含铬废物焚烧中CrOH+H→CrO+H2反应机理研究

本文用量子化学密度泛函UB3LYP方法,在6-311 G**基组水平上研究了含铬固体废物焚烧过程中CrOH H→CrO H2的微观反应机理。在相同理论水平上用内禀反应坐标理论(IRC)对最小能量途径进行计算,并进行了详细的讨论。分别计算了正、逆反应的活化能。采用经典过渡态理论计算了正、逆反应的反应速率常数。     

羧酸吡啶类分子间氢键对光致异构化及光化学稳定性影响的谱学研究

以丁二酸胆甾醇单酯(CSA)作为质子给体,以4-对烷氧基苯甲酰氧基-4′-苯乙烯基吡啶(NCn)作为质子受体,通过羧酸和吡啶之间的氢键作用形成氢键诱导液晶化合物(CSA·NCn)。 利用紫外光谱研究了含苯乙烯基吡啶基团的液晶化合物NCn及其与丁二酸胆甾醇单酯(CSA)的氢键复合物CSA·NCn在溶液中的光致变色及光化学反应。 结果表明,在乙醇溶液中紫外光照射下二者均发生顺反异构化,分子间氢键对顺反异构化反应没有太大的影响;NCn化合物在氯仿溶液中,紫外光照射下发生光化学反应,而CSA·NCn的氯仿溶液,紫外光照射下只发生顺反异构化,这一方面说明光化学反应发生在吡啶的氮端,同时也表明这类氢键液晶化合物中的氢键比较稳定,光照下不发生解离;在NCn和CSA·NCn的乙醇溶液中加入H₂SO₄,两者均发生质子化。 表明强酸可以破坏CSA·NCn化合物中的氢键,使含吡啶端基解离出来,同H+发生质子化。     

姜黄素苯胺希夫碱稀土配合物的光致变色性能研究

以稀土Ce,La,Nd (Ⅲ) 硝酸盐和配体姜黄素缩二苯胺Schiff碱和姜黄素缩二(4-甲基苯胺)Schiff碱,合成了六种稀土姜黄素配合物。并采用元素分析、红外吸收光谱、摩尔电导、热重-差热等方法对六种配合物进行表征,确定了所合成配合物的化学组成。研究了各种配合物的紫外-可见光谱、荧光光谱的光致变色性能和在有机溶剂中的溶致变色性能。试验表明随着光照时间的延长,配合物的紫外-可见吸收强度和荧光发射峰的强度不断减弱,峰的位置也发生了一定程度蓝移,溶液颜色变浅。停止照射,溶液恢复到光照射前的颜色,光致变色过程可以重复进行,这说明配合物具有良好的光致变色性能,消色反应遵循一级反应动力学规律。配合物在不同的溶剂中紫外-可见吸收光谱的峰强度和位置也有所不同。对配体及配合物与具有光致变色性能的姜黄素与二乙烯三胺形成的一系列配合物的光谱性质进行了比较和讨论。没有发现配体有光致变色的性质,与姜黄素二乙烯三胺所形成的一系列稀土配合物比较,具有光致变色性能配合物引入了苯胺/对甲苯胺配体基团,增大了配体的共轭面,从而引起配合物的紫外-可见吸收强度的增大和荧光发射峰面积的增加。     

乙腈-水和乙二醇-水均相溶液中光诱导杜醌激发三重态与色氨酸、酪氨酸的氢原子转移反应（英文）

本文用激光闪光光解技术研究了光诱导生物醌杜醌激发三重态(~3DQ~*)和色氨酸(Trp)与酪氨酸(Tyr)在乙腈-水(MeCNH_2O)及乙二醇-水(EG-H_2O)均相溶液中的光化学反应,分析了反应的机理,并基于Stern-Volmer方法测量了反应速率常数.光解DQ体系可以生成~3DQ~*,3DQ~*与Trp、Tyr发生的氢原子转移反应占主导地位.对于DQ/Trp/MeCN-H_2O和DQ/Trp/EG-H_2O溶液,3DQ~*与Trp反应生成杜醌中性自由基DQH·、以碳为中心的色氨酸中性自由基Trp/NH和以氮为中心的色氨酸中性自由基Trp/N·.对于DQ/Tyr/MeCN-H_2O和DQ/Tyr/EG-H_2O溶液,3DQ~*与Tyr反应生成DQH·和酪氨酸中性自由基Tyr/O·.~3DQ~*与Trp、Tyr的氢原子转移反应速率常数都在10~9 L·mol~(-1)·s~(-1)量级,反应近似受扩散控制.MeCN/H_2O均相溶液中~3DQ~*与Trp、Tyr的反应速率常数要明显高于EG/H_2O均相溶液中的反应速率常数,这与Stokes-Einstein方程定性一致.     

