新型锍鎓盐类光生酸剂的合成及产酸性能研究

成功合成了两种新型锍鎓盐类光生酸剂,其结构经¹1HNMR和MS分析确认,并对其基本物性及在405、365nm光下乙腈溶液中的分解及产酸性能进行了研究,通过计算得出了分解及产酸量子产率.结果表明,两种化合物有较高的热分解温度和在常用有机溶剂中有较好的溶解性;在405nm光源下,4-(9′-苯基蒽基)苯基三氟甲磺酸锍鎓盐(PAGS1)和4-(4′-N,N-二乙基-1′-苯乙烯基)苯基三氟甲磺酸锍鎓盐(PAGS2)的分解量子产率分别为10%和15%,产酸量子产率为8.1%和13%;但在365nm光源下,分解及产酸量子产率均很低,说明两种光生酸剂对于405nm波长的光较敏感,适宜作为405nm光源下的光生酸剂.     

磺酸肟酯类光产酸剂的制备及性能研究

本文合成了4种磺酸肟酯类非离子型光产酸剂,用核磁氢谱确认了产物结构,并测试了其热稳定性、紫外吸收特性及产酸效率.结果表明,合成的4种磺酸肟酯类光产酸剂在350-450 nm和深紫外区(DUV,248 nm)都有很好的吸收,在420 nm波段曝光下,(5-对三氟甲基苯磺酸酯亚胺-5H-噻吩-2-亚胺)-苯乙腈(P-2)产酸率最高,可达0.96;(5-对甲基苯磺酸酯亚胺-5H-噻吩-2-亚胺)-苯乙腈(P-1)在365 nm和420 nm两个波段下,均有较高的产酸率.利用实时红外(RT-IR)研究了相同浓度下4种光产酸剂对乙烯基醚化合物引发的光聚合动力学,同时研究了光产酸剂浓度对光聚合反应的影响,发现产酸剂浓度为2%时,光照30 s乙烯基醚化合物的双键转化率(DC%)即能达到80%.     

还原态脒类LED光产碱剂的合成及性能研究

光产碱剂作为光固化材料体系中的关键组分,对光固化速率及固化材料性能有重要影响。本文以氧杂蒽酮作为生色团,脒类化合物DBN作为强碱基团,设计并合成了一种新型单组分氧杂蒽酮还原态脒类光产碱剂,并系统探究了其光物理和光化学行为。结果表明,氧杂蒽酮还原态脒类光产碱剂在345 nm区域具有较强吸收,光解后释放的强碱DBN可有效引发巯基-环氧体系聚合。与商品化苄基还原态脒类光产碱剂相比,氧杂蒽酮生色团的引入使光产碱剂的吸收波长红移,能更好地匹配365 nm LED光源;与离子型硫杂蒽酮光产碱剂相比,氧杂蒽酮还原态脒类光产碱剂在光解过程中不产生二氧化碳,且催化效率更高,具有良好的应用前景。     

硫杂蒽酮类光产碱剂的合成及其光化学性能研究

以硫代水杨酸和苯硫乙酸为原料,通过两步法成功合成了一种新型的单组分硫杂蒽酮类光产碱剂。利用核磁氢谱、核磁碳谱和高分辨率质谱对光产碱的结构进行了表征,通过稳态光解及电子自旋共振波谱等对光解产物进行了系统研究。该光产碱剂在400nm附近有较强的吸收,可有效引发巯基-环氧光聚合,其引发活性优于文献报道的高效光产碱体系。     

UV/Vis-LED激发的香豆素吡啶鎓盐光引发剂的合成及性能

设计合成了3种基于香豆素骨架的紫外-可见发光二极管(UV/Vis-LED)可激发的新型吡啶鎓盐光引发剂, 并研究了这3种香豆素吡啶鎓盐的构效关系及其作为单组分自由基光引发剂在丙烯酸酯体系中的光引发活性. 紫外-可见吸收光谱分析表明, 这3种香豆素吡啶鎓盐在300~400 nm区域有较强吸收. 在LED@365 nm和LED@405 nm光源辐照下, 研究了3种光引发剂的稳态光解和光聚合动力学. 研究表明, 这3种香豆素吡啶鎓盐光引发剂在相应光辐照下都具有较好的光解速率. 此外, 3种光引发剂对丙烯酸酯都具有较好的引发活性. 构效关系研究表明, 吡啶环4号位引入推电子的甲氧基会使其引发丙烯酸酯单体聚合的活性降低; 而引入吸电子的乙酰基会使其引发丙烯酸酯单体聚合的活性增加. 差示扫描量热(DSC)实验表明, 此类吡啶鎓盐光引发剂具有较好的热稳定性. 当3种光引发剂与丙烯酸单体混合时可提升体系的热稳定性; 通过电子自旋共振(ESR)证明了活性物种的产生, 并对该类引发剂的引发机理进行了探讨.     

