光致异构全光逻辑门理论与实验研究

基于双光抽运探测模型，利用偶氮苯聚合物光致异构和光致双折射效应，建立了全光逻辑门的理论分析模型，提出了一种新颖的全光逻辑门设计方案.该方案基于输入抽运光和信号光的强度或偏振态，设计了“与”门、“或”门、“异或”门和“异或非”门等基本功能的全光逻辑门.以掺杂分散红1(DR1)的聚甲基丙烯酸甲酯(PMMA)薄膜为样品进行实验，得到了比较好的逻辑门运算实验结果，与理论分析相符合.     

Fluorescent Molecular Logic Gates and Pourbaix Sensors in Polyacrylamide Hydrogels

Polyacrylamide hydrogels formed by free radical polymerisation were formed by entrapping anthracene and 4-amino-1,8-naphthalimide fluorescent logic gates based on photoinduced electron transfer (PET) and/or internal charge transfer (ICT). The non-covalent immobilisation of the molecules in the hydrogels resulted in semi-solid YES, NOT, and AND logic gates. Two molecular AND gates, examples of Pourbaix sensors, were tested in acidic aqueous methanol with ammonium persulfate, a strong oxidant, and displayed greater fluorescence quantum yields than previously reported. The logic hydrogels were exposed to aqueous solutions with chemical inputs, and the fluorescence output response was viewed under 365 nm UV light. All of the molecular logic gates diffuse out of the hydrogels to some extent when placed in solution, particularly those with secondary basic amines. The study exemplifies an effort of taking molecular logic gates from homogeneous solutions into the realm of solid-solution environments. We demonstrate the use of Pourbaix sensors as pE-pH indicators for monitoring oxidative and acidic conditions, notably for excess ammonium persulfate, a reagent used in the polymerisation of SDS-polyacrylamide gels.     

Synthesis and photoinduced isomerization ofansa{·5,·5′-[1,1′-(1-silacyclopent-3-ene-1,1-diyl)bis(indenyl)]} dichlorozirconium The crystal structure of itsmeso form

ansa{·⁵,·⁵′-[1,1′-(1-silacyclopent-3-ene-1,1-diyl)bis(indenyl)]} dichlorozirconium (1a,b) was synthesized. The crystal structure ofmeso-[(1,4-CH₂CH=CHCH₂)Si(C₉H₆)₂ZrCl₂] (1b) was established by X-ray diffraction analysis. Photoinduced interconversion of the racemic (1a) andmeso forms was studied under various conditions. The photostationary state (rac: meso=55∶45) was established rapidly when solutions ofansa-zirconocene were irradiated with visible light. Deceased Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 11, pp. 2351–2356, November, 1998.     

Molecular design of light-sensitive nanodimensional systems

A universal approach to the molecular design of light-sensitive nanodimensional systems with specific characteristics was developed on the basis of unsaturated and macrocyclic compounds. It was possible to construct various nanodimensional systems within the scope of a single class of compound using a limited number of components. The use of photostructural transformations to control complex formation and mechanical movements in molecular devices and machines is discussed. Translated from Teoreticheskaya i éksperimental’naya Khimiya, Vol. 45, No. 1, pp. 1–7, January-February, 2009.     

荧光分子开关的研究进展

荧光分子开关是超分子化学领域的研究热点之一,本文根据开关动作完成的方式对近年来研究的各类荧光分子开关进行了简要的归类总结,并介绍了一些具有特殊功能的荧光分子开关器件.     

利用二氢吡啶光诱导芳香化反应合成3,5-二氰基-2,4,6-三甲基吡啶

3,5-二氰基-2,4,6-三甲基吡啶在新型光电功能材料的合成中有重要的应用价值.本文在CCl₄中光照1,4-二氢-3,5-二氰基-2,4,6-三甲基吡啶,高产率地合成了3,5-二氰基-2,4,6-三甲基吡啶.     

Lattice vibration and photoinduced light scattering in Co-, Cr- and Fe-doped lithium niobate

Raman scattering and photoinduced light scattering in Co-, Cr- and Fe-doped lithium niobate were examined. The A₁(TO) modes appear in E symmetry spectrum of the doped lithium niobate. Their intensities vary with different dopings. In the spectrum of z(yy)x geometry, the properties of the lowest-frequency E(TO) mode of the Cr-doped lithium niobate are different from those of pure, Co- and Fe-doped lithium niobate. The intensity of the A₁(TO) mode at 637cm^-1 I is decreased in doped lithium niobate compared with the pure crystal. We attribute these properties to both the photorefractive effect which is enhanced by dopants and to the different occupation of the doping ions. A light climbing effect was observed in Co- and Cr-doped lithium niobate for the first time. A higher photodamage threshold and quicker light climbing speed were found in Co- and Cr-doped lithium niobate in comparison with the light climbing effect in the Fe-doped lithium niobate. The results from the photoinduced light scattering experiments were compared with those from a Raman spectroscopic study.     

苝四羧酸多联体化合物的合成及其光谱特性研究

本文合成了8个 四羧酸多联体化合物;测定了这些化合物的吸收光谱、荧光光谱。研究了由供电子分子键连的多联体分子的光谱特性及其分子体系内稳态荧光猝灭机理。首次从吸收光谱和荧光光谱上分析和考察了四羧酸多联体化合物分子体系内的光致电子转移反应。     

高分子体系中降冰片二烯的光异构化反应

本文合成了降冰片二烯和咔唑为侧基的甲基丙烯酸酯共聚物,并与仅带有降冰片二烯侧基的聚甲基丙烯酸酯进行了光异构化反应的对比研究。实验结果表明,当入射光波长小于350nm时,两种降冰片二烯聚合物均发生了光异构化反应;当入射光波长大于350nm时,只有共聚物的降冰片二烯侧基能够异构化为相应的四环烷。利用荧光猝灭实验及化学诱导动态核极化(CIDNP)等研究了咔唑的敏化机理,利用三氟乙酸作催化剂实现了四环烷的反向异构化。