2-[(4-羟基苯基)偶氮]蒽醌的合成及其阴离子识别

以酚羟基为识别位点,蒽醌基和偶氮基为信号报告基团,设计合成了识别阴离子的主体分子2-[(4-羟基苯基)偶氮]蒽醌.紫外-可见吸收光谱结果表明,在DMSO介质中,主体分子可以“裸眼”识别F-和Ac-,吸收光谱发生显著变化,溶液颜色由黄色变为蓝绿色,其它阴离子不影响其对F-和Ac-的识别.初步探讨了识别机理,表明主体分子与阴离子之间形成氢键促进了分子内电荷转移,使吸收光谱发生显著红移,溶剂对主体分子与阴离子之间的反应存在影响.     

含磺酸基的聚硅氧烷类光致变色液晶的合成及性能

通过重氮化反应合成了末端为磺酸基的刚性基元,再经过取代、加成、酯化反应最终合成了偶氮苯类聚硅氧烷液晶。通过UV表明其具有类似小分子的光致变性。并用POM、DSC对其液晶行为进行了表征,结果表明该化合物属于近晶A型液晶,相变区间为191.04—274.95℃,液晶范围较宽,有望作为光控开关和新型信息存储材料。     

基于侧边抛磨光纤传感器的混合液晶薄膜光折变特性研究

利用侧边抛磨光纤(SPF)传感器抛磨区对外界折射率敏感的特性,研究了混合有偶氮苯(AZO)和手征材料(ZLI811)的液晶混合物薄膜在紫外光照射下产生的光折变效应.将液晶、AZO 和 ZLI811 等 3 种材料的混合物涂覆在经过标定的 SPF 传感器的抛磨区上,制备成混合物薄膜.用 UV 光照射光敏薄膜导致 SPF 中传输光功率改变.实验表明:混合物薄膜在 UV 光照射下有光敏特性,会产生折射率变化,其折射率从1.474 变到1.470.这表明此光敏薄膜材料是负光折变材料.这种光敏薄膜材料可应用于制作新型全光纤光控器件和传感器.     

复合胺砜溶液吸收CO_2传质动力学研究

利用湿壁塔法测量复合胺砜溶液吸收CO_2的动力学特性,实验工况包括不同的反应温度(293.15～323.15 K)和不同的溶液浓度(0.5～6.6 mol/L)。本文简化了气液传质模拟,计算了不同工况下的吸收速率常数、总反应速率常数、二级反应速率常数及增强因子等动力学参数,同时根据实验结果拟合得到了二级反应速率常数和增强因子的经验公式,并得到了复合胺砜溶液与CO_2反应的表观反应活化能为为20.38 kJ/mol。     

紫外光辐照对偶氮苯光谱特性的影响

采用紫外可见吸收、稳态荧光光谱和荧光衰减测量技术,观察了4-硝基-4'-氨基偶氮苯(NAA)在氯仿溶液中的光致变色现象及分子的跃迁能级和能级寿命。结果表明:NAA分子的顺反异构化反应并非一级反应;分子处于反式异构体和顺式异构体的跃迁能分别为255.6,240.2 kJ/mol;分子处于反式异构体的能级寿命为0.02 ns,处于顺式异构体的能级寿命为3.54 ns。顺反异构体的含量、NAA分子之间及NAA分子与溶剂分子之间的相互作用影响NAA分子激发态的能级寿命。     

UV光谱研究[Cp-Fe-Cp]BF4和[Cp-Fe-Naph]BF4的光解动力学及机理

本文测定了两种新型阳离子光聚合引发剂二茂铁四氟硼酸盐（[Cp-Fe-Cp]BF4)和环戊二烯基－铁－萘四氟硼酸盐（[Cp-Fe-Naph]BF4)在二氯甲烷和环氧氯丙烷中的紫外－可见吸收光谱，研究了紫外光照射对吸收光谱的影响，通过实时紫外－可见吸收光谱分析，研究了两种光引发剂在环氧氯丙烷中的光解动力学。发现二者的吸收光谱随光照时间的变化规律一致，而且光解反应均为一级反应，速率常数分别为0.72和0.65min^-1，从而提出了二茂铁四氟硼酸盐的光引发机理。     

Supramolecular assemblies of azobenzene‐β‐cyclodextrin dimers and azobenzene modified polycaprolactones

