Fast-scan voltammetry of cyclic nitroxide free radicals

Fast-scan cyclic voltammetry at carbon fiber microelectrodes is used to detect the cyclic nitroxide 2,2,6,6-tetramethylpiperidinyl-1-oxy free radical (TEMPO) and three analogs. The electrochemical behavior of the TEMPO analogs at unmodified carbon fiber electrodes is found to differ greatly from their behavior at glassy carbon electrodes. After the electrode is coated with the polymer Nafion, the electrodes exhibit increased sensitivity to TEMPO and 4-amino-TEMPO. Voltammograms of the nitroxides at Nafion-coated electrodes indicate that the oxidized form (oxoammonium ion) and the free radical form have greatly different mobilities through the polymeric coating. Response times to changes in nitroxide concentration vary from subsecond at bare electrodes (all four analogs) and 4-hydroxy-TEMPO at modified electrodes to 1-3 s for TEMPO and 4-amino-TEMPO at modified electrodes. The detection limit for 4-amino-TEMPO is 50 μM at an unmodified electrode and 5 μM at a Nafion-coated carbon fiber electrode. The sensitivity of the Nafion-modified electrode to TEMPO, 4-hydroxy-TEMPO, and 4-amino-TEMPO can be improved by choosing a resting potential at which the oxoammonium ion form of the nitroxide is preconcentrated into the Nafion film. Using fast-scan cyclic voltammetry and the modified carbon fiber electrodes, the reaction of two nitroxide free radicals with ascorbate can be monitored. This work shows that fast-scan voltammetry at microelectrodes is a sensitive method that can be used to follow reactions of cyclic nitroxide free radicals in solution.     

Dynamic hologram recording characteristics in DuPont photopolymers

Hologram formation and diffusion reactions in photopolymer films are examined at different stages of exposure and at different spatial frequencies. Different properties of the grating formation process are evaluated from efficiency data, including the relative rates of diffusion and photoinitiated polymerization, dye absorption, and residual efficiency enhancement after UV curing. It was also found that gratings with larger periods (~1.4 mum) are susceptible to erasure effects with postexposure laser illumination. In addition, crossed gratings were found to have an extended dynamic range. This effect can have a significant impact on the number of holograms formed with rotational or peristrophic multiplexing.     

Application of a photopolymer to a holographic reflector for reflective liquid-crystal displays

A photopolymer for fabrication of volume-type transmission holograms, which are used primarily on the holographic reflector for reflective LCD's, is reported. This photopolymer consists of bisphenol-type epoxy resin and an acrylic monomer with diaryliodonium salt and 3-ketocoumarin as a complex initiator. The chemistry of the imaging formation is based on the radical polymerization of the monomer initiated by a holographic exposure, followed by the cationic polymerization of epoxy resin by UV exposure after postexposure baking. The yellowish color of the hologram derivatives that resulted from the sensitizing dye and from the photospeed were improved to satisfy the specifications for the holographic reflector. The holographic reflector now gives brighter images.     

三元巯基/乙烯基硅氮烷UV固化制备聚合物陶瓷前驱体

采用差光量热扫描研究了三元巯基化合物与乙烯基硅氮烷紫外光固化特性,结果表明,随着光引发剂浓度和辐照强度的增加,体系聚合速率增大,体系终止方式以自由基双基偶合终止为主。聚合反应为一级,且聚合速率与乙烯基浓度有关,而与巯基浓度无关。对制备的聚合物陶瓷前驱体的基本性能进行分析表明,玻璃化转变温度随巯基化合物用量的减少而降低,在巯基-乙烯基硅氮烷等摩尔比时,体系的固化度最大。     

可见激光立体光造型树脂协同引发体系引发机理的研究

用紫外／可见光谱及荧光／磷光光谱研究了在514nm波长下能引发丙烯酸－环氧树脂聚合的由染料，紫外光引发剂，叔胺组成的协同引发体系的引发机理，染料吸收可见光被激发，其激发三线态与叔胺形成激基复合物，并由此生成叔胺自由基，叔胺自由基与紫外引发剂发生电子转移作用生成活性更大的自由基引发聚合。     

Silver-nanoparticle immobilized initiator and co-initiators for free radical polymerization

The specific properties of silver-nanoparticle immobilized initiator and co-initiators for free radical polymerization were studied. The silver-nanoparticle immobilized benzophenone photoinitiates the free radical polymerization in both UV and visible regions. The photoinitiation ability of Bp-MPCs in visible region suggests a possible two-photon action even at low intensity of an incident light. The co-initiation process by MA-MPCs is more efficient in comparison to the co-initiation observed for corresponding free mercaptoamino acid. This behavior can be attributed to: (i) specific interaction of sulfur electron with surface plasmon electrons that make an electron transfer from mercaptoamino acid to excited electron acceptor more efficient, or (ii) to a locally higher concentration of electron donor (in the ligand shell) in comparison to classical a single-phase solution.     

