侧链基团对聚合物薄膜瞬态发光性能的影响

采用飞秒激光光谱技术比较研究了两种卟啉侧链聚合物:卟啉丙烯酸酯-苯乙烯共聚物P[(por)A-S]和卟啉铁(Ⅲ)丙烯酸酯-苯乙烯共聚物P[(por)FeA-S]的瞬态发光性能。并采用纳秒激光光谱技术测量了小分子卟啉(TPP)的荧光动力学过程。结果表明:P[(por)FeA-S]具有比P[(por)A-S]快得多的荧光弛豫过程,而P[(por)A-S]的荧光寿命远小于小分子卟啉的荧光寿命。对上述过程进行了分析,P[(por)A-S]的荧光衰变主要来源于聚合物分子链间的相互作用;而P[(por)FeA-S]的荧光衰变除了来源于聚合物分子链间的相互作用外,中央金属离子与配位体之间的电荷转移也对卟啉发色基团的激发态超快无辐射弛豫具有重要的影响,对上述过程的产生机理进行了讨论。     

激子旋转弛豫对低掺杂卟啉侧链聚合物荧光衰变过程的影响

利用激子旋转扩散理论研究了一类低掺杂卟啉侧链聚合物中卟啉侧链基团的旋转对其发光动力学过程的影响.研究表明,卟啉侧链基团的旋转行为是导致激发态无辐射能量弛豫的重要途径.基团旋转越容易,能量弛豫速度越快,这可导致一个快速的荧光衰变动力学过程.在卟啉低掺杂浓度和聚合物分子链间距离较大的情况下,卟啉侧链基团的旋转成为影响荧光寿命和发光效率的主要因素.对实验测得的两种样品的荧光弛豫过程进行了拟合,理论结果与实验结果符合较好. 关键词： 激子旋转弛豫 瞬态荧光 卟啉侧链聚合物     

Study of photooxidation of styrene-butadiene copolymers by surface pressure measurements at the air-water interface

Block and random copolymers of butadiene and styrene as well as polybutadiene and polystyrene homopolymers have been investigated with respect to their monolayer properties and photooxidation behavior. Whereas polystyrene and block copolymers of styrene and butadiene form stable monolayers, polybutadienes and random copolymers do not interact with the aqueous subphase. The monolayer properties of block copolymers with different styrene content indicate that polybutadiene also contributes to the surface pressure. Photo-oxidation of random and block copolymers of styrene and butadiene leads to a significant enhancement in surface pressure of the monolayers due to the generation of groups which can effectively interact with the aqueous surface. FTIR spectral studies show the formation of carbonyl, hydroxyl, and hydroperoxyl groups in the polymers on photooxidation. A comparison of the pressure-area isotherms of random and block copolymers oxidized in solution indicates that there is an energy transfer from butadiene to styrene units in the case of random copolymers, resulting in a protective effect of butadiene units from oxidation. In addition, in the monolayers of oxidized block copolymers, a phase transition occurs which is attributed to the extrusion of polystyrene blocks from the monolayer. The surface pressure-area isotherms and the rates of photooxidation are strongly dependent on the microstructure of polybutadiene as well as on whether oxidation is performed in solution or at the oxygen-water interface.     

Influence of hydrogen bonding on the generation and stabilization of liquid crystalline polyesters,poly(esteramide)s and polyacrylates

Induction and stabilization of liquid crystallinity through hydrogen bonding (HB) are now well-established. Interesting observations made on the influence of HB on LC behaviour of amido diol-based poly(esteramide)s, poly(esteramide)s containing nitro groups and azobenzene mesogen-based polyacrylates will be discussed. The use of amido diol as an important precursor for the synthesis of novel PEAs containing inbuilt di-amide linkage enabled generation of extensive hydrogen bondings between the amide-amide and amide-ester groups which stabilized the mesophase structures of the PEAs. The contributions of hydrogen bonding to the generation and stabilization of mesophase structures were plainly evident from the observation of liquid crystallinity even in PEAs prepared from fully aliphatic amido diols. Replacement of terephthaloyl units by isophthaloyl moiety totally vanquished liquid crystalline phases while biphenylene and naphthalene units did only reduce the transition temperatures as expected. The occurrence of the smectic phases in some of the polymers indicated possibly self-assembly through the formation of hetero intermolecular hydrogen bonded networks. A smectic polymorphism and in addition, a smectic-to-nematic transition, were observed in the monomers and polymers based on 1,4-phenylene[bis-(3-nitroanthranilidic acid)] containing nitro groups. A smectic polymorphism was also observed as a combined effect of hydrogen bonded carboxyl groups and laterally substituted alkyl side chains in the case of azobenzene mesogen containing side chain polyacrylates. It was further shown that the presence of the mesophase enhances the non-linear optical (NLO) response of these polymers.     

