Si(111) surface modified with alpha,beta-unsaturated carboxyl groups studied by MIR-FTIR

A Si(111) surface modified with alpha,beta-unsaturated carboxyl groups was fabricated using activated alkynes such as propiolic acid and propiolic acid methyl ester via hydrosilylation reaction. The obtained coverage of carboxyl groups was roughly estimated to be 55-60% in both cases from the Si-2p and C-1s X-ray photoelectron specroscopy (XPS) peak intensities. The detailed surface structures were investigated by multiple internal reflection Fourier transform infrared (MIR-FTIR) measurement. It was revealed that this reaction was promoted by visible light irradiation at room temperature. The Si surface modified with functional groups prepared under such a moderate condition is adaptable to functional devices which are easily damaged under UV irradiation or high temperature conditions.     

Controlling Chain Coupling and Single‐Chain Ligation by Two Colours of Visible Light

While photochemical synthesis offers access to spatiotemporal reaction control, its potential to selectively address specific reactions by the colour of light is usually limited by ubiquitous spectral absorption overlaps of the reactive groups. Herein, a new concept is introduced that actively suppresses one ligation reaction by triggering the cycloreversion of the [2+2] cycloaddition of styrylpyrene. Combination of the photoreversible styrylpyrene chemistry with the [4+4] cycloaddition of 9‐triazolylanthracene makes it possible to initially induce chain coupling using UV light and to subsequently ligate the formed single‐chain nanoparticle (SCNP) with a second polymer chain using blue light. Seizing upon the first sequence‐independent λ‐orthogonal reactivity established here, the same macromolecular architecture was obtained in reverse irradiation sequence, by blue and subsequent violet light irradiation—completely foregoing high‐energy UV light.     

基于聚醚胺(PEA)动态交联网络的多重响应性表面褶皱图案

刺激响应性表面图案赋予了材料动态可调的表面性能,是智能材料领域研究的热点,然而如何通过简单有效的方法构建这类动态表面图案也是该领域的难点.本文将动态硼酸酯键和光可逆二聚基团引入到聚醚胺(PEA)交联网络中,通过双层褶皱体系构建一系列具有光和湿度刺激响应性表面褶皱图案.在365 nm紫外光照和加热的条件下,蒽基团(AN)的光二聚与硼酸键的形成使得上表层聚醚胺模量变大,产生微米级表面褶皱图案;在254 nm紫外光照射或水蒸气作用下,聚醚胺网络解交联,表面褶皱图案消失;利用光化学时空分辨的特性,通过光掩膜板光照还可以制备多层次动态表面褶皱图案.这种多重刺激响应性表面褶皱图案为构建智能聚合物表面提供了新思路,在传感和防伪等领域具有潜在的应用前景.     

自组装光致形变功能偶氮分子玻璃微球

通过逐滴滴加去离子水的方法, 探究了具有快速光响应的偶氮分子玻璃(IAC-4)在初始浓度范围为1.0~5.0 mg/mL条件下的自组装, 制备了形貌规整、 尺寸均一的胶体球, 并利用动态光散射技术(DLS)测定了IAC-4胶体球的流体力学半径. 通过测定一系列初始浓度的IAC-4溶液的临界水含量, 探究了IAC-4在自组装过程中析出、 聚集成核和核生长的规律. 研究发现, 临界水含量与IAC-4初始浓度的关系符合二元混合溶剂中固体溶质的溶解度变化规律. 通过调节去离子水的滴加量, 研究了自组装过程中, IAC-4聚集体流体力学半径呈现先增大后减小的趋势. IAC-4胶体球的水分散液, 通过室温干燥得到的固态IAC-4微球在线性偏振激光(488 nm, 100 mW/cm²)垂直辐照下表现出快速的光响应特性. 当辐照时间为1 min时, IAC-4微球快速地拉伸形变, 形成平均长径比为1.44的椭圆形粒子. 随着光辐照时间延长, 平均长径比持续增大. 当辐照时间为7 min时, IAC-4微球被拉伸为棒状粒子, 其平均长径比可高达3.32.     