Click chemistry is employed to couple two β‐cyclodextrins at both ends of azobenzene moiety yielding dumbbell‐shaped amphiphiles (AZO‐β‐CD dimer) constructed by rigid aromatic building blocks as “body”, and hydrophilic cyclodextrins as “head” with almost quantitative yield and purity. Bulk aggregates formed by the self‐assembly of the supraamphiphiles through π–π stacking and hydrophobic effect are observed. Meanwhile, the rationally designed polyesters, named as AZO‐PCL with controllable molecular weights and low polydispersities, are successfully synthesized by ring‐opening polymerization of ε‐caprolactone in the presence of p‐aminoazobenzene as initiator. In the aqueous phase, very stable spherical particles are formed by host–guest interactions between AZO‐β‐CD and AZO‐PCLs; the spherical aggregates inherit the photo‐responsiveness of azobenzene. The detailed aggregation and disaggregation behaviors are fully investigated by TEM, SEM, NMR, 2D NOESY, IR, UV and XRD measurements. Compared to the previous works, our newly developed system can be fabricated with more readily manners, avoiding tedious synthetic process; the reversible and dynamic nature of the non‐covalent interactions also can be modulated alternatively by UV or visible light. Thus, such dumbbell‐shaped supra‐amphiphiles are of great potential applications in the controlled delivery systems. Copyright © 2014 John Wiley & Sons, Ltd.     

Optically switchable all-fiber optic polarization rotator

This study demonstrates an all-fiber optical polarization rotator and switch based on a side-polished fiber (SPF) overlaid with a photoresponsive liquid crystal (LC) containing a nematic LC and a photosensitive azobenzene molecule. The trans-cis photoisomerization of azobenzene modulates the overlaid LC's birefringence, changes the refractive index (RI) of the photoresponsive LC-overlaid SPF, and further controls and switches the phase retardation. This design achieves a 10° phase shift under switching time of less than 1 s. The demonstration has potential for an optically tunable in-line 2 × 2 fiber-optic switch or microstructured fiber-based photonic device controlled by the polarization of light.     

Photochromism of new unsymmetrical diarylethenes with a quinoline moiety

Three unsymmetrical diarylethenes with a 6‐membered quinoline moiety were synthesized to investigate the effects of the substituents on their photochromism, and fluorescence, and the structure of one diarylethene was determined by single crystal X‐ray diffraction analysis. Quinoline was connected directly to the central perfluorocyclopentene ring as an aryl moiety and available to participate in photoisomerization reaction in solution, amorphous films, and crystalline phase. These diarylethenes exhibited good photochromism with excellent thermal stability and obvious fatigue resistance. The electron‐donating methoxy group could enhance the absorption maxima of closed‐ring isomers and the quantum yields of cyclization and cycloreversion, but the electron‐withdrawing trifluoromethyl had an opposite effect. In addition, they functioned as notable fluorescence switches in both solution and polymethylmethacrylate films, and the trifluoromethyl group and the methoxy group both increased the emission intensity. The results revealed that the quinoline moiety and substituents played a vital role in the process of photoisomerization reactions for these diarylethenes.     

Light-stimulated electro-optics by azo-doped aerosil/7CB nanocomposites

Photoactive nanofilled nematic is proposed. Stable three-component photoresponsive nanocomposite was prepared from photo-insensitive nanofilled nematic by inclusion of 3?wt.% azobenzene-containing photoactive mesogen 4-(4′-ethoxyphenylazo)phenyl hexanoate (EPH). The host nanofilled nematic was produced from the room-temperature nematic liquid crystal 4-n-heptyl cyanobiphenyl (7CB) and 3?wt.% filler of Aerosil 300 hydrophilic silica nanospheres of size 7?nm. Apparent effect of stimulation with a relatively weak continuous illumination by UV light (375?nm wavelength) takes place for both the alternating-current electric field-dependent optical transmittance and the electro-optic amplitude-frequency modulation by thin films (25?µm thick) of the EPH/aerosil/7CB nanocomposite. The light-stimulated electro-optics of EPH-doped aerosil/7CB films and the corresponding reversible light control are achieved through trans-cis-trans photoisomerization of the photoactive agent EPH. As such, the initial electro-optical response of the studied photoactive nanocomposites is recovered with continuous blue-light illumination. The examined EPH/aerosil/7CB nanocomposites exhibit photo-controllable electro-optical response that is of practical interest.     