Effect of the chiral chain length on structural and phase properties of ferroelectric liquid crystals

Studies of structural and phase properties obtained on several ferroelectric liquid crystalline materials with 2-alkoxypropionate group used as a chiral centre and without any lateral substitution are presented. In dependence on the chiral chain length these compounds exhibit the cholesteric N* phase, the ferroelectric smectic C* and a low-temperature SmX phase. Values of the spontaneous polarization and spontaneous tilt angle have been determined within the whole range of the SmC* phase. A low-temperature SmX phase has been identified as the orthogonal hexatic SmB* phase. The molecular parameters, namely the layer spacing in the SmC* and SmB* phases and the average intermolecular distances (D) between neighbouring parallel molecules in all investigated phases have been determined using the results of the X-ray diffraction obtained on non-oriented samples. The effect of the chiral chain length on mesomorphic, structural and physical properties of the studied ferroelectric liquid crystalline materials is discussed.     

偶氮侧链聚合物液晶的光学性质及其光存储应用

有机聚合物是一类非重要的非线性光学材料，它在光通信和高密度光存储等高技术领域中有良好的应用前景，文章介绍了偶氮侧链聚合物液晶的光学性质及其在光存储领域中的应用。     

Ultrasound-promoted synthesis of 3-trichloromethyl-5-alkyl(aryl)-1,2,4-oxadiazoles

The alternative synthesis of 12 1,2,4-oxadiazoles using ultrasound irradiation from trichloroacetoamidoxime and acyl chlorides is reported. Seven of them are novel compounds. The 3-trichloromethyl-5alkyl(aryl)-1,2,4-oxadiazoles have been synthesised in better yields and shorter reaction times compared to the conventional method. This protocol can be applicable for preparation of 1,2,4-oxadiazoles containing aryl or alkyl groups attached at their C-5 side-chain.     

Order and strain in main-chain smectic liquid-crystalline polymers and elastomers

The layer correlations in main-chain smectic liquid-crystal polymer and elastomer systems have been studied using high-resolution X-ray scattering. In contrast to side-chain smectic polymers, in main-chain systems the polymer chains are oriented parallel to the layer normal. As a result they couple directly to the lamellar structure and any polymer defect is translated into layer distortions. For the homopolymers the resulting X-ray lineshapes are well described by Lorentzians. This is interpreted as an average of algebraically decaying order in domains with dimensions of hundreds of nm and a wide dispersion of sizes. The elastomers show much broader peaks than the correponding polymers. This is attributed to strong non-uniform strain within the finite-size domains due to defects of the layer structure. An erratum to this article is available at .     

Mesomorphic properties of a bent-shaped liquid crystalline monomer

We have prepared a new bent-shaped monomer designed for main chain liquid crystalline polymers. The mesomorphic behaviour of the monomer was fully characterized by DSC, polarizing optical microscopy and electro-optical measurements. Based on X-ray analysis of the monomer, its structural properties were established and a possible molecular arrangement in the mesophases is proposed. A direct comparison of the material shows that an introduction of an isolated double bond can slightly modify the mesomorphic properties of the liquid crystalline monomer in comparison with the alkyl-chain analogous bent-shaped compound studied previously.     

Total synthesis and development of bioactive natural products

The first total synthesis and development of a variety of bioactive natural products have been accomplished by using carbohydrates as a chiral source. In addition, practically useful intermediates have been created, analogs of natural products have been prepared, their structure-activity relationships studied, and the large-scale preparations of medicinally useful compounds established. The key target molecules have been the "Big Four" antibiotics (macrolides, aminoglycosides, beta-lactams and tetracyclines), pyranonaphthoquinone antibiotics, glycosidase inhibitors, and a side-chain of cephem antibiotics.     