Molecular design of polymer coatings capable of photo-triggered stress relaxation via dynamic covalent bond exchange

Polymer coatings are frequently used to modify surface properties of inorganic substrates. However, the disparity in physical properties between polymer film and substrate often leads to residual stress development, which can be deleterious to the overall performance of coated materials. This work reports the molecular design of polymer films that dissipate stress upon irradiation with ultraviolet (UV) light. These polymers are synthesized by post-polymerization modification of the reactive polymer, poly(2-vinyl-4,4-dimethyl azlactone), to introduce dynamic crosslinks capable of light-initiated addition transfer fragmentation chemistry. Using a custom-built optical cantilever, contrasting film stress responses are observed between films containing dynamic bonds and analogous control films after UV light irradiation, which indicate successful stress relaxation. Further experiments demonstrate the complete relaxation of residual stress in dynamic films after an extended exposure, thereby generating a “stress-free” film. Films fabricated using this approach can be easily tailored to incorporate additional moieties to introduce desired surface properties for future application in a wide array of coatings.     

Time-Dependent Differential and Integral Quantum Yields for Wavelength-Dependent [4+4] Photocycloadditions

The [4+4] photocycloaddition of anthracene is one of most relevant photoreactions and is widely applied in materials science, as it allows to remote-control soft matter material properties by irradiation. However, highly energetic UV irradiation is commonly applied, which limits its application. Herein, the wavelength dependence of the photodimerization of anthracene is assessed for the first time, revealing that the reaction is induced just as effectively with mild visible light (410 nm). To fully establish [4+4] cycloadditions within defined chemical environments, a conceptual framework for the solution kinetics of the photo-dimerization up to long reaction times is established by developing a novel photoreaction rate law that is dependent on individual rate coefficients of the key reaction steps. These coefficients can be determined based on low conversion photochemical experiments. Both differential and integral quantum yields can subsequently be predicted that are strongly time-dependent, highlighting the need for a detailed reaction pathway analysis. The presented approach simplifies a complex photochemical scenario, making the photochemical anthracene dimerization, or potentially any other photochemical dimerization, amenable to a time-dependent understanding at the elementary reaction level.     

Visibly observed photocrosslinking reaction in indolyl based pendant liquid crystalline polymers: Synthesis and optical property

Visibly observed photocrosslinkable pendant liquid crystalline polymers containing indolyl based chalcone were synthesized by free‐radical polymerization and characterized spectroscopically. The differential scanning calorimetry and polarized optical microscopy were used to examine liquid crystalline property. The photocrosslinking and luminescence properties were monitored by UV‐Vis spectrophotometer and spectrofluorimeter, respectively. It demonstrates the chalcone unit did not manifest cis ? trans‐isomerization reaction along with 2π+2π photodimerization upon irradiation with UV light like other chalcones hitherto reported. The photocrosslinking was visibly monitored in solution through change of fluorescent color to colorless. The spacer lengths play a key role in the reaction. The fluorescence maximum was blue shifted around 70 nm in chloroform solution upon irradiation with UV light confirms the 2π+2π photodimerization of chalcone unit. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 5208–5220, 2009     

Ag修饰的Fe_3O_4/TiO_2复合磁性纳米纤维的制备及光催化性能

通过静电纺丝法制备了含有Fe3O4纳米粒子的TiO2纳米纤维,采用水热法对该纤维表面进行纳米Ag修饰,制备出具有较强磁性和较好光催化性能的复合纤维.采用X射线衍射(XRD)、扫描电子显微镜(SEM)、透射电子显微镜(TEM)和紫外-可见光谱(UV-Vis)等对样品的结构和形貌进行表征,并以罗丹明B(Rh B)水溶液降解为模型反应,考察样品在紫外光照射下的光催化性能.结果表明,所制备的TiO2为锐钛矿结构,Fe3O4纳米粒子均匀分布在TiO2纤维中,Ag纳米颗粒比较均匀地分散在磁性TiO2纤维表面.经过纳米Ag修饰后,材料的光吸收能力大为增强,吸收带红移并扩展到可见光区.在紫外光照射40 min后,合成样品对Rh B的降解率达到99.5%.此外,Fe3O4纳米粒子的存在使该材料具有较强的磁性,可通过外加磁场将其分离回收.     

TiO2和ZnO表面CO光催化氧化活性研究

在TiO2和ZnO表面CO光催化氧化研究中发现,365 nm紫外光照下TiO2表面无活性,而ZnO表面却有明显的CO光催化氧化活性.研究表明,主要是由于紫外光照下,ZnO光分解而TiO2没有光分解,从而在表面产生不同吸附形态的氧所致.而且,ZnO表面CO光催化氧化反应活性可在27 h内保持稳定,暗示气相光催化反应中,ZnO不会因为光腐蚀而使其催化活性降低.     

