrylic monomer and the 1-position of IP. The monomeric units in the alternating copolymers of acrylic monomers with 2-substituted 1,3-diolefins were generally linked at the α-position of acrylic monomer and the 1-position of 1,3-diolefin. On the other hand, in the Diels-Alder adducts of acrylic monomer with 2-substituted 1,3-diolefin, the reaction takes place between the α-position of acrylic monomer and the 4-position of 1,3-diolefin. The regioselectivity of the alternating copolymers and the Diels-Alder adducts is quite compatible with the expectations from molecular orbital theory.     

Y型三苯胺生色分子的二阶极化率

通过Knoevenagel反应合成了3个Y型三苯胺生色分子N,N-二{4-[2-(2-苯并噻唑基)乙烯基]苯基}苯胺(BBtVPA)、N,N-二{4-[1-(2-苯并噻唑基)-1,3-丁二烯-4-基]苯基}苯胺(BBtBPA)和N,N-二{4-[1-(2-二氰基甲叉-3-氰基-5,5-二甲基-2,5-二氢-4-呋喃基)-1,3-丁二烯-4-基]苯基}苯胺(BCfBPA), 以及4个一维偶极分子4-[2-(2-苯丙噻唑基)乙烯基]-N,N-二苯基苯胺(BtVPA)、1-(2-苯并噻唑基)-4-[4-(N,N-二苯基)氨基]苯基-1,3-丁二烯(BtAPB)、1-[(2-二氰基甲叉-3-氰基-5,5-二甲基-2,5-二氢)-4-呋喃基]-4-[4-(N,N-二苯基氨基)]苯基-1,3-丁二烯(CfAPB)和4-[2-(2-二氰基甲叉-3-氰基-5,5-二甲基-2,5-二氢呋喃-4-基)乙烯基]-N,N-二苯基苯胺(CfVPA). 测定了生色分子的紫外吸收和荧光性质, 在二氯甲烷中, Y型分子BBtVPA, BBtBPA和BCfBPA的最大吸收波长分别为425, 443和613 nm, 比偶极分子红移了约30 nm, Y型分子BBtVPA和BBtBPA的最大荧光发射峰分别位于516和558 nm, 比偶极分子稍有红移. 根据双能级模型理论, 用溶致变色法测定了生色分子的二阶非线性极化率(β), Y型分子BBtVPA, BBtBPA和BCfBPA的β0分别为40×10-30, 64×10-30和238×10-30 esu, 比相应的偶极分子分别提高了0.9~2.8倍. 结果表明, 提高吸电子基团强度, 增大共轭体系有助于获得更大的β值.     

抗抑郁化合物SIPI5358与环糊精形成的非共价复合物

用电喷雾电离质谱(ESI-MS)和串级质谱(MS/MS),并结合紫外光谱、荧光光谱等方法,研究一种芳烷醇哌嗪类抗抑郁化合物SIPI5358与α-、β-、γ-环糊精(CD)制备得到的非共价复合物.质谱分析结果显示,SIPI5358分子可以和α-CD生成配合比为1∶1的非共价复合物,而与β-、γ-CD生成不同配合比的非共价复合物.串级质谱的结果进一步验证β-CD与SIPI5358非共价复合物的组成.用紫外光谱和荧光光谱实验对液相中非共价复合物的形成进行了辅助研究,结果均再次验证了非共价复合物的生成.荧光光谱实验测得SIPI5358与β-CD反应的生成常数Kf=3.45×103 mol.L-1.     

C3 cyclopolymerization. IV.1 Cationic polymerization of 1,3-bis(4-vinylnaphthyl) propane and the polymer structure yielded

The compound 1,3-bis(4-vinylnaphthyl)propane was prepared by a convenient dehydration of 1,3-bis[4-(1-hydroxyethyl)naphthyl]propane. The structure was confirmed by nuclear magnetic resonance (NMR) spectroscopy. The monomer was polymerized by antimony pentachloride, tin tetrachloride, titanium tetrachloride, or boron trifluoride etherate at 0°C in toluene, 1,2-dichloroethane, or a mixed solvent of 1,2-dichloroethane and nitromethane. Most of runs except for antimony pentachloride–catalyzed ones gave mainly benzene-soluble polymers. The structures of the polymers were studied by several spectroscopic methods. Comparison of NMR and fluorescence spectroscopic data of the polymers with those of syn-and anti-[3.3](1,4)napthalenophane was especially valuable in leading to the conclusion that they were cyclopolymers containing predominantly syn-[3.3]-(1,4)naphthalenophane units in the main chain.     

