光诱导

The structural and photocatalytic properties of TiO〓 as well as surface acidity were greatly improved by sulfation. SO〓〓/TiO〓 solid superacid with Hammett constant Ho less than -12.14 was prepared by treating the TiO〓 with 1.0mol. L〓 sulfuric acid solution and then calcining at 450℃ for 3h. When compared to unmodified TiO〓, the SO〓〓/TiO〓 superacid catalyst exhibited higher anatase content, smaller crystal size, higher specific surface area, centralized pore size distribution, and the blue-shifted band edge of uv-vis adsorption spectra. Furthermore, the SO〓〓/TiO〓 superacid also showed excellent reaction activity and stability for CH〓Br photocatalytic decomposition even under the moist reaction conditions. The apparent quantum efficiency of SO〓〓/TiO〓 was 10 times of that of TiO〓 catalyst for the photocatalytic degradation of bromomethane. Therefore, the SO〓〓/TiO〓 superacid catalyst is promising for practical application in environmental remediation.It was found that both L and B acid sites exist on SO〓〓/TiO〓 photocatalyst while only L acid sites on TiO〓 photocatalyst. On the basis of experimental results, the synergistic model of superacidic centers was proposed for SO〓〓/TiO〓 photocatalyst to explain the photocatalytic behavior and the mechanism of superacidifing effects, assuming that the adjacent L and B acid sites induced by SO〓〓 comprise cooperatively the superacidic center on superacid photocatalyst. The group cooperation of the superacidic center could strengthen the surface acidity, increase surface acid sites and the adsorbtion of O〓, promote separation of photogenerated electron-hole pair, enhance the interfacial transfer of charges and reversibility of water adsorption. Consequently the excellent photocatalytic activity, reaction stability and resistibility to humidity of SO〓〓/TiO〓 superacid photocatalyst may attributed to the group cooperated effect of the superacidic center on the photocatalyst.

研究结果表明：SO〓〓与TiO〓表面的结合为螯合式双配位结构；TiO〓光催化剂表面经H〓SO〓浸渍处理后，提高了表面酸性，改善了催化剂结构和光催化性能，当H〓SO〓浸渍浓度为1.0mol.L〓、烧结温度为450℃时，可制得SO〓〓/TiO〓超强酸催化剂(H〓＜-12.14)，其结构和光催化活性得到明显改善，与TiO〓相比，SO〓〓/TiO〓光催化剂的锐钛矿含量高、晶粒小、BET比表面积大、孔径分布集中、光谱吸收边蓝移，具有优异的光催化氧化活性、稳定性及抗湿性能，光催化降解溴代甲烷的表观量子效率比TiO〓催化剂提高了一个数量级，是一种有实际应用前景的高效光催化剂；由此提出了SO〓〓/TiO〓超强酸催化剂表面集团协同作用的超强酸中心模型，认为在SO〓〓/TiO〓超强酸催化剂表面，由SO〓〓诱导的相邻L酸中心和B酸中心组成了集团协同作用的超强酸中心，其集团协同作用显著地增强了催化剂表面酸性、增大了表面酸量及O〓吸附量、促进了光生电子和空穴的分离及界面电荷转移，具有可逆吸附水的性能，是SO〓〓/TiO〓超强酸催化剂具有优异的光催化氧化活性、很好的活性稳定性及抗湿性能的重要原因。

The apparent quantum efficiency of SO〓〓/TiO〓 was 10 times of that of TiO〓 catalyst for the photocatalytic degradation of bromomethane. Therefore, the SO〓〓/TiO〓 superacid catalyst is promising for practical application in environmental remediation.It was found that both L and B acid sites exist on SO〓〓/TiO〓 photocatalyst while only L acid sites on TiO〓 photocatalyst. On the basis of experimental results, the synergistic model of superacidic centers was proposed for SO〓〓/TiO〓 photocatalyst to explain the photocatalytic behavior and the mechanism of superacidifing effects, assuming that the adjacent L and B acid sites induced by SO〓〓 comprise cooperatively the superacidic center on superacid photocatalyst. The group cooperation of the superacidic center could strengthen the surface acidity, increase surface acid sites and the adsorbtion of O〓, promote separation of photogenerated electron-hole pair, enhance the interfacial transfer of charges and reversibility of water adsorption. Consequently the excellent photocatalytic activity, reaction stability and resistibility to humidity of SO〓〓/TiO〓 superacid photocatalyst may attributed to the group cooperated effect of the superacidic center on the photocatalyst.