Azo polymer microspherical cap array: soft-lithographic fabrication and photoinduced shape deformation behavior

In this work, azo polymer microspherical cap arrays possessing unique photoprocessible properties have been fabricated through a soft-lithographic contact printing approach. In the process, hexagonal polystyrene (PS) colloidal arrays, obtained by the vertical deposition method, were used as masters. Poly(dimethylsiloxane) (PDMS) stamps with aligned hemisphere air voids on the surfaces were obtained by casting the precursor against the colloidal arrays. By using the stamps and a solution of an epoxy-based azo polymer (BP-AZ-CA) as "ink", the microspherical cap arrays were fabricated by pressing the "inked" surfaces against substrates. Uniform 2D arrays of the submicrometer spherical caps could be obtained on the substrates after peeling off the stamps and drying. The characteristic sizes of the arrays depended on some adjustable features, such as the diameters of PS spheres and concentrations of the "inks" used in the process. After exposure to a linearly polarized Ar+ laser single beam, the spherical caps could be stretched along the polarization direction, and the arrays were consequently transformed into ellipsoidal cap arrays. Upon irradiation of interfering p-polarized Ar+ laser beams, only the spherical caps in the bright fringes were deformed by the light irradiation, which resulted in more complicated surface relief patterns. The observation gives another well-defined example of the photoinduced mass migration in the submicrometer scale. The approach can potentially be applied to fabrication of microlens arrays with different converging rate in two directions.     

新型可溶性偶氮聚酰亚胺及其作为液晶光定向层应用的初步研究

以 4 ,4′ 二 (1,2 苯二酸酐 4 羧酸酯 )偶氮苯为二酐单体 ,4 十六烷氧基 4′ ,4″ 二氨基三苯甲烷为二胺单体 ,通过缩聚反应合成了可溶性偶氮聚酰亚胺 .采用红外光谱、氢核磁共振、紫外光谱和热分析等手段 ,对产物的结构、热性能及光学性能等进行了表征 .在紫外光辐照下 ,上述聚合物表现出明显的光色效应 .经线性偏振紫外光 (LPUV)辐射后的上述偶氮聚酰亚胺定向层能诱导液晶盒中液晶分子发生定向沿面排列 ,且取向均匀 .上述实验表明 ,合成的偶氮聚酰亚胺是一类潜在的液晶光定向材料 .     

Photo-Oxidation-Controlled Surface Pattern with Responsive Wrinkled Topography and Fluorescence

Wrinkles and photo-oxidation reactions are widely found in soft materials, which are intimately associated with the failure of materials and structures. It is expected that the photo-oxidation process could also have a positive effect on the material and its surface. Here, we report the photo-oxidation of 2-(4-dietheylaminophenyl)-4,5-bis(4-methoxyphenyl) imidazole (DEA-TAI) into a wrinkled bilayer system to control surface wrinkle and fluorescent patterns, in which a supramolecular polymer network composed of carboxylic acid-containing copolymer (PS-BA-AA; PS=poly(styrene), BA=butyl acrylate; AA=acrylic acid) and DEA-TAI were used as the skin layer. Ultraviolet (UV) irradiation can induce photo-oxidation of the imidazole ring of DEA-TAI to weaken the intermolecular hydrogen bonding between PS-BA-AA and DEA-TAI, resulting in the release of stress in the bilayer system. The wrinkled morphology and fluorescence of the surface can be simultaneously regulated by photo-oxidation of DEA-TAI under UV light, and the resulting wrinkles are extremely sensitive to the pH value, which can be quickly and reversibly erased by NH₃ gas. Smart surfaces with specific hierarchical wrinkles and fluorescence can be achieved by selective irradiation with photomasks, which may find potential applications in smart displays and multi-code information storage.     

Reversible photoinduced change in molecular ordering of diarylethene derivatives at a solution-HOPG interface

A diarylethene-pyrene diad and a diarylethene-pyrene-diarylethene triad were synthesized to investigate the photoinduced two-dimensional ordering change at a solution-HOPG interface. The molecular arrangements were detected by STM. The different photochromic isomers showed different orderings reflecting the differences in their molecular structures. For the diarylethene-pyrene-diarylethene triad, a new ordering appeared upon irradiation with UV light and returned to the original ordering upon subsequent irradiation with visible light. The new arrangement was assigned to the ordering of the closed-closed isomers based on the images of the isolated open- and closed-isomers. The relationship between the nature of the two-dimensional ordering and the molecular structure is discussed.     