F?rster双分子猝灭作用对卟啉侧链聚合物荧光衰变的影响

通过采用时间分辨荧光光谱技术测量了一种卟啉侧链聚合物薄膜：卟啉丙烯酸酯—苯乙烯共聚物poly［porphyrin acrylate-styrene］ (P［(por)A-S］)在高激发密度下的瞬态荧光特性.实验发现,P［(por)A-S］样品的荧光衰减随聚合物分子浓度的增大而加快.利用Frster机制的双分子猝灭理论对其浓度猝灭的原因进行了分析,理论结果与实验结果符合较好.研究表明,在高激发密度的情况下,Frster机制的双分子作用是加快卟啉侧链聚合物初始荧光衰减和降低其发光效率的主要因素. 关键词： 双分子猝灭 Frster机制 瞬态荧光 卟啉侧链聚合物     

偶氮聚合物薄膜的全光极化研究

报告了分散红共聚物膜HMMM-DR1,HMMM-DR19和偶氮侧链聚合物膜PCN6和PCN2的合成和制备, 并以HMMM-DR1和PCN6为代表比较研究了这两种具有不同吸收性质材料的全光极化特性,研究了他们的实时极化和弛豫过程,对他们的全光极化性质作了最基本的表征.研究了倍频光吸收对薄膜光极化效率的影响,讨论了偶氮聚合物材料光诱导二阶非线性极化率的效率和倍频光透射率之间的折衷关系,这对实用化的全光器件的研制是至关重要的.实验确证了在PCN6薄膜中实现了准相位匹配.对厚膜中光诱导二阶非线性极化率的弛豫抑制效应作出解释.     

Spectroscopic studies on conjugated polymers in mesoporous channels: influence of polymer side-chain length

The influence of mesoporous environment on the conjugated polymers was studied by UV-Vis absorption and Photoluminescence spectroscopy. The applied polymers were three novel poly(p-phenylenevinylene) derivatives (DDMA-PPV). These polymers have dibenzothiophen-5,5-dioxide units in their backbones, but are different from each other in the length of alkoxy side-chains. The polymers were incorporated into the mesoporous channels of SBA-15 by sorption from their dilute solutions. The confined polymers exhibited different trends in the shifts of the absorption onsets and the emission peaks depending on the length of the side-chains. The polymer with shorter side-chain showed red-shifts in both the absorption and emission spectra, whereas the polymer with longer side-chain showed blue-shifts. These phenomena were caused by the combined influences from the electronic confinement and the conformation distortion. Moreover, these trends were enhanced when the polymers were loaded in amine-modified SBA-15.     

Theory of microphase separation on side-chain liquid-crystalline polymers with flexible spacers

We model a melt of monodisperse side-chain liquid-crystalline polymers as a melt of comb copolymers in which the side groups are rod-coil diblock copolymers. We consider both excluded-volume and Maier-Saupe interactions. The first acts among any pair of segments while the latter acts only between rods. Using a free-energy functional calculated from this microscopic model, we study the spinodal stability of the isotropic phase against density and orientational fluctuations. The phase diagram obtained in this way predicts nematic and smectic instabilities as well as the existence of microphases or phases with modulated wave vector but without nematic ordering. Such microphases are the result of the competition between the incompatibility among the blocks and the connectivity constraints imposed by the spacer and the backbone. Also the effects of the polymerization degree and structural conformation of the monomeric units on the phase behavior of the side-chain liquid-crystalline polymers are studied.     

Cinchona alkaloid-based polymer-bound phase-transfer catalysts: Efficient enantioselective alkylation of benzophenone imine of glycine esters

Summary Cross-linked polystyrene-bound and poly(ethylene glycol)-bound phase-transfer catalysts as well as homopolymers of cinchona alkaloid derivatives have been synthesised. Both soluble and insoluble polymers have been investigated. The enantioselective alkylation of N-diphenyl methylene glycine t-butyl ester has been successfully carried out in heterogeneous and homogeneous systems. High enantioselectivities (up to 96%) have been obtained. The polymer-bound catalysts have been easily recovered and conditions for efficient recycling have been studied.     

