光敏型阴离子表面活性剂的合成及表面性能

本文制备了一种含有偶氮苯基团的阴离子表面活性剂,其表面活性及对方解石矿物的润湿性能,可以用紫外光照射进行调控。在紫外光照射后,表面活性剂的临界胶束浓度(cmc)、最低表面张力(γcmc)、分子极限占有面积(Amin)增大,饱和吸附量(Гmax)和降低表面张力的效率(pC20)降低,对方解石的润湿能力增强。     

Reversible Single Molecular Switch Operating at 300 K on a Surface

A single 4‐pyridylazobenzene molecule is observed at room temperature on a Si(111)‐B surface by using scanning tunnel microscopy. The reversible conformational switching of this molecule is induced by tunneling electrons and observed at room temperature. This process is based on an intramolecular rotation of a single phenyl group without isomerization of the N?N double bond.     

An Incremental System To Predict the Effect of Different London Dispersion Donors in All-meta-Substituted Azobenzenes

Predictive models based on incremental systems exist for many chemical phenomena, thus allowing easy estimates. Despite their low magnitude in isolated systems London dispersion interactions are ubiquitous in manifold situations ranging from solvation to catalysis or in biological systems. Based on our azobenzene system, we systematically determined the London dispersion donor strength of the alkyl substituents Me, Et, iPr up to tBu. Based on this data, we were able to implement an incremental system for London dispersion for the azobenzene scheme. We propose an equation that allows the prediction of the effect of change of substituents on London dispersion interactions in azobenzenes, which has to be validated in similar molecular arrangements in the future.     

A Tri‐Stimuli‐Responsive Shape‐Memory Material Using Host–Guest Interactions as Molecular Switches

A thermo‐, photo‐ and chemoresponsive shape‐memory material is successfully prepared by introducing α‐cyclodextrin (αCD) and azobenzene (Azo) into a poly(acrylate acid)/alginate (PAA/Alg) network. The tri‐stimuli‐responsive formation/dissociation of αCD‐Azo acts as molecular switches freezing or increasing the molecular mobility. The resulting film herein can be processed into temporary shapes as needed and recovers its initial shape upon the application of light irradiation, heating, or chemical agent independently. Furthermore, the agar diffusion test suggests that the α‐CD‐Alg/Azo‐PAA has good biocompatibility for L929 fibroblast‐like cells.

     

Synthesis, Photophysics and Morphology of a Conjugated Polymer with Azobenzene Building Block in the Backbone

A conjugate polymer poly[p‐(phenyleneethylene)‐alt‐(phenyleneazophenyleneethylene)] (PPEPAPE) containing azobenzene building block in the polymer backbone was synthesized via Sonogashira cross‐coupling of 4,4′‐diiodoazobenzene and 1,4‐diethynyl‐2,5‐didodecyloxybenzene. All the monomers and the resulting polymer were well characterized. The polymer had a relatively high molecular weight and showed very good solubility (≧10 mg/mL) in common organic solvents. The photophysics of this polymer in solution and in film was investigated. The surface morphology of the films was studied by scanning electron microscope (SEM) and the relationship between the morphology and absorbance was discussed. This polymer has good film‐forming property, broad absorbance and no emission, which might make it a good candidate for the photovoltaic material in the solar cell.     

Effect of crosslinking on the photoinduced orientation of azo groups in thin polymer films

A series of amorphous copolymers containing disperse red 1 and crosslinkable acrylic groups were prepared. The crosslinked polymers were prepared in thin films by thermal polymerization of the acrylic groups in the copolymers. The orientation induced by irradiation with a linearly polarized laser was measured as birefringence at several temperatures, and the effect of crosslinking on the photoinduced orientation was investigated. Crosslinking enhanced the stability of the photoinduced birefringence. In particular, crosslinking helped to maintain the birefringence both at high temperatures and after the linearly polarized laser was turned off. The birefringence dynamics was analyzed with biexponential curve fitting. Crosslinking influenced not only the birefringence levels but also its rate of growth. The growth rate of the photoinduced birefringence decreased by crosslinking, whereas the relaxation was not significantly affected. Although crosslinking restrained the mobility of the azo chromophores, a certain fraction could orient or move randomly even in highly crosslinked polymer networks. © 2001 John Wiley & Sons, Inc. J Polym Sci Part B: Polym Phys 39: 1686–1696, 2001     

线-圆双偏振态光束抽运有机聚合物全光开关

为了有效降低偶氮苯聚合物薄膜全光开关信号的本底,提高全光开关信号的调制深度,利用线偏振光合成圆偏振光的原理,设计了一种新的线-圆双偏振态光束抽运光路。实验用532 nm光作为抽运光,632.8 nm的He-Ne激光作为探测光。532 nm的光先分为功率相等但偏振正交、相位差为π/2奇数倍的两束线偏振光,然后再合成一束抽运光。通过调制其中的一束来实现线偏振与圆偏振抽运光之间的转换,从而实现样品光致双折射的产生与擦除。以掺杂分散红1(DR1)的聚甲基丙烯酸甲酯薄膜(PMMA)为样品进行实验。结果表明,用此光路,样品全光开关信号的调制深度达到92%,远远高于传统的单一线偏振光束抽运光路的实验结果。     

相转移催化合成2,6,2′,6′-四甲基偶氮苯

以2,6-二甲基苯胺(1)为原料,铁氰化钾和氢氧化钠为缩合剂,采用季铵盐(C8~10H17~21)3N CH3Cl-(A-1)相转移催化合成了2,6,2′,6′-四甲基偶氮苯。正交实验确定最佳反应条件为:150 mmol,n(铁氰化钾)∶n(1)=5∶1,w(A-1)=5%,于95℃反应15 min,收率45.87%。