Functionality and structure of polymers. I. Photoreaction and fluorescence of polyesters having pendant anthryl groups

Various polyesters having pendant (9-anthryl)methyl groups were prepared from 2-(9-anthryl)methylpropane-1,3-diol and the esters or chlorides of dicarboxylic acids. These polyesters are poly[2-(9-anthryl)-methylpropane-1,3-diyl-oxy-(9-anthryl)methylmalonyl-oxy](PA-1A), poly-[2-9-anthrylmethylpropane-1,3-diyl-oxysuccinyloxy](PA-2), poly-[2-9-anthrylmethylpropane-1,3-diyl-oxyadipyloxy](PA-4), poly[2-(9-anthryl)methylpropane-1,3-diyl-oxysebacyloxy] (PA-8), poly[2-(9-anthryl)methylpropane-1,3-diyl-oxy-(1-naphthyl)methylmalonyloxy](PA-1N), and poly[2-(9-anthryl)methylpropane-1,3-diyl-oxyterephthaloyloxy](PA-Ph). Although the absorption spectrum of the anthryl group is not influenced by the change in the environment in which the anthryl group is located, the fluorescence spectra show characteristic change reflecting the environment around the chromophore. Dimer, aggregates, or excimer fluorescence of anthryl groups and energy transfer from naphthyl to anthryl groups for PA-1N were discussed. The rates of photodimerization of anthryl groups determined spectroscopically in dilute solutions for these polyesters and their monomer model compound(1,3-diacetoxy-2(9-anthryl)methylpropane) (MA), were in the following order; PA-8 > PA-4 > PA-1A > PA-2 > PA-Ph > MA. The effects of polymer structure on the photoreaction were discussed on the basis of information on molecular interactions obtained by fluorescence spectroscopy. The fraction of intramolecular cyclization was estimated from dependence of the rate of photoreaction on the concentration of the polyesters. When anthryl groups are linked by a long, flexible polymethylene chain (PA-8), intramolecular process predominates whereas intermolecular dimerization proceeds almost exclusively for a rodlike molecule(PA-Ph). These results are discussed from the viewpoint of the structure–functionality relationship in polymeric systems.     

大粒车前子多糖组分PLP-1的结构表征

研究了由大粒车前子多糖分离纯化所得组分PLP-1的一级精细结构特征. 通过单糖组成分析、部分酸水解及甲基化分析,并结合NMR,GC和GC-MS等技术测定了PLP-1的一级结构. 结果表明,PLP-1由Ara（33.98%）,Xyl（58.23%）,Rha（2.36%）,Glc（2.23%）,Gal（2.36%）和Man（0.83%）组成,糖醛酸以GlcA形式存在. PLP-1中主要糖残基有α-T-linked Araf（9.58%）,β-T-linked Xylp（8.71%）,α-1,3-linked Araf（18.22%）,β-1,3-linked Xylp（8.05%）,β-1,4-linked Xylp（5.85%）,β-1,2,4-linked Xylp（16.98%）和β-1,3,4-linked Xylp（27.52%）,GlcA以α-T-linked GlcAp形式存在;此外还有1,2-linked Rhap,T-linked Glcp,1,6-linked Glcp,T-linked Galp,1,3-linked Galp和1,3,6-linked Galp等少量其它残基. 根据所得结果推断出PLP-1可能的一级结构.     

Synthesis, characterization and fluorescence study of new polyacrylates containing stilbene

