Mechanism of singlet-oxygen induced delayed fluorescence of bacteriopheophytin in laser excitation

The relative intensity of photosensitized phosphorescence of singlet oxygen (¹O₂) at 1270 nm (L₁₂₇₀) and¹O₂-induced delayed fluorescence (L_df) of bacteriopheophytin a (BPh) (770 nm) in air-saturated solutions of BPh in hexafluorobenzene in excitation by 337-nm pulses of a nitrogen laso is investigated. It is established that L_df≪L₁₂₇₀. The ratio of the initial intensity of delayed fluorescence and phosphorescence of¹O₂(L_df)₀/(L₁₂₇₀)₀ changed from 0.02 to 0.30 as a function of the energies of laser pulses (2.5–5.0 mJ/cm¹) and the BPh concentration (6–18 μM). As the index of quantum efficiency of the delayed fluorescence, the authors used the coefficient

Effect of Deuteration on Quasiline Electronic‐Vibrational Spectra of Phthalocyanine

Quasiline electronicvibrational spectra of fluorescence and absorption (excitation of fluorescence in selective recording) of the molecules of phthalocyanine deuterated around the periphery of benzene rings (H₂Phcd ₁₆) and the center of the macrocycle (D₂Phc) are obtained. The vibrational frequencies of the ground state are almost insensitive to this deuteration (except for vibrations with the participation of angular deformations). In excitation spectra, changes in deuteration are more pronounced due to the effects of nonadiabatic vibronic interaction of the vibrational sublevels of the S ₁ state and of the purely electronic level S ₂.     

Study on dispersion stability of copper phthalocyanine (CuPc) blue pigment in water improved by plasma treatments

Oxygen plasma was used to modify the copper phthalocyanine (CuPc) blue pigment. It is effective in improving stability of CuPc pigment in aqueous dispersion. Treatment conditions, e.g., treating time, gas pressure and discharge power, had great influence on the surface properties of pigments. X-ray photoelectron spectroscopy (XPS) indicated that the CuPc blue pigment surface was partially oxidized and polar groups including COH, COOH, C?O were incorporated. Dispersion stability of pigment in water was greatly increased. The plasma modified CuPc blue pigment was applied to on cotton fabric. Rubbing fastness and K/S value of the pigment prints were enhanced.     

1 064, 532和680 nm波长的反射-吸收复合型防护膜的研制

针对1 064, 532 和 680 nm波长激光, 以聚碳酸酯 （PC） 为镀膜基底, 钕玻璃激光中心波长为1 064 nm, 采用六分之一加三分之一膜系的反射膜系设计,以氧化锆为高折射率膜层材料,氯化酞菁铝掺杂的氧化硅为低折射率膜层材料,通过溶胶-凝胶法镀21层膜,并在多层反射膜与PC基底之间插入张力匹配层,实现了钕玻璃激光器1 064 nm主频和532 nm二倍频波长激光的反射,以及680 nm波长红宝石激光的同时吸收,1 064,532和680 nm波长处的透射率分别为1.67％,18.24％和2.4％。     

I2-Promoted Intramolecular Oxidative Cyclization of Butenyl Anilines: A Facile Route to Benzo[b]azepines

A metal-free approach for the synthesis of seven-membered N-heterocycles has been developed by the I₂-promoted intramolecular cross-coupling/annulation of butenyl anilines. This cyclization reaction involves C−H activation and C−C bond formation and exhibits good functional group tolerance. A series of benzo[b]azepine derivatives are obtained in moderate to good yields.     

Highly stereoselective synthesis of (Z)-3-methoxy-1-methyleneisoindoles via DMAP catalyzed cyclization of methyl 2-alkynylbenzimidates

A DMAP (4-dimethylaminopyridine) catalyzed cyclization of methyl 2-alkynylbenzimidates has been developed, which affords 3-methoxy-1-methyleneisoindoles with excellent Z-stereoselectivity under mild and transition-metal-free conditions. The (Z)-3-methoxy-1-methyleneisoindole products can be converted to corresponding 3-amino-1-methyleneisoindoles, 3-methoxy-isoindoles, 3-methyleneisoindolinones and isoindolinones with high efficiency.     

酞菁铜与Q-CdS超微粒子界面的光致电荷转移研究

半导体超微粒子与有机分子界面的光致电行转移过程是当前光化学和材料科学研究的一个活跃领域［‘，2］；研究的目的主要有两个方面，一是研究半导体超微粒子表面光致电行转移的特性；二是研究有机分子对超微粒子的光敏化作用．目前，超微粒子的功能化研究日益深入，其独特的光     

纳米碳材料非金属催化的研究进展

纳米碳材料直接作为催化剂的非金属碳催化是目前材料科学与催化领域的前沿方向之一.相对于传统金属催化剂,纳米碳材料催化剂具有高效环保、低能耗、耐腐蚀等优点.在烃类转化、化学品合成、能源催化等领域表现出优异的催化性能和发展潜力.综述了近年来纳米碳非金属催化研究的最新进展,主要包括新型纳米碳材料的表面性质、催化特性、反应机理和宏观制备等关键问题,并对纳米碳催化存在的挑战和前景进行了展望.     

Reaction of substituted iron phthalocyanines with dioxygen in acidic medium

The reaction of acidic form of the substituted icon phthalocyanine complex (3-PhS- 5-Bu^t)⁴pcFe (pcFe) with dioxygen in o-dichlorobenzene in the presence of dichloroacetic acid (HX) was investigated. The oxidation of HpcFeX gives the corresponding radical cation, which was confirmed by the stoichiometry of reduction of the product formed in this reaction with a two-electron reducing agent. The kinetic equation obtained on the basis of dependences of the oxidation rate on the HpcFeX, HX, and O₂ concentrations are consistent with the reaction mechanism that implies the formation of a HpcFeX complex with O₂ and its transformation to give a radical cation under the action of HX.Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 1592–1597, August, 2004.     

Direct Electrochemical Determination of Glyphosate at Copper Phthalocyanine/Multiwalled Carbon Nanotube Film Electrodes

A copper phthalocyanine/multiwalled carbon nanotube film‐modified glassy carbon electrode has been used for the determination of the herbicide glyphosate (Gly) at ?50 mV vs. SCE by electrochemical oxidation using differential pulse voltammetry (DPV). Cyclic voltammetry and electrochemical impedance spectroscopy showed that Gly is adsorbed on the metallic centre of the copper phthalocyanine molecule, with formation of Gly‐copper ion complexes. An analytical method was developed using DPV in pH 7.4 phosphate buffer solution, without any pretreatment steps: Gly was determined in the concentration range of 0.83–9.90 μmol L^?1, with detection limit 12.2 nmol L^?1 (2.02 μg L^?1).