Effect of etching parameters on antireflection properties of Si subwavelength grating structures for solar cell applications

We fabricate the aluminum-doped zinc oxide (AZO) subwavelength gratings (SWG) on Si and glass substrates by holographic lithography and sequent CH₄/H₂/Ar reactive ion etching process. The etch selectivity of AZO over photoresist mask as well as the nano-scale shape is optimized for better antireflection performance. To analyze the antireflective properties of AZO SWG surface, the optical reflectivity is measured and then calculated together with a rigorous coupled-wave analysis. The reflectance spectrum can be considerably changed by incorporating the SWG into AZO film. As the SWG height of AZO on Si substrate increases, the magnitude of interference oscillations in the reflectance spectrum tends to be reduced with the larger difference between its maxima. The use of optimized SWG can significantly reduce the surface reflection of AZO film at the desired wavelengths. The measured reflectance data of AZO SWG are reasonably consistent with the simulation results. No considerable change in transmission characteristics is observed for AZO SWG structures.     

Hunting for smectic C in calamitic azobenzene ionic liquid crystals with different cationic head groups

The tilted smectic C phase is a rather uncommon phase in ionic liquid crystals (ILCs), whereas the orthogonal smectic A phase is the most common phase in ILCs. We now present 2 new groups of mesogens with an azobenzene core that exhibit smectic C as well as smectic A phases. Their phase sequences and tilt angles were studied by polarizing microscopy, and their temperature‐dependent layer spacings and orientational order parameters were investigated by X‐ray diffraction. We present 1 new amidinium azobenzene mesogen that forms enantiotropic smectic C and A phases and another amidinium as well as 2 new guanidinium azobenzene mesogens that exhibit monotropic smectic C and enantiotropic smectic A phases. With this study, we show that azobenzene is indeed an SmC‐promoting group in ILCs. Comparing these results with our earlier results on azobenzenes with an N‐methylimidazolium head group (N Kapernaum et al, ChemPhysChem 2016, 17, 4116‐4123), we show that the aromaticity of the imidazolium head group plays an important role in the formation of smectic C phases.     

Effect of fluorine groups and different terminal chains on the electro-isomerization of azobenzene liquid crystals

A series of azobenzene liquid crystals with one or two terminal acrylate groups were synthesized and their polymers were fabricated.The azobenzene liquid crystals and their polymers achieved the photoisomerization from the liquid crystalline trans-isomer to the isotropic cis-isomer with UV irradiation.Then,the cis to trans isomerization induced by an electric field was studied,the time required for electro-isomerization was measured,the texture change and absorption variation from cis to trans form induced by the electric field were observed clearly,and the time required for electro-isomerization was much shorter than that for thermal relaxation.The influence of the polar group(fluorine),terminal acrylate group,and flexible alkyl chain on the time of electro-isomerization was studied.The results show that the compounds with polar fluorine group require shorter time for electro-isomerization and the polymerization of terminal acrylate group delays the electro-isomerization.     

液晶显示用取向材料聚甲基丙烯酸肉桂酰氧基乙酯的光控取向研究

通过实验研究了光聚合物材料聚甲基丙烯酸肉桂酰氧基乙酯（ＣＥＭＣ）的光化学反应过程, 以及对液晶材料ＬＣ－６７１０Ａ 的取向能力． 通过原子力显微镜（ＡＦＭ）观察了取向层表面在光化学反应前后的变化, 测量了光控取向膜液晶盒中液晶分子的预倾角及单面光控取向扭曲向列液晶显示器（ＴＮＬＣＤ）的电光特性和时间响应特性曲线, 研究了液晶分子排列取向的机理．     

Antireflective properties of AZO subwavelength gratings patterned by holographic lithography

We fabricate the aluminum-doped zinc oxide (AZO) subwavelength gratings (SWG) on Si and glass substrates by holographic lithography and sequent CH₄/H₂/Ar reactive ion etching process. The etch selectivity of AZO over photoresist mask as well as the nano-scale shape is optimized for better antireflection performance. To analyze the antireflective properties of AZO SWG surface, the optical reflectivity is measured and then calculated together with a rigorous coupled-wave analysis. The reflectance spectrum can be considerably changed by incorporating the SWG into AZO film. As the SWG height of AZO on Si substrate increases, the magnitude of interference oscillations in the reflectance spectrum tends to be reduced with the larger difference between its maxima. The use of optimized SWG can significantly reduce the surface reflection of AZO film at the desired wavelengths. The measured reflectance data of AZO SWG are reasonably consistent with the simulation results. No considerable change in transmission characteristics is observed for AZO SWG structures.