三元巯基／乙烯基硅氮烷UV固化制备聚合物陶瓷前驱体

采用差光量热扫描研究了三元巯基化合物与乙烯基硅氮烷紫外光固化特性,结果表明,随着光引发剂浓度和辐照强度的增加,体系聚合速率增大,体系终止方式以自由基双基偶合终止为主。聚合反应为一级,且聚合速率与乙烯基浓度有关,而与巯基浓度无关。对制备的聚合物陶瓷前驱体的基本性能进行了分析,结果表明,玻璃化转变温度随巯基化合物用量的减少而降低,在巯基-乙烯基硅氮烷等摩尔比时,体系的固化度最大。     

基于低表面能树脂的海洋防污涂料的研究进展

从基团转移聚合、阳离子聚合、阴离子聚合、活性官能团之间的反应和自由基聚合5个方面简单综述了低表面能树脂的聚合机理;详细介绍了以有机硅树脂、氟碳树脂、氟硅树脂以及不含氟硅元素树脂为基体的防污涂料;分析讨论了低表面能海洋防污涂料的控制因素;并展望了低表面能防污技术的发展方向。     

电子束作用下树脂体系的固化行为

根据电子束固化复合材料树脂体系的原理,从引入辐敏性的基团入手,合成了含硅丙烯酸酯的活性稀释剂、芳香族酰亚胺活性单体、含丙烯酸的PMR型聚酰胺酸和单官能、双官能的马来酰亚胺单体。在此基础上,对合成所得到的产物和几种环氧树脂进行了辐射交联实验,并考察与分析了不同树脂的辐射固化反应行为。与此同时对合成所得产物进行了表征,对固化物性能进行初步测试。所得研究结果,对电子束固化树脂体系的进一步研究具有重要的参考价值。      

Influence of curing agents on gelation and exotherm behaviour of an unsaturated polyester resin

A judicious choice of curing agents such as initiator and promoter and their ratio to the resin can avoid reduced gel-time and shortened exothermic reactions in applications such as liquid composite moulding processes. In this study, effects of different ratio of initiator and promoter to the unsaturated polyester resin on curing of the resin were investigated by measuring gel-time and peak exotherm using ASTM D2471 standards. Methyl ethyl ketone peroxide (MEKP) was used as an initiator and a cobalt salt was employed as an accelerator for the free radical polymerization of curing resin at ambient temperatures. It was observed that the resin gelation starts closely with the initial rise in exotherm temperature and time of gelation decreases with the increase in initiator or accelerator volume proportions. It was also found that the exotherm-peak and rate of temperature rise indicating that the curing rate increases with the initiator or accelerator proportions also increased. A nonlinear regression analysis of all gel-time and cure data were performed to quantify the dependence of curing parameters on the volume proportions of accelerator and initiator. Thus, for this polymerization initiation system, the gel-time and cure parameters can be predicted for any initiator and cobalt levels within the ranges studied.     

紫外光固化墨水应用研究新进展

UV喷墨墨水中包含着预聚物、单体、光引发剂、颜料、助剂等组分,其中预聚物是构成UV喷墨墨水组分的基本骨架,其性能对固化过程和固化膜的性质起决定作用;单体作为活性稀释剂影响墨水体系的黏度和固化速度;光引发剂的作用是吸收紫外光能量,同时产生游离基,促使油墨发生聚合反应,是光固化体系的关键组分。介绍了常见UV喷墨墨水中预聚物、单体和光引发剂的组成、特性以及最新应用研究动向。     

Synthesis of poly(styrene-b-styrenesulfonic acid) and its blend with PPO for proton exchange membrane

Poly(styrene-b-styrenesulfonic acid sodium salts) (PS-b-PSSNa) were synthesized via stable free radical polymerization (SFRP) using 2,2,6,6-tetramethyl-1-piperidinyloxy (TEMPO) radical and the block copolymers were blended with poly(2,6-dimethyl-1,4-phenylene oxide) (PPO) to prepare polymer electrolyte membranes (PEM). The ratio of block length and total molecular weight of PS-b-PSSA were varied, and weight ratio of PPO/PS-b-PSSA was also controlled. The blend membranes showed good proton conductivity, low methanol permeability, and good thermal property.     