研究结果表明：SO〓〓与TiO〓表面的结合为螯合式双配位结构；TiO〓光催化剂表面经H〓SO〓浸渍处理后，提高了表面酸性，改善了催化剂结构和光催化性能，当H〓SO〓浸渍浓度为1.0mol.L〓、烧结温度为450℃时，可制得SO〓〓/TiO〓超强酸催化剂(H〓＜-12.14)，其结构和光催化活性得到明显改善，与TiO〓相比，SO〓〓/TiO〓光催化剂的锐钛矿含量高、晶粒小、BET比表面积大、孔径分布集中、光谱吸收边蓝移，具有优异的光催化氧化活性、稳定性及抗湿性能，光催化降解溴代甲烷的表观量子效率比TiO〓催化剂提高了一个数量级，是一种有实际应用前景的高效光催化剂；由此提出了SO〓〓/TiO〓超强酸催化剂表面集团协同作用的超强酸中心模型，认为在SO〓〓/TiO〓超强酸催化剂表面，由SO〓〓诱导的相邻L酸中心和B酸中心组成了集团协同作用的超强酸中心，其集团协同作用显著地增强了催化剂表面酸性、增大了表面酸量及O〓吸附量、促进了光生电子和空穴的分离及界面电荷转移，具有可逆吸附水的性能，是SO〓〓/TiO〓超强酸催化剂具有优异的光催化氧化活性、很好的活性稳定性及抗湿性能的重要原因。

The UV and IR spectroscopic studies of the monomer films showed that the photoreaction ratio of monomer (about 50%) was higher than the corresponding photosensitive polymer (about 10%, PVCi). The polarized IR spectra proved that obvious anisotropic absorption was displayed in the irradiated photosensitive film. With polarizing microscopy method, we found that these kinds of photoalignment films exhibited good alignment ability, and the stability of the photoalignment film could reach about 100℃. 2 A photosensitive self-assembled monolayer was fabricated that contained photo-cycloadditable groups, such as, coumarin and cinnamate. The reaction process were detected by contact angle method because the IR absorption of monolayer was very weak. The photosensitive self-assembled monolayer promote uniform alignment of nematic liquid crystals by LPUV, and it thermal stability could reach about 130℃. 3 A cationic bolaform amphiphiles was synthesized that had two photosensitive double bonds, and can be polymerized by ultraviolet. A layer-by-layer self-assembled deposition film was prepared in aqueous solution by using this material and poly (sodium 4-styrenesulfonate). The UV-Vis. spectra proved that the multilayers film was uniform and layer-by-layer. When LPUV irradiated the film, the photopolymerizable double bond underwent [2+2] cycloaddition, and the production of the reaction distributed along the polarized direction of incident LPUV. Polarized UV-Vis. spectra indicated that the irradiated self-assembled multiplayer film was anisotropic, and the dichromic ration is about 0.09, it is higher than the spin-coating method of photosensitive polymer or monomer. We used this anisotropic film as alignment layer of nematic liquid crystals, and obtained a uniform and stability alignment result, the static contrast ratio is about 100, which is very close to application of liquid crystal device. This thesis is an instance that the photochemical material was used in the physics region of liquid crystals, the route that was from photosensitive monomer, self-assembled monolayer film to self-assembled multiplayer film was undergone, by this logical research method photoailgnment of liquid crystal was extended and consummated.

围绕上述思路开展了如下工作：1合成了三种可进行光二聚反应的光敏小分子单体，LPUV 辐照制作了光控取向膜；用紫外-可见光谱法和红外光谱法分析了薄膜中的光化学反应，发现小分子的光反应程度可达到50%以上，至少比光敏高分子高出5倍；薄膜的偏振红外光谱证实，经过LPUV 辐照后薄膜出现了明显的各向异性；将小分子光控取向膜制成液晶器件，在偏光显微镜下观察看到均匀一致的液晶取向；并且热稳定性达到100℃左右，接近实用化要求。2制备了含肉桂酸、香豆素基团的自组装单层膜；采用接触角的方法监测自组装反应的动力学过程；紫外-可见光谱证实了自组装单层膜在石英基板表面形成；自组装单层膜经LPUV 辐照后能诱导液晶均匀取向，而且热稳定性可达130℃，热稳定性进一步提高。3合成了含有光敏双键的双季铵盐，在水溶液状态下将它和聚乙烯基苯磺酸钠沉积生成layer-by-layer 自组装多层膜，紫外-可见光谱证实这是一个逐层均匀的沉积；在LPUV 照射下，自组装膜中的光敏双键按照偏振方向发生[2+2]环加成反应，形成取向膜，用二向色性值评价的分子取向度高于高分子及小分子光控取向膜的水平；实验证明用自组装多层膜制成的液晶器件亮暗态均匀，静态对比度约为100，达到实用化器件的水平。

These photoperiodic response curves show that Photoperiodic response may be temperature-compensated or temperature-sensitive and based on quantitative or qualitative photoperiodic time measurement. These photoperiodic response curves also show that effects of ultra-short and ultra-lo...