Electro-optical properties of polymer stabilized cholesteric liquid crystal film

Liquid crystals (LCs) and polymers are extensively used in various electro-optical applications.In this paper,normal mode polymer stabilized cholesteric LC film is prepared and studied.The effects of chiral dopant and monomer concentrations on the electro-optical properties,such as contrast ratio,driving voltage,hysteresis width and response time,are investigated.The reasons of electro-optical properties influenced by the concentrations of the materials are discussed.Through the proper material recipe,the electro-optical properties of polymer stabilized cholesteric LC film can be optimized.     

Structural conditions of deformation and fracture of oriented crystalline polymers

Deformation of supermolecular structure elements of oriented crystalline polymers and nucleation of initial submicroscopic cracks induced by stress have been studied by the small-angle x-ray scattering technique. It is shown that the intrafibrillar amorphous interlayers have low strength and high deformability. The rupture of the weakest amorphous interlayers leads to nucleation of initial submicrocracks. The influence of submicrocracks on deformation around such cracks is revealed. The micromechanics of deformation and fracture of polymers is discussed.     

一种新型卟啉侧链聚合物的飞秒荧光动力学

研究了一种新型的卟啉侧链聚合物丙烯腈丙烯酸卟啉酯共聚物{poly[porphyrin acrylate-acrylonitrile](p[(por)A-AN]}的链间和链内的卟啉分子的相互作用对聚合物薄膜发光性质的影响。通过采用飞秒荧光光谱技术测量了p[(por)A-AN]薄膜的荧光动力学过程。测量结果表明:纯p[(por)A-AN]薄膜(~450ps)显示出了比混合物薄膜p[(por)A-AN]/polystyrene(PSE)(~1.3 ns)快得多的荧光弛豫过程。而p[(por)A-AN]/PSE混合物薄膜显示出较纯p[(por)A-AN]薄膜增强的荧光效率。增加p[(por)A-AN]分子内卟啉侧链基团的浓度导致纯p[(por)A-AN]薄膜和p[(por)A-AN]/PSE混合物薄膜的荧光效率的增强和寿命(由近26~36 ps)的增加。分子间和分子内卟啉侧链基团之间的无辐射能量转移和分子内卟啉侧链基团的旋转运动在p[(por)A-AN]的荧光动力学过程中起着重要的作用。     

Quenching of fluorescence of conjugated poly(p-phenylene) polymers by benzil and dimethylaminobenzil molecules

We have studied the mechanisms for quenching of the fluorescence of conjugated poly(p-phenylene) polymers by benzil and dimethylaminobenzil molecules. We have shown that molecules in the diketone series are quenching agents for the fluorescence of the indicated polymers, and can serve as singlet-triplet converters capable of populating the triplet state of the polymer. We have observed that the efficiency of quenching of the fluorescence of the studied polymers depends considerably on the presence of bulky side groups in the polymer or in the activator molecules. Based on analysis of the data obtained, we conclude that in the case of a rigid planar structure for the polymer, a significant contribution to quenching of its fluorescence comes from not only singlet-singlet energy transfer but also charge transfer, leading to formation of intermolecular complexes (exciplexes). __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 73, No. 6, pp. 756–762, November–December, 2006.     

Frustrated smectic liquid crystalline phases in lactic acid derivatives

ABSTRACT

We have prepared and studied a series of compounds with different types of molecular core and lactate unit in the chiral terminal chain. We draw a survey and comparison of their mesomorphic properties with respect to the occurrence of twist grain boundary (TGB) phases. The materials exhibit extremely wide TGBA phase more than 60K broad, unique TGBA-TGBC-SmC*-SmC_A* phase sequence and unique re-entrant TGBA phase below the SmA phase. TGB phases have been induced in binary mixtures of molecules with different molecular shape and chirality (chiral lactic acid derivative and non-chiral hockey-stick mesogen). Unique effect is observed for compounds with TGBA phase, where the applied electric field transforms the planar texture into the homeotropic one, homogeneously dark in crossed polarizers. The process is analogy of the Frederiks transition so far known only for nematics. This effect, changing the bright state to the dark one, is promising for applications.