In-situ synthesis of polymer – silica nanocomposites by living radical polymerisation using TEMPO initiator

In situ synthesis of polystyrene nanocomposites by living free radical polymerisation using intercalated TEMPO (2,2,6,6 tetramethyl piuperidine-N-oxy)-mediated chain transfer agent in the layers of montmorillonite clay is reported. An ammonium initiator to be used for nitroxide-mediated radical polymerisation (NMRP) was synthesised in a three-step procedure. The esterification of 11-bromo-1-undecanol with α-phenyl chloroacetyl chloride yielded α-phenyl chloroacetylated undecanol. Second, the chlorine groups were converted to nitroxide-mediated groups by coupling with 1-hydroxy-2,2,6,6-tetramethyl-1-piperidinyloxy (TEMPO–OH). The subsequent reaction of NMRP macroinitiator with trimethylamine produced the NMRP surface modifier. These modified clays were then dispersed in styrene (St) monomers in different loading degrees to carry out the in situ free radical polymerisation. The intercalation ability of the chain transfer agent and exfoliated nanocomposite structure were evidenced by both X-ray diffraction (XRD) spectroscopy and transmission electron microscopy. Thermal properties and morphologies of the resultant nanocomposites were also studied.     

On the UV-induced polymeric behavior of Chinese lacquer

To dry Chinese lacquer rapidly for the protection and restoration of archeological findings coated by lacquer or excavated lacquer wares and the development of new application of this lacquer, we carried out UV curing technology to improve its curing rate using a high-pressure mercury lamp as a UV source in the absence of any additional photoinitiator. The effects of mainly specific components in Chinese lacquer sap and the role of each reactive group of urushiol, namely hydroxyl groups, hydrogen on the phenyl ring, and olefins in the side chain, in the course of UV exposure were well-investigated. The UV-cured Chinese lacquer films were also characterized by FT-IR, (1)H NMR, SEM, TGA, and Py-GC/MS. The results showed that urushiol was the main component to form Chinese lacquer films, and decomposed to generate the urushiol semiquinone radicals, which sequentially induced the polymerization of Chinese lacquer by radical polymerization, as well as radical substitution under UV irradiation. In addition, the TG analysis suggested that polysaccharide and glycoproteins were integrated with the UV-cured films by covalent bonding. Furthermore, this method could be suitable to fast cure other phenol bearing long aliphatic unsaturated chain, such as CNSL.     

大分子链转移剂活性对聚合物分散液晶电光性能的影响

采用可逆加成-断裂链转移(RAFT)、引发转移终止(Iniferter)、反向原子转移自由基聚合(RATRP)等活性自由基聚合方法,合成了分子量相近而带有不同端基的大分子链转移剂。通过紫外光聚合诱导相分离法制备聚合物分散液晶(PDLC)膜。通过研究大分子链转移剂光引发活性,发现采用RAFT聚合制备的大分子链转移剂具有较高的光活性,带有Iniferter活性基团的大分子链转移剂光活性很低。对不同大分子链转移剂制备的PDLC膜的电光性能进行比较,发现采用RAFT法合成的具有高光活性的大分子链转移剂能够使PDLC膜具有较高的开态透光率和较低的驱动电压。加入大分子链转移剂会导致PDLC记忆效应升高。     

QCAR models to predict wild mushrooms radical scavenging activity, reducing power and lipid peroxidation inhibition

Wild mushrooms have become attractive as a source of physiologically beneficial compounds including antioxidants such as phenolic compounds and tocopherols. The concentrations of antioxidant compounds (phenolics and α-tocopherol) and EC₅₀ values of antioxidant activity (concentration required to achieve 50% of radical scavenging activity and lipid peroxidation inhibition, or 0.5 of absorbance in reducing power) were analyzed by partial least square (PLS) regression analysis. Three QCAR (Quantitative Composition-Activity Relationship) models were constructed and their robustness and predictability were verified by internal and external cross-validation methods. Antioxidant activity correlated well with phenolics and α-tocopherol contents, the major antioxidants in wild mushrooms. The models proved to be useful tools in the prediction of mushrooms radical scavenging activity, reducing power and lipid peroxidation inhibition.     

