Photochemical Synthesis and Magnetic Property Investigation of a Mixed-valence 11-Tungstophosphate

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Silicon-carbon unsaturated compounds. 73. Photolysis of cis- and trans-1,2-dimethyl-1,2-diphenyl-1,2-disilacyclohexane in the presence of tert-butyl alcohol and acetone

Irradiation of cis-1,2-dimethyl-1,2-diphenyl-1,2-disilacyclohexane (1a) in the presence of tert-butyl alcohol in hexane with a low-pressure mercury lamp bearing a Vycor filter proceeded with high stereospecificity to give cis-2,3-benzo-1-tert-butoxy-1,4-dimethyl-4-phenyl-1,4-disilacyclooct-2-ene (2a), in 33% isolated yield, together with a 15% yield of 1-[(tert-butoxy)methylphenylsilyl]-4-(methylphenylsilyl)butane (3). The photolysis of trans-1,2-dimethyl-1,2-diphenyl-1,2-disilacyclohexane (1b) with tert-butyl alcohol under the same conditions gave stereospecifically trans-2,3-benzo-1-tert-butoxy-1,4-dimethyl-4-phenyl-1,4-disilacyclooct-2-ene (2b) in 41% isolated yield, along with a 12% yield of 3. Similar photolysis of 1a and 1b with tert-butyl alcohol-d₁ produced 2a and 2b, respectively, in addition to 1-[(tert-butoxy)(monodeuteriomethyl)(phenyl)silyl]-4-(methylphenylsilyl)butane. When 1a and 1b were photolyzed with acetone in a hexane solution, cis- and trans-2,3-benzo-1-isopropoxy-1,4-dimethyl-4-phenyl-1,4-disilacyclooct-2-ene (4a and 4b) were obtained in 25% and 23% isolated yield. In both photolyses, 1-(hydroxymethylphenylsilyl)-4-(methylphenylsilyl)butane (5) was also isolated in 4% and 5% yield, respectively. The photolysis of 1a with acetone-d₆ under the same conditions gave 4a-d₆ and 5-d₁ in 18% and 4% yields.     

硅、氮共掺杂碳点荧光粉的制备及发光性能

采用N-苯基对苯二胺和3-氨基丙基三甲氧基硅烷为原料,通过光化学催化法合成了高荧光强度的硅、氮共掺杂碳点（Si/N-CDs）。通过透射电子显微镜（TEM）、X射线光电子能谱（XPS）、荧光光谱、X射线衍射（XRD）和红外光谱（FT-IR）等对Si/N-CDs进行了表征。制备的 Si/N-CDs形貌呈球形,平均直径约6.45 nm,在365 nm紫外光照射下发明亮的蓝绿色荧光,量子产率可达30.8%,连续30 d测试Si/N-CDs均保持高的荧光强度。用Si/N-CDs替代传统的红/绿/蓝三基色稀土荧光粉中的蓝/绿稀土荧光粉,并与红色荧光粉（Sr,Ca）AlSiN₃∶Eu²⁺复合制备白光二极管（White Light Emitting Diode, WLED）。在60 mA电流下运行WLED,可实现86.9的高显色指数和7.76 lm/W的发光效率,色坐标是（0.3773, 0.3734）,色温为4062 K,并且色点位于黑体普朗克轨迹上,表明制备的WLED可以产生高质量的照明效果。硅、氮共掺杂碳点具有简便的制备方法和优异的光学性质,并能够代替蓝/绿色稀土荧光粉与红光荧光粉复合制备高质量照明的WLED,扩展了碳点在发光器件中的应用。同时,Si/N-CDs兼具低毒性、稳定的光学性质和简单的合成工艺,使其在蓝色和绿色稀土荧光粉的替代中具有潜在的商业应用前景。     

A critical review on photochemical conversions in flow analysis

Photochemical conversions are cost-effective and environmental friendly processes that require mild experimental conditions and avoid generation of highly acidic wastes. Treated samples are then compatible with most of the analytical techniques. These characteristics become more relevant when the photoconversions are accomplished to flow analysis, thus allowing exploitation of incomplete reactions, the effective use of the photogenerated unstable radicals and in-line sample treatment. Decreasing of reagent consumption and waste generation, sample processing in a closed environment, and improvement of efficiency of the photochemical processes are other inherent advantages. These aspects are critically reviewed in this article, which emphasizes applications to fractionation and speciation analysis, photo-induced luminescence, miniaturization, and in-line waste treatment. Design of flow-through photochemical cells, use of auxiliary reagents in homogeneous and heterogeneous media, and configurations of flow manifolds are also discussed.     

Direct Arylation of 5‐Iodouracil and 5‐Iodouridine with Heteroarenes and Benzene via Photochemical Reaction

A method for the direct arylation of 5‐iodouracil and 5‐iodouridine was found to proceed in moderate yields. By irradiating mixtures of 5‐iodouracil or 5‐iodouridine and a series of five‐membered heterocycles such as 1H‐pyrrole, furan, 2‐methylfuran, 1‐methyl‐1H‐pyrrole, thiophene, as well as benzene in MeCN/H₂O with a Hg lamp, 5‐aryluracils and 5‐aryluridines were synthesized. The reaction proceeded smoothly without the requirement of adding any transition metals or ligands.     