硫鎓盐产酸剂的合成及其产酸效率

合成了6种适用于248 nm光致抗蚀剂的硫鎓盐产酸剂,其中吩噻(噁)体系的产酸剂为自行设计合成. 利用IR、H NMR、UV等测试技术进行了结构表征和紫外吸收测定,各化合物的最大紫外吸收在250～285 nm之间,吸收域较宽,适用性较强.同时,利用酸敏染料罗丹明B遇酸异构变色的特点,使用紫外!可见分光光度计定量检测了6种产酸剂在乙腈溶剂中的产酸效率,其中硫杂蒽酮系列的产酸剂产酸性能最好. 最后使用荧光追踪法研究了溶剂极性对产酸效率的影响,发现产酸剂的产酸性能同溶剂的选取密切相关,随着溶剂极性的减小,产酸效率随之降低. 对6种硫鎓盐的产酸效率检测结果可以为产酸剂进一步用于248 nm光致抗蚀剂配方提供详细的参考.     

三嗪类化合物的合成及其产酸性能研究

合成了一系列的三嗪类光生酸剂1a—1e,确定了它们的结构,并对1e在乙腈溶剂中365和405nm光下的曝光分解产酸性能进行了初步的定量研究.结果表明,在测定浓度范围内分解量子产率和产酸量子产率基本上都不随浓度的变化而变化,在405nm光下比在365nm光下有更高的分解和产酸量子效率.有关这类化合物的光生酸性能与曝光波长的关系正在进一步研究中.     

193nm化学放大光刻胶研究进展

193 nm光刻胶主要有化学/非化学放大、分子玻璃和无机-有机杂化等类型。目前,商业化193 nm光刻胶基本为化学放大型,主要成分包括聚合物树脂、光致产酸剂、添加剂(碱性添加剂、溶解抑制剂等)和溶剂等。本文从光刻胶的成分出发介绍193 nm化学放大胶的研究进展,概述目前应用及研究中出现的代表性193 nm化学放大胶,总结其优缺点及未来可能的发展方向。     

非离子型产酸剂——N-羟基邻苯二甲酰亚胺对甲苯磺酸酯的合成与性能研究

以邻苯二甲酸酐、盐酸羟胺和对甲苯磺酰氯为起始原料,合成了非离子型光致产酸剂——N-羟基邻苯二甲酰亚胺对甲苯磺酸酯,对其进行了红外、核磁共振和紫外表征,测定了其化学结构、溶解性和紫外吸收等性能.结果表明,这种非离子型产酸剂较离子型产酸剂在常用溶剂中有非常良好的溶解性,并在248 nm处有好的透明性,可用于深紫外光刻工艺体系.     

含碘鎓盐光产酸剂和增感染料的化学增幅型i-线正性光致抗蚀剂

4,4’-二甲苯基三氟甲磺酸碘鎓盐可以被染料增感,在365 nm光照时分解产酸.尽管产生的酸与染料的胺基发生作用,依然能在后烘过程中催化缩醛聚合物酸敏基团的分解,但需要稍高的后烘温度和稍长的后烘时间.基于此,本文将酚醛树脂、缩醛聚合物、碘鎓盐产酸剂和染料组成了一种新型的化学增幅型i-线正性光致抗蚀剂材料,在曝光量为10...     

MUTATION AND SISTER CHROMATID EXCHANGE INDUCTION IN CHINESE HAMSTER OVARY (CHO) CELLS BY PULSED EXCIMER LASER RADIATION AT 93 nm AND 308 nm AND CONTINUOUS UV RADIATION AT 254 nm

We compared mutagenesis and sister chromatid exchange (SCE) induction by 193 nm and 308 nm pulsed excimer laser radiation with 254 nm low intensity continuous wave UV light in Chinese hamster ovary (CHO) cells in culture. The 254 nm radiation was most mutagenic of the radiations, in accordance with expectation, and also was most effective in increasing the level of SCEs. The 193 nm radiation was mutagenic at the ouabain resistance locus, but not at the HGPRT locus. However, 193 nm radiation was also strongly cytotoxic at energies producing measurable mutations. This radiation also caused a dose-related increase in SCEs. Pulsed excimer radiation at 308 nm was mutagenic at both loci, and also increased the incidence of SCEs. Comparison of the ratio of mutants/surviving cells at the D37 after radiation showed similar values for 254 nm and 308 nm at the HGPRT locus, but at the ouabain resistance locus, the ratio for the 308 nm radiation was about 5 times that for 254 nm radiation. These results indicate that some risk for mutagenesis may accompany the use of excimer radiation in the UVA region in therapeutic applications.     