根据这4种光周期反应类型显示的结果，光周期反应可能是温度补偿或温度敏感的；基于数量的时间测量或基于质量的时间测量的；极短日照或极长日照对滞育诱导的影响是不同的；诱导夏季滞育的长日照和诱导冬季滞育的短日照对滞育诱导效果是不同的。

Two series of polyurethane acrylate grafted acrylic resins (Acr-g-TPU-PETA and Acr-gPPU-PETA) self-emulsifying systems are obtained by grafting -NCO group modified polyurethane acrylates with acrylic copolymer prepared from n-butyl acrylate, styrene,βhydroxyethyl methacrylate and acrylic acid The self-emulsifying systems showed Newtonian fluidity with viscosity closed to that of water, the solid contents were around 30% The T〓 of 15～4℃ for dried film before photocuring favored film formation at room temperature DSC and DMA results showed that PU-PETA is compatible with acrylic resin in the grafted resin The TG and dTG curves for Acr-g-PU-PETA samples were substantially different from the corresponding blends, and the brodened dTG peaks for photocured grafted resin suggest that there might be multiple interactions among chain segments The photocued film of the grafted resins self-emulsifying system exhibited good overall properties with polyurethane acrylate grafts ranging from 30% to 50%, and Acr-g-TPU-PETA series showed better properties than Acr-gPPU-PETA series The adhesion of the photocured film was 1～2 grade, impact strength was 50kg-cm and flexibility was 1mm The Shore hardness and the adhesion of the film decreased markedly if PETA was replaced by HEMA as photoactive group due to the lower C=C double bond content in the grafted resin The polyhydroxy amine-linked thioxanthones photoinitiators can be evenly dispersed in self-emulsifying system without color spot appearing in the dried film The films photocured with IV〓～IV〓 generally exhibited higher Shore hardness, gloss and solventresistance than that cured with Irgacure 2959 and did not induce the rusting of the iron substrate Pigmenting with titanium oxide had no effect on the photocuring The polyhydroxy amine-linked thioxanthone IV〓 and IV〓 can be new candidates for the formulation of titanium oxide pigmented photocurable water-borne coatings for their pale-yellow appearance and slight interference with the color of the coatings WB 4759 with high water-solubility coalesced and separated from the dried resin film, and even induced the rusting of iron substrate.

以丙烯酸丁酯，甲基丙烯酸-β-羟乙酯，丙烯酸及苯乙烯合成厂丙烯酸共聚树脂，并与含-NCO端基的聚氨酯丙烯酸酯接枝反应，经水性化后，得到两个系列（Acr-g-TPU-PETA和Acr-g-PPU-PETA）各5个不同配比的丙烯酸树脂接枝聚氨酯丙烯酸酯自乳化体系，粘度与水相近，为牛顿流体，固含量30％左右。光固化前干燥涂膜的玻璃化转变温度在-15℃～4℃之间，有利于室温下成膜。DSC及DMA谱表明两种树脂基本相容。Acr-g-PU-PETA的热失重行为明显不同于共混材料，接枝样dTG峰明显宽化，表明接枝样中链段之间的相互作刚有多重性，丙烯酸树脂与聚氨酯之间有一定的相容性。接枝树脂自乳化体系光固化涂层的综合性能以聚氨酯丙烯酸酯成分为50％～30％者相对较好，且以Acr-g-TPU-PETA系列更理想。光固化膜的附着力为1～2级，冲击强度为50kg·cm，柔软性多为1mm。以HEMA代替PETA作为接枝树脂的活性基团，碳—碳双键密度太低，光固化膜交联点太少，硬度和附着力均较差。多羟基胺连硫杂蒽酮光引发剂能均匀分散于树脂自乳化体系和接枝树脂干膜中，不出现色斑，光固化膜肖氏硬度一般高于以Irgacure 2959为光引发剂的光固化膜，光泽度及耐丁酮溶剂性能均有所提高，不会诱导铁基生锈，钛白着色对光固化结果几乎没有影响。本论文所合成的多羟基胺连硫杂蒽酮光引发剂IV〓与IV〓为浅黄色，对光固化涂层的颜色干扰较小，为配制钛白着色光固化水性涂料提供了新的光引发剂。水溶性太强的WB 4759在干膜中易聚结析出，且对所附着的铁基有诱导锈蚀作用。

Second, we discuss two materials which are cinnamoyl chloride and azobenzene. The cinnamoyl chloride can induce the photo-dimerization reaction under linear-polarized UV light. Similarly, azobenzene can induce the cis-trans photoisomerization under UV light.