A new urethane acrylic monomer with stilbene in its structure, trans-4-(2-methacryloyloxyethylcarbamoyloxymethyl)stilbene (SUM), was synthesized to be further free radically copolymerized with methyl methacrylate (MMA). The structures of SUM and the resulting copolymer, trans-4-(2-methacryloyloxyethylcarbamoyloxymethyl)stilbene-co-methyl methacrylate (SUMMA) were characterized by ¹H NMR, UV-vis and FTIR spectroscopy, differential scanning calorimetry (DSC), TGA and fluorescence spectroscopy. From the ¹H NMR spectrum of the formed copolymer, a composition of about 1:2.6 (SUM/MMA) was determined. The photochemical behavior of the stilbene moieties in polymer was investigated in solution (DMF) and in film state comparatively to that of SUM, following the decreasing under UV irradiation of the π-π∗ absorption band characteristic to the trans-isomer in the UV spectra. Morphologic changes in the surface of the polymeric film during the photoisomerization were visualized by means of atomic force microscopy (AFM) and it is proposed that the new formed cone-shaped structures from the irradiated surface to be attributed to J-aggregates. Analysis of fluorescence shows that the stilbene derivatives showed both monomer emission at 358 (SUM) and 357 nm (SUMMA), and excimer (aggregate) emission at 391 and 412 nm (SUM), and at 374 and 398 nm (SUMMA) in solution. Quenching of the active species (SUMMA) by aliphatic amines shows that this process involves an electron transfer from the ground-state amine to excited stilbene, more efficiently being triethylamine.     

Adduct Formation Between γ-Cyclodextrin and the Bifluorophore 1,3-Bis(1-pyrenyl)propane

The complexation of the bifluorophore 1,3-bis(pyrenyl)propane with γ-cyclodextrin in water has been studied by means of steady state and time-resolved fluorescence spectroscopy. It was found that in the association with γ-cyclodextrin the propane chain of 1,3-bis(pyrenyl)propane folds and the two pyrene units enter the same cyclodextrin cavity where they form weakly bound ground state dimers, which upon excitation emit excimer fluorescence. In addition to this 1:1 excimer emitting complex, two more complexes were detected, which emit monomer pyrene fluorescence. One has 1:1 stoichiometry, i.e. isomeric to the previous complex, and the other, with 2:1 stoichiometry, is comprised of two γ-cyclodextrin units and one 1,3-bis(pyrenyl)propane.     

一种蓝光单体的合成及其荧光性能研究

吡唑啉衍生物在生物医药[1,2]应用的领域非常广泛.吡唑啉还是一种优质的发光材料[3],其发射波长位于450nm左右,具有很高的荧光量子效率,且发光波长窄,色纯度好,是一种纯正的蓝光.当吡唑啉环3位引入给电子基时,化合物则具有很高的荧光量子产率,可制得具有高热稳定性的空穴传输蓝光发光材料[4-6]和荧光探针[7].它还可以将吸收的不可见的紫外光转变为蓝色的可见光反射出来,从而增加了光线的反射率,使被其处理过的物体白度和光泽提高,所以吡唑啉又被做为荧光增白剂和荧光染料[8,9]进行广泛地应用.     

Amino-imino tautomerization reaction of the 4-aminopyrimidine/acetic acid system

The amino-imino tautomerization of the 4-aminopyrimidine (4APM)/acetic acid (AcOH) system through dual hydrogen bonding in n-hexane at room temperature was investigated using UV absorption and fluorescence spectroscopies, fluorescence time-profile measurements, and molecular orbital calculations, with those of the imino-model compound of 3-methyl-4(1H)-pyrimidinimine (3M4PMI). From the experimental results, it was confirmed that the imino-tautomer was formed in the first excited singlet state (S1) state through the double-proton transfer of the dual hydrogen-bonded complex of 4APM with AcOH. The fluorescences of the free 4APM monomer (band maximum at 353nm), imino-tautomer (at 414nm), and 3M4PMI monomer (at 437nm) exhibit the single-exponential decays of 98, 73, and 19ps time constants, respectively. The shorter decay time of the imino-tautomer fluorescence compared with the free monomer one is suggestive of the low activation energy process in the S1 state. From the result of the shortest decay time of the 3M4PMI fluorescence, it can be deduced that 3M4PMI has a non-planar structure in the S1 state. The theoretical calculations on the S0 and S1 state double-proton transfer for the 4APM/AcOH dual hydrogen-bonded system were performed with the use of formic acid (FoOH) in place of AcOH for the sake of simplicity. Only one peak of transition state was resolved in the S0 and S1 states. The energy barrier for the S1 state double-proton transfer of the 4APM/FoOH complex-->3H-4(1H)-pyrimidinimine/FoOH tautomer was estimated to be approximately 2kJmol(-1) using the CIS/6-31G(d) methods. On the other hand, the energy barrier for the S0 state reverse proton transfer of the 3H-4(1H)-pyrimidinimine/FoOH tautomer-->4APM/FoOH complex was estimated to be almost zero kJmol(-1) at B3LYP/6-31G(d) level.