柔印橡胶版和感光树脂版印刷性能对比实验

目的比较柔印感光树脂版和橡胶版的表面特性,分析影响版材油墨传输性能和图像再现的原因。方法通过表面能、硬度和粗糙度来表征印版的表面特性,制作相同加网线数的2种版材;在相同的印刷条件下,通过分光光度计和显微镜分析2种版材的油墨转移和图文再现特性。结果感光树脂版表面能比橡胶版高,但橡胶版表面粗糙度比感光树脂版大。从印刷效果来看,感光树脂版的油墨转移效果更好,实地油墨密度更高,而橡胶版的网点扩大程度更小。采用UV油墨印刷时,感光树脂版的印刷反差略高,而采用水性油墨印刷时,两者的印刷反差基本相同。此外,橡胶版比感光树脂版可实现更精确的线条和文字。结论针对特定柔性版,可通过分析研究印版的表面特性,为印刷工艺合理选择版材。     

一种可聚合光引发剂的合成及性能

以2-羟基-2-甲基-1-苯基丙酮、异佛尔酮二异氰酸酯和丙烯酸羟乙酯合成了一种可聚合紫外光引发剂。用红外光谱、核磁共振谱和紫外-可见吸收光谱对合成产物进行了分析和表征。通过综合热分析仪(Photo-DSC)研究了合成产物和2-羟基-2-甲基-1-苯基丙酮在光固化体系中的引发效率及其固化后的相对迁移率。结果表明,合成的产物为目标可聚合紫外光引发剂,将其添加在紫外光固化体系中,随着添加量从3%增加到15%,引发效率逐渐增强。按照相同自由基浓度条件计算,12%合成产物的引发效率接近于5%1173,但是其固化过程中的迁移率却不到1173的10%。     

Raman spectroscopy for the characterization of the polymerization rate in an acrylamide-based photopolymer

Investigations of polymerization rates in an acrylamide-based photopolymer are presented. The polymerization rate for acrylamide and methylenebisacrylamide was determined by monitoring the changes in the characteristic vibrational peaks at 1284 and 1607 cm(-1) corresponding to the bending mode of the CH bond and CC double bonds of acrylamide and in the characteristic peak at 1629 cm(-1) corresponding to the carbon-carbon double bond of methylenebisacrylamide using Raman spectroscopy. To study the dependence of the polymerization rate on intensity and to find the dependence parameter, the polymerization rate constant is measured at different intensities. A comparison with a commercially available photopolymer shows that the polymerization rate in this photopolymer is much faster.     

Post-Trapping Derivatization of Radical-Derived EPR-Silent Adducts: Application to Free Radical Detection by HPLC/UV in Chemical, Biochemical, and Biological Systems and Comparison with EPR Spectroscopy

Free radicals are conventionally detected by electron paramagnetic resonance (EPR) spectroscopy after being trapped as spin adducts. Albeit this technique has demonstrated utmost efficacy in studying free radicals, its application to biological settings is intrinsically hampered by the inevitable bioreduction of radical-derived paramagnetic adducts. Herein, we describe a reliable technique to detect and quantify free radical metabolites, wherein reduced alkyl- and phenyl-5,5-dimethyl-1-pyrroline N-oxide (DMPO) adducts are converted into ultrastable N-naphthoate esters. To mimic the ubiquitous in vivo microenvironment, bioreductants, exogenous thiols, and sodium borohydride were studied. Nitroxyl reduction was confirmed using EPR and triphenyltetrazolium chloride. The formation of the N-naphthoyloxy derivatives was established by liquid chromatography/mass spectrometry (LC/MS). The derivatives were chromatographed using a binary eluent. HPLC and internal standards were synthesized using Grignard addition. The labeled DMPO adduct is (1) fluorescent, (2) stable as opposed to nitroxyl radical adducts, (3) biologically relevant, and (4) excellently chromatographed. Applications encompassed chemical, biochemical, and biological model systems generating C-centered radicals. Different levels of phenyl radicals produced in situ from whole blood were successfully determined. The method is readily applicable to the detection of hydroxyl radical. Analogously, DMPO, the spin trap, could be detected with extreme sensitivity suitable for in vivo applications. The developed method proved to be a viable alternative to EPR, where for the first time the reductive loss of paramagnetic signals of DMPO-trapped free radicals is transformed into fluorescence emission. We believe the proposed methodology could represent a valuable tool to probe free radical metabolites in vivo using DMPO, the least toxic spin trap.