光化学合成维生素D

本文报道了维生素D的发现以及它们的光化学合成与进展。中国科学院理化技术研究所开发了一条从胆固醇合成 7 DHC的新路线,提出了一条光化学合成维生素D3 的创新技术路线,并已经转让实施。同时还提出一条光化学合成维生素D2 的创新技术路线。     

Specific cationic photoinitiators for near UV and visible LEDs: Iodonium versus ferrocenium structures

Two iodonium salts based on a coumarin chromophore are investigated for polymerization upon light emitting diode irradiations (LEDs). They work as one‐component photoinitiators. They initiate the cationic polymerization of epoxides (under air) and vinylethers (laminate) upon exposure to violet LEDs (385 and 405 nm). Excellent polymerization profiles are recorded. Their efficiency is quite similar to that of a ferrocenium salt. Interpenetrating polymer networks can also be obtained through a concomitant cationic/radical photopolymerization of an epoxy/acrylate blend monomer. The light absorption properties of these new salts as well as the involved photochemical mechanisms are investigated for the first time through electron spin resonance, laser flash photolysis, steady state photolysis experiments. Molecular orbital calculations are also used to shed some light on the initiation mechanisms. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42759.     

光化学研究进展综述

主要对生物光化学、海洋光化学、环境光化学等进展进行综述,并对光化学应用和发展前景进行展望,提出了今后的重点研究方向.     

降低超大规模集成电路用高纯水中总有机碳的能量传递光化学模型

本文提出用185nm紫外线降低高纯水中总有机碳(TOC)的能量传递光化学模型.计算了水的流量、TOC的浓度、照射腔的尺寸与所需紫外光能量的关系,从而解决了在工程设计中185nm紫外灯的选择和计算方法.根据理论计算出的结果和实验十分一致,证实了本模型的正确性.使高纯水中的TOC由4200μg/l 降至0.3μg/l,是目前国内外高纯水中TOC浓度的最好水平.     

Synthesis of a PPV‐fluorene derivative: Applications in luminescent devices

Synthesis of a polyfluorene/poly(p‐phenylene vinylene) derivative, the Poly [(9,9′‐di‐hexylfluorenediylvinylene‐alt‐1,4‐phenylenevinylene)‐co‐((9,9′‐(3‐t‐butylpropanoate) fluorene‐1,4‐phenylene)] (LaPPS 42) was performed following Wittig and Suzuki routes. Polyfluorenes and derivatives have been used in electroluminescent devices, and the synthesis described here has the advantage in pave the way to get distinct structures having different emission spectra. An extensive study of its electrochemical, thermomechanical, optical, and structural properties was carried out, as well as its application in electroluminescent devices. Polymer light‐emitting diodes (PLEDs) and polymer light‐emitting electrochemical cells (PLECs) were built using LaPPS 42 as active layer, and their electric and optical characterizations confirm they have a potential as active element in electroluminescent devices. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42579.     

Polypropylene plasticization and photodegradation with a TiO2/poly(ethylene oxide)/methyl linoleate paint photocatalyst system

The photodegradation of polypropylene (PP) film was performed by a TiO₂/polyethylene oxide (PEO)/plant oil paint photocatalyst system. The photodegradation underwent two stages of development as follows: Initially PP reacted with linoleic acid radical originated from the photoreaction of plant oil component. Second, the linoleic acid graft‐polymer was decomposed, and then PP chain scission was caused. The process was studied using methyl linoleate (ML) in detail. The melting point of the 24 h‐photodegraded PP slightly decreased, and those of the 48 h‐ and 96 h‐ones drastically did as compared with the pristine PP. The crystallinity (χ_c) decreased at the 48 h photodegradation time and drastically increased at the 96 h one. The 24 h‐photodegraded PP showed the 77% Young's modulus, 88% tensile strength, and 103% strain at break values to those of the pristine PP. The ML graft‐polymerization and decomposition brought about the PP plasticizing and chemi‐crystallization, causing the PP degradation. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 39909.     