Induction of Lambda Prophage by 213 nm Laser Radiation: A Quantitative Comparison with 193 nm Excimer Radiation Using Image Analysis

Abstract— We compared the DNA damage produced by radiation from two UV laser wavelengths, 213 nm and 193 nm, with that produced by noncoherent 254 nm radiation. Following irradiation of Escherichia coli BR339, a bacteriophage lambda lysogen containing the lacZ gene, prophage induction was measured by assaying for β-galactosidase. Because of the limited penetration by UV laser wavelengths an agar overlay of the lysogen was used as the irradiation target. Irradiation of 254 nm was performed in buffer suspension followed by transfer of 5 μL spots onto assay plants. Computer image analysis was used to monitor the rate of product formation, observed as an increase in optical density of the irradiated zones on assay plates. We found that the rate of product formation was a more reproducible unit of comparison than the optical density present at the end of the reaction. Although the rate of product formation was not linearly related to enzyme concentration, the data could be fit to a simple logarithmic function. Using this method, we concluded that the DNA damaging ability of 213 nm radiation was 10 times more efficient than 193 nm radiation and about 100 times less efficient than 254 nm noncoherent radiation.     

新型硫鎓盐产酸剂的合成及其产酸效率研究

本文合成了六种适用于248nm光致抗蚀剂的产酸剂,其中吩噻口恶 体系的产酸剂由本研究室自主设计合成。六种产酸剂均通过IR,HNMR,UV等进行了结构表征,并利用酸敏染料遇酸异构变色的特点定量检测了六种产酸剂的产酸效率,同时使用荧光追踪法研究了溶剂极性对产酸效率的影响,优选出了硫杂蒽酮系列的产酸剂,为进一步用于248nm光致抗蚀剂提供参考。     

XERODERMA PIGMENTOSUM FIBROBLASTS INCLUDING CELLS FROM XP VARIANTS ARE ABNORMALLY SENSITIVE TO THE MUTAGENIC AND CYTOTOXIC ACTION OF BROAD SPECTRUM SIMULATED SUNLIGHT

Abstract— The cytotoxic and mutagenic effects of broad spectrum simulated sunlight, as delivered by a Westinghouse Sun Lamp FS 20 filtered to eliminate wavelengths below 290 nm, were determined in diploid human skin fibroblasts which differ in their ability to repair pyrimidine dimers, and compared with results obtained with UV 254 nm radiation. The cell strains tested included normal fibroblasts; excision repair-deficient xeroderma pigmentosum (XP) cells from patients XP12BE (complementation group A). XP7BE (group D). and XP2BI (group G): and an XP variant patient (XP4BE) whose cells excise pyrimidinc dimers at a normal rate, but exhibit abnormal replication of DNA containing unexcised lesions. Cytotoxicity was assayed from loss of colony-forming ability. The group A cells were most sensitive to the killing effect of the Sun Lamp; the group D and G cells were slightly less sensitive; the XP variant cells showed intermediate sensitivity; and normal cells were most resistant. When the Sun Lamp survival curves for the group A, group D, the XP variant and normal cells were compared with their respective UV 254 nm survival curves, the relationships between the strains were virtually identical (i. e. the curves were related by a constant fluence modification factor). suggesting a common lesion for cell killing. The marker for mutagenesis was resistance to 6-thioguanine. The group A XP cells proved most sensitive to mutations induced by the simulated sunlight: the variant cells were intermediate; and the normal cells were the most resistant. Again, when the curves for mutations induced in these cell strains by simulated sunlight were compared with their respective 254 nm UV mutation curves, these were related by a constant fluence modification factor. suggesting a common lesion for mutagenesis. These results. taken together with published data indicating that at equicytotoxic levels of UV254 nm radiation and the filtered Sun Lamp. the number of pyrimidine dimers in the DNA of XP12BE cells was equal. support the hypothesis that the dimer is the lesion principally involved in both effects. Our data also support the hypothesis that mutations are involved in the sunlight-induced skin cancer of XP patients.     