Visible-light-induced photocatalytic degradation of 4-chlorophenol and phenolic compounds in aqueous suspension of pure titania: demonstrating the existence of a surface-complex-mediated path

The visible-light-induced degradation reaction of 4-chlorophenol (4-CP) was investigated in aqueous suspension of pure TiO2. Contrary to common expectations, 4-CP could be degraded under visible illumination (lambda > 420 nm), generating chlorides and CO2 concomitantly. The observed visible reactivity was not due to the presence of trace UV light since the visible-light-induced reactions exhibited behaviors distinguished from those of UV-induced reactions. Dichloroacetate could not be degraded under visible light, whereas it degraded with a much faster rate than 4-CP under UV irradiation. The addition of tert-butyl alcohol, a common OH radical scavenger, did not affect the visible reactivity of 4-CP, which indicates that OH radicals are not involved. Other phenolic compounds such as phenol and 2,4-dichlorophenol were similarly degraded under visible light. The surface complexation between phenolic compounds and TiO2 appears to be responsible for the visible light reactivity. Diffuse reflectance UV-vis spectra showed that 4-CP adsorbed on TiO2 powder induced visible light absorption. The visible light reactivity among several TiO2 samples was apparently correlated with the surface area of TiO2. The visible-light-induced photocurrents on a TiO2 electrode could be obtained only in the presence of 4-CP. It is proposed that a direct electron transfer from surface-complexed phenol to the conduction band of TiO2 upon absorbing visible light (through ligand-to-metal charge transfer) initiates the oxidative degradation of phenolic compounds. When the surface complex formation was hindered by surface fluorination, surface platinization, and high pH, the visible-light-induced degradation of 4-CP was inhibited. The evidence of visible-light-induced reactions and the experimental conditions affecting the visible reactivity were discussed in detail.     

Reversible self-organization of a UV-responsive PEG-terminated malachite green derivative: vesicle formation and photoinduced disassembly

This paper describes the assembly and disassembly of vesicles formed by a UV-responsive poly(ethylene glycol) terminated malachite green derivative. The UV-responsive amphiphile with both a hydrophobic malachite green group and a hydrophilic PEG group can self-organize into vesicles in water before UV irradiation. However, upon UV irradiation, the photochromic moiety can be ionized to its corresponding cation, leading to the disassembly of these vesicles. In addition, the cation can thermally recover its electrically neutral form, and the disassembled species can form vesicles reversibly on the basis of a thermal reverse reaction. The reverse reaction is temperature-controlled and can be speeded up by thermal treatment. By using various characterization techniques, e.g., transmission electron microscopy, dynamic light scattering, UV-visible spectroscopy, and NMR spectroscopy, we have confirmed that the vesicle structures can be formed, disassembled, and recovered by the above-mentioned treatments. It is anticipated greatly that this line of research may provide new insights into the mechanism behind stimuli-responsive formation and rupture of molecular assemblies, facilitating the design and synthesis of new surface active molecules for the fabrication of stimuli-responsive materials with designed functions.     

Structural changes in self-assembled monolayers initiated by ultraviolet light

Self-assembled monolayers of 2-anthracenethiol and 2-naphthalenethiol on gold (111) were irradiated with low-power UV light. Scanning tunneling microscope images recorded in situ show unusual structural changes. In the case of 2-anthracenethiol, structures measuring 4-7 nm wide and 30-40 nm in length are formed. Images taken 10 min after irradiation ceased to show further surface reorganization. With 2-naphthalenethiol SAMs, smaller structures form upon irradiation, which subsequently revert to resemble the original structure after time.     

Tunable metallization by assembly of metal nanoparticles in polymer thin films by photo- or electron beam lithography