二氟沙星在中性水溶液中的光化学性质

对二氟沙星在中性水溶液中的光化学性质进行了研究. 在pH值为7.17 的水溶液中二氟沙星的紫外吸收峰位于273 nm (摩尔消光系数ε=33000 dm³·mol^-1·cm^-1), 323 nm (ε=15500 dm³·mol^-1·cm^-1), 335 nm (ε=15500 dm³·mol^-1·cm^-1)处. 荧光吸收和发射光谱均显示二氟沙星具有pH效应, 其pK_a(电离平衡常数)测定分别为5.9 和9.8. 二氟沙星的荧光量子产额较低, 在pH=3.00 时达到最大值, 为0.06. 同时对二氟沙星在中性水溶液中的激光光解和脉冲辐解进行详细研究. 激光光解研究发现在水溶液中二氟沙星的三重激发态位于620nm, 其摩尔消光系数为7900 dm³·mol^-1·cm^-1. 通过能量转移的方法得到其三重激发态的能量为263.5 kJ·mol^-1,三重激发态的量子产额为0.21. 在激光激发下, 二氟沙星进行单光子电离其量子产额为0.02. 脉冲辐解研究表明二氟沙星可以与水合电子(e_aq^-)及羟基自由基(·OH)快速反应, 其二级反应动力学常数分别为1.72×10¹⁰和1.0×10¹⁰ dm³·mol^-1·s^-1. 本文对二氟沙星光化学性质的研究有助于确定其光敏毒性的产生机理.     

二氟沙星在中性水溶液中的光化学性质(英文)

对二氟沙星在中性水溶液中的光化学性质进行了研究.在pH值为7.17的水溶液中二氟沙星的紫外吸收峰位于273 nm(摩尔消光系数ε=33000 dm3·mol-1·cm-1),323 nm(ε=15500 dm3·mol-1·cm-1),335 nm(ε=15500 dm3·mol-1·cm-1)处.荧光吸收和发射光谱均显示二氟沙星具有pH效应,其pKa(电离平衡常数)测定分别为5.9和9.8.二氟沙星的荧光量子产额较低,在pH=3.00时达到最大值,为0.06.同时对二氟沙星在中性水溶液中的激光光解和脉冲辐解进行详细研究.激光光解研究发现在水溶液中二氟沙星的三重激发态位于620nm,其摩尔消光系数为7900 dm3·mol-1·cm-1.通过能量转移的方法得到其三重激发态的能量为263.5 kJ·mol-1,三重激发态的量子产额为0.21.在激光激发下,二氟沙星进行单光子电离其量子产额为0.02.脉冲辐解研究表明二氟沙星可以与水合电子(e-aq)及羟基自由基(·OH)快速反应,其二级反应动力学常数分别为1.72×1010和1.0×1010dm3·mol-1·s-1.本文对二氟沙星光化学性质的研究有助于确定其光敏毒性的产生机理.     

聚乙二醇光化学法制备金纳米微粒及共振散射光谱研究

采用共振散射光谱、紫外-可见吸收光谱、透射电镜对聚乙二醇(PEG)-Au3+纳米光化学反应进行了研究。讨论了金纳米粒子合成条件的影响,发现金纳米粒子的尺寸与PEG分子量大小有关。建立了一个利用不同分子量PEG制备一系列粒径为6～60 nm金纳米粒子的光化学合成新方法。根据PEG分子的空间位阻、疏水性等解释了PEG分子量不同而获得不同粒径金纳米粒子的原因。提出了一个合理的纳米光化学反应机理。     

聚二甲基硅氧烷微流控芯片的紫外光照射表面处理研究

研究了紫外光化学表面改性对聚二甲基硅氧烷(PDMS)微流控芯片的片基间粘接力及毛细管通道电渗流性能的影响.PDMS片基经紫外光射照后,粘接力增强,可实现PDMS芯片的永久性封合,同时亲水性得到改善,通道中的电渗流增大.与文献报道的等离子体表面处理方法比较,采用紫外光表面处理,设备简单,操作方便,耗费少,是一种简单易行的聚二甲基硅氧烷芯片表面处理方法.     

二氧化硫与戊烷的气相光化学反应研究

Baclock等^[1]的研究表明,在SO2与烃的光化学反应体系中,单重态SO2通过系间窜跃转化为三重态SO2参与光化学反应,Penzhorn等^[2,3]的研究表明,在SO2与C4以下气相烃的光化学反应中有多种产物存在,产物的复杂性预示反应为自由基链反应。Smith等^[4]等认为体系中存在烃的逐步氧化,同时证明SO2与烷烃光化学反应中自由基链反应的重要性,文献报道的研究多以凝聚态产物为切入点^[5],为避免器壁对光化学反应的影响,本文以气相物质为研究对象,对挥发性烷烃中结构最简单的戊烷与二氧化硫的光化学反应的气相反应产物,反应机理和影响因素等进行了研究。