D‐π‐a‐type oxime sulfonate photoacid generators for cationic polymerization under UV–visible LED irradiation

Four D‐π‐A‐type nonionic oxime sulfonate photoacid generators (PAGs) have been designed and synthesized for use in light‐emitting diode (LED) excitable cationic photoinitiators, in which N,N‐diphenylamino was used as electron donor with trifluoroacetophenone‐based oxime sulfonates (trifluoromethanoesulfonate and p‐toluenesulfonate) as electron acceptor and substituted fluorene and biphenyl groups as the π‐conjugated systems. PAG‐Ben‐Tol (with biphenyl and p‐toluenesulfonate) and PAG‐Flu‐Tol (with fluorene and p‐toluenesulfonate) showed high quantum yields of photoacid generation (0.33–0.50) and very good thermal stability (over 250 °C). The absorbance spectra of these PAGs were consistent with the emission spectra of commercially gained UV–visible LED light sources. The potential of these PAGs for cationic photoinitiators was tested in two cationic monomer systems. These PAGs needed low light intensity and low concentration for photopolymerization with high conversions of monomer, for example, over 80%, gained at 3.0 mW cm⁻² from 365 to 470 nm LEDs. The photochemical mechanisms of these PAGs are comprehensively investigated and discussed in detail. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2018 , 56, 1146–1154     

UV and IR absorption spectra of C3 embedded in solid para-hydrogen

This paper presents the UV and IR absorption spectroscopy of small carbon molecules of C₃ observed using a high-resolution Fourier-transform spectrometer. The C₃ molecules were produced by irradiation of dimers or larger clusters of acetylene with an ArF laser (λ=193 nm). Sharp UV absorption features with multiple structures were observed in the electronic transition of C₃. The sharp UV absorption demonstrates the potential of solid para-hydrogen as a matrix for high-resolution spectroscopy of UV–vis electronic transitions.     

Causes of Cell Death Following Ultraviolet B and C Exposures and the Role of Carotenes

Abstract— Ultraviolet B radiation (wavelength 290–310 nm) does not induce any specific lethal effects in the fungus Phy-comyces blakesleeanus , according to a heterokaryon test that responds to the nature of the lethal damage. This agent is about 10 times less lethal than UVC radiation from germicidal lamps (254 nm), but it kills cells through the same photoreactivable lesions, due to the UV absorption of DNA. Carotenes do not protect Phycomyces against UV damage, either B or C, lethal or not. This was shown by Darwinian competition experiments between strains containing very different carotene concentrations and between strains containing similar concentrations of different carotenes (phytoene, lycopene, β-car-otene). A shading effect of carotenes against UV radiation is likely, but it was insignificant under the conditions of the experiments.     

Effects of C3-aromatic heterocycles on 1,3,5-triaryl-2-pyrazoline sulfonium salt photoacid generators as light-emitting diode-sensitive cationic photoinitiators

Four 1,5-diphenyl-3-aromatic heterocyclyl-2-pyrazoline-based sulfonium salt photoacid generators (PAGs) with different aromatic heterocycles substituted on C3 atom and dimethyl sulfonium group on C5 atom were synthesized. These PAGs were highly photosensitive in the 365–425 nm light-emitting diode region, and the intramolecular charge transfer from the pyrazoline ring to sulfonium salts induced efficient photolysis and high Φ_H⁺. The heterocycles as well as their substituted positions significantly influenced the energy of the S₂ orbital, which was determined by the electrochemical and absorption properties of the PAGs. The raising of the S₂ orbital energy enlarged the energy gap of S₀–S₂ and S₁–S₂, resulting in blue shift of the absorption spectra and increase in the quantum yield of photoacid generation (Φ_H⁺), respectively. When the energy of excited electrons was higher than that of the S₂ orbital, the transition from S₀ to S₂ (π–π*) occurred before the C-S cleavage on S₁ and the PAGs showed high Φ_H⁺ values (0.52–0.72). The transition from S₀ to S₁ (π–σ*) occurred when the energy of electrons is lower than that of the S₂ orbital, and the PAGs showed low Φ_H⁺ value. The photopolymerization kinetics demonstrated that these PAGs were highly efficient cationic photoinitiators.