The technique of patterning of surfaces with metal-rich structures on micro- or nanoscales was developed by assembling metal nanoparticles into a thin film of polymer in a controllable way. Palladium (Pd) nanoparticles were incorporated into a thin film of poly(methyl methacrylate) (PMMA) using palladium (II) bis(acetylacetonato), Pd(acac)(2), as a precursor vaporized in a nitrogen atmosphere. Depending upon its dose, the irradiation of a PMMA film by UV light or an electron beam (EB) enhances its reducing capability against Pd(acac)(2). This dependency on dose can be used to control the formation and assembly of Pd nanoparticles. Using this technique, binary patterns consisting of metal-rich and metal-poor regions in the polymer film can be created simply by irradiating the surface of the polymer through a binary photomask. Besides the creation of binary patterns, it is also possible to create grayscale patterns where the density of Pd nanoparticles can be tuned to provide shades of gray by the use of light with continuously modulated intensity. Because the electron beam also enhances the reducing power of PMMA against Pd(acac)(2), it is thus possible to obtain highly metallized films with nanoscale pattern features. The PMMA film can be selectively removed by oxygen plasma treatment or by pyrolysis. Thus, highly metallized surfaces with binary or grayscale patterns can be obtained by selective removal of the PMMA films. The metallized regions possess relatively high resistivity against CF(4) plasma compared to the bare silicon surface; therefore, the metallized surface patterns can be transferred onto the underlying silicon substrate by CF(4) plasma treatment. Because of the nanosize effect of metal nanoparticles, the thermal treatment at 900 degrees C, which is significantly lower than the melting temperature of the bulk Pd, yields continuous metallic features by binding the assembled nanoparticles.     

Polyimides with main-chain photosensitive groups: Synthesis, characterization and their properties as liquid crystal alignment layers

In this work, a series of polyimides containing main-chain chalcone groups and side-chain cinnamate or acetate groups were synthesized. In the synthetic route, three dianhydride monomers were prepared by the reactions of 1,3-dihydro-1,3-dioxoisobenzofuran-5-carbonyl chloride with 1,3-bis(4-hydroxylphenyl)prop-2-en-1-one, 1,3-bis(4-(2-hydroxyethyl)phenyl)prop-2-en-1-one, and 1,3-bis(4-hydroxyphenyl)-pent-1-en-3-one-4-en, respectively. The precursor polyimides were obtained by the polycondensation of the dianhydride monomers with 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane and the in situ imidization. After the polymerization, the final products were obtained by introducing the side groups through the reactions of the polyimide precursors with cinnamoyl chloride or acetic anhydride. The chemical structures and properties of the polyimides were characterized by elemental analysis, ¹H NMR, ¹³C NMR, FTIR, GPC, and thermal analysis. The polyimides show high thermal stability and good solubility in aprotic polar organic solvents. The polyimides can undergo sensitive [2+2] photocycloaddition reaction upon the UV light irradiation. After irradiation with linearly polarized UV light, the polyimide thin films can induce 5CB liquid crystal molecules to homogeneously align in the liquid crystal cells. Both the alignment ability and pretilt angles of the molecular orientation depend on the chemical structures of the polyimides.     

Visible light-induced degradation of ethylene glycol on nitrogen-doped TiO2 powders

The photocatalytic degradation processes of ethylene glycol (EG) during the UV or visible light irradiation of pure anatase and nitrogen (N)-doped TiO2 powders (TiO(2-x)N(x), x = 0, 0.002, 0.003, and 0.007) were investigated using time-resolved diffuse reflectance (TDR) and solid-state NMR spectroscopies. The TDR spectra and time traces observed for the charge carriers indicated that the scavenging of photogenerated holes (h+) by EG occurred during the 355-nm laser photolysis of the N-doped TiO2 powders, while no direct oxidation reaction of EG by h+ occurred during the 460-nm laser photolysis, although the charge carriers were sufficiently generated upon excitation. The solid-state magic-angle spinning (MAS) NMR measurements revealed that EG is preferentially chemisorbed on the surface of the N-doped TiO2 powders, in contrast to the pure TiO2, and degrades under visible light irradiation.     

Synthesis,characterization and photocatalytic properties of CaNb2O6 with ellipsoid-like plate morphology

Ellipsoid-like two-dimensional (2D) plates of calcium niobate (CaNb₂O₆) were synthesized via the hydrothermal route without any surfactants or templates by controlling the reaction conditions, viz. the pH value, reaction time and temperature. The prepared powders were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), fluorescence spectroscopy, and diffuse reflectance UV–vis spectroscopy. It was found that the plates were consisted of uniaxially aligned nanorods and can absorb UV light with wavelengths of less than 340 nm. Compared with the powder of the same material prepared by the solid-state reaction method, the ellipsoid-like 2D plates exhibited a much lower room temperature luminescence intensity and higher photocatalytic activity for the degradation of Rhodamine B dye solution under UV light irradiation. The enhanced photocatalytic activity of the plates was assigned to their higher optical absorption capability, higher diffusion rate of charge carriers and higher surface area resulting from their reduced dimensionality.