基于阳极氧化法的TiO2纳米管制备及生成过程分析

运用阳极氧化法制备TiO₂纳米管,探讨了TiO₂纳米管紫外光催化净化头孢噻肟钠抗生素废水的效果,采用扫描电镜（SEM）和X射线衍射仪（XRD）对TiO₂纳米管进行了表征分析。SEM结果显示,制备的TiO₂材料表面呈阵列排布的多孔状,内径大小均匀,管径分布在30~45nm之间,管阵列呈蜂窝状,与钛板表面垂直,对比煅烧前后的TiO₂纳米管XRD图,发现煅烧后样品的XRD图出现了TiO₂锐钛矿型特征衍射峰和金红石型特征衍射峰。讨论了TiO₂纳米管的生成机理,认为纳米管的形成过程主要有最初氧化层的形成、孔核的形成、由孔核演变成微孔、微孔生长并出现空隙、形成纳米阵列管过程。     

Anticorrosion reinforcement of waterborne polyacrylate coating with nano-TiO2 loaded graphene

Photocathodic protection coatings have been widely applied in various areas such as ship and architectural protection, or chemical industry. In this work, a composite of titanium dioxide loaded with reduced graphene oxide (RGO/TiO₂) was prepared and used as filler on waterborne polyacrylate (PA) coating to reinforce the metal protection against corrosion. Compared with the current filler of zinc phosphate used for anticorrosive coating, the photoelectrochemical properties of RGO/TiO₂-PA coating exhibit improved photocathodic protection under visible light illumination since RGO/TiO₂ composite has significant superiority in enhancing metal protection due to its dispersion, micropore blocking ability, and photoelectrochemical conversion performance. The mechanism of anticorrosion reinforcement of RGO/TiO₂-PA coating was hypothesized that graphene provides an extrabarrier layer to obstruct corrosive in dark condition and photocathodic protection under lighting. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48733.     

Electrospinning preparation,characterization, and enhanced photocatalytic activity of an Silicotungstic acid (H4SiW12O40)/poly(vinyl alcohol)/poly(methyl methacrylate) composite nanofiber membrane

Silicotungstic acid (H₄SiW₁₂O₄₀)/poly(vinyl alcohol) (PVA)/poly(methyl methacrylate) (PMMA) composite nanofiber membranes were prepared by an electrospinning technique. A PMMA emulsion was mixed with PVA and H₄SiW₁₂O₄₀ evenly in water (electrospinning solvent). The configuration and elemental composition of the membranes were characterized by scanning electron microscopy, Fourier transform infrared spectroscopy, and X‐ray photoelectron spectroscopy. The results indicate that H₄SiW₁₂O₄₀ with an intact Keggin structure existed in the composite membrane. The as‐prepared H₄SiW₁₂O₄₀/PVA/PMMA membranes exhibited enhanced photocatalytic efficiency (>84%) in the degradation of methyl orange (MO); it outperformed H₄SiW₁₂O₄₀ powder (4.6%) and the H₄SiW₁₂O₄₀/PVA nanofiber membrane (75.2%) under UV irradiation. More importantly, the H₄SiW₁₂O₄₀/PVA/PMMA membranes could be easily separated from the aqueous MO solution, and the photocatalytic efficiency of the membranes decreased inappreciably after three photocatalytic cycles. This may have been due to the enhanced water tolerance of the membranes and the stability of H₄SiW₁₂O₄₀ in the membranes. The photocatalytic process was driven by the reductive pathway with a much faster degradation rate because of the presence of PVA. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43193.     

Xanthene dyes/amine as photoinitiators of radical polymerization: A comparative and photochemical study in aqueous medium

The efficiency of several xanthene dyes as photoinitiators of the free radical polymerization in aqueous medium was evaluated. These results show that dyes with triplet quantum yield higher than 0.1 present similar efficiencies, independently of their different chemical structure. A detailed study of the photophysics of the dyes under the polymerization conditions was carried out using laser time-resolved spectroscopies. These studies show that the active radicals are those which formed in the interaction of excited triplet state of the dye with the amine through an electron transfer process. In spite of this, the photoinitiation efficiency is not correlated with the triplet quantum yield. Also, the photophysics studies show that the quantum yield of the different pathways of the decomposition of the charge transfer intermediate is an important parameter to predict the efficiency of these photoinitiator systems. The experimentally measured active radical formation is well correlated with that calculated from the polymerization rate. The presence of heavy atoms in the xanthene ring increases the triplet quantum yield, but decreases the active radical yield, and then the polymerization rate.