第二部分采用光诱导配向的方式，将偶氮苯与PI结合，再利用偏极化紫外光曝光使其产生顺-反异构化反应，再用polarized-ATR-FTIR研究其三度空间之分子排列，做为未来显示器配向膜的参考。

What we focused on were the photo-induced selective fissions ofα and β bonds, properties of low-lying electronic states, and mechanisms of photochemical reactions for the above molecules, which are the leading research fields enjoying the interest and attention of chemists.

在本论文中，我们应用CASSCF、MP2、MR-CI、DFT等精确的量子化学计算方法，以BrCH〓COCl、CH〓COCOOH、CH〓COCN、HCOCN、CH〓CHS、〓CS和HCSCN等体系为对象，对目前国际上感兴趣的前沿课题——光诱导的α和β键的选择性解离、低电子激发态的结构和性质以及光化学反应机理等进行了详细的理论研究，并得到了具有重要意义的结果。

This research take late-maturing variety adzuki bean Jihong-4 as the experiment material, After the photoperiod inducement at different leaf ages treatment, the result showed that the activity of NR under LF treatment is higher than CK treatment on the whole, and is lower than SD treatment; The content of the dissociation amino acid under these three treatments show a descend trend along with the leaf ages accretion, but the inducement increasing the content of dissociation amino acid, different leaf ages leaves show some difference, and alternating rise with SD treatment; Inducement can reduce the content of soluble sugar, and continuous inducement shows a accumulation effect; 2LF is the most sensitivity stage for soluble protein under photoperiodic inducement, From this stage, each leaf indumenta can reducing the content soluble protein, but continuous inducement reducing rising it.

本研究通过光周期诱导的方法，对中晚熟品种冀红4号红小豆进行不同叶龄进行处理，结果表明：所有叶龄处理下硝酸还原酶活性基本高于自然光处理而低于连续短日照处理下的；随着叶龄增大，各处理游离氨基酸总量均呈下降趋势，但光周期诱导可提高游离氨基酸含量，不同叶龄表现有所差异，与连续诱导交替上升；诱导可降低可溶性糖的含量，并连续诱导出现累积效应；2LF是光周期诱对可溶性蛋变化最敏感的时期，这个时期起单个叶龄诱导可降低可溶性蛋白含量，但连续诱导却可提高；LF处理下的类胡萝素总体含量高于另两个处理，而LF处理下的叶绿素含量在仅3叶龄前高于CK处理下的，随后出现下降趋势。

Five expressed genes contributed to the flowering process and embryonic development such as prolamine, gene for allergenic protein, chalcone synthase, putative peptide methionine sulfoxide reductase and acyl carrier protein Ⅱ gene were chosen to hybridize with a 1510-RNA-blot (time-point phenotypes) array. The 1510 RNA blots were prepared into an RNA array for the purpose of conferring and validating global transcriptional profiles on booting, flowering and filling quantitatively and qualitatively at a statistic level. The results verified: Prolamine and allergenic protein were high-expressed in filling grains after being regulated by development, Chalcone synthase and methionine sulfoxide reductase were high-expressed in the leavies induced by light, in the root stressed for nitrogen deficiency.

为了全局性分析基因表达谱以及进一步验证它们与开花过程的相关性，选取参与水稻开花过程和胚胎发育过程的基因：查尔酮合酶、酰基载体蛋白Ⅱ、醇溶蛋白、S-腺苷基甲硫氨酸还原酶、过敏反应蛋白等为探针，与1500个水稻RNA斑点阵列进行杂交时，结果证实：醇溶蛋白和过敏反应蛋白受发育调节在乳熟成穗中高表达，查尔酮合酶和S-腺苷基甲硫氨酸还原酶在叶片中受光诱导、在根中受缺氮胁迫高表达。

As relative phenomena, optically induced level shift or split i.e.

作为相关现象，第一章综述了光诱导的能级移动和分裂现象即ac Stark效应的发现、发展、研究方法及其应用。

It has been put forward that there exists single Ball point and double Ball points on the symmetrical connecting-rod curves of equilateral mechanisms.

从鲍尔点的形成原理出发，分析对称连杆曲线上鲍尔点的产生条件，提出等边机构的对称连杆曲线上有单鲍尔点和双鲍尔点。

The factory affiliated to the Group primarily manufactures multiple-purpose pincers, baking kits, knives, scissors, kitchenware, gardening tools and beauty care kits as well as other hardware tools, the annual production value of which reaches US$ 30 million dollars.

集团所属工厂主要生产多用钳、烤具、刀具、剪刀、厨具、花园工具、美容套等五金产品，年生产总值3000万美元，产品价廉物美、选料上乘、质量保证，深受国内外客户的青睐