酞菁铜衍生物的合成与性能研究

对合成的硝基和氨基四取代酞菁铜，从产率、可溶性和光谱性能等几个方面讨论了两种类型酞菁铜化合物作为太阳能电池光敏剂的可行性。实验结果表明，两种酞菁铜衍生物均是较好的光敏剂。     

酞菁钴类化合物的合成与应用

介绍了酞菁钴配合物及其酞菁钴衍生物的不同合成方法及其催化剂、溶剂等,并介绍了酞菁钴及其衍生物在石油工业、化肥工业、电池行业、功能性材料及酞菁染料等各领域的应用。指出研究双核及多核酞菁金属类化合物的合成、开发酞菁金属化合物的绿色化学合成路线,是今后的发展方向。     

酞菁镍晶体的化学工艺合成与探究

通过用1,3-二亚氨基异吲哚啉和二水乙酸合镍为反应原料,在不同有机溶剂中,以不同物质的量的催化剂,用溶剂热合成法直接合成酞菁镍晶体的过程,来探究酞菁镍晶体的最优化合成工艺。通过控制不同的反应条件,如反应温度、反应时间、催化剂等来确定反应最佳条件,为酞菁镍晶体的合成工艺提供理论依据。通过实验得出合成酞菁镍的最优化工艺条件是反应温度为270℃,溶剂为喹啉,体积为14 m L,反应时间为8 h。     

光动力治疗药物合成进展

光动力疗法（Photodynamic Therapy,PDT）是利用光敏剂发生光动力反应进行疾病诊断和治疗的一种新技术。光敏剂经历了第一代光敏剂卟啉及其衍生物、第二代光敏剂酞菁类化合物以及第三代光敏剂,已经逐步走向成熟。本文主介绍了这三代光敏剂的性质及合成。     

新型两亲性酞菁锌LB膜的研究

本文合成了一种新型的两亲性酞菁分子，研究了它在不同溶剂中的聚集行为，考察了酞菁及酞菁与正十六烷混俣的成膜性能，制备了混合的多层ＬＢ膜，并利用紫外光谱研究ＬＢ膜内的分子聚集状况，用分子激子理论对实验结果和以分析，还应用偏振紫外的方法对ＬＢ膜内酞菁分子大环的取向进行了研究。     

四葡萄糖基锌酞菁的合成及其光驱动~1O_2生成速率常数的测定

糖酞菁是光动力疗法研究中非常受关注的光敏剂之一。该文合成了两种光动力疗法用光敏剂四葡萄糖基锌酞菁,并通过高分辨质谱及1HNMR对其进行了结构表征,发现不同于[2(3),9(10),16(17),23(24)-四(1,2:5,6-二-O-异丙叉基-α-D-葡萄呋喃糖基)酞菁]锌(Ⅱ)〔缩写为Pc-(Glup)4〕,[2(3),9(10),16(17),23(24)-四(α-D-葡萄呋喃糖-3-基)酞菁]锌(Ⅱ)〔缩写为Pc-(Glu)4〕中的糖基以α-,β-构型两种形式同时存在。对Pc-(Glup)4和Pc-(Glu)4进行了UV-vis和光驱动1O2生成速率常数的测定,结果表明,在甲醇中Pc-(Glu)4以单体形式存在,而Pc-(Glup)4则发生了聚集,它们的1O2生成速率常数分别为8.0×10-4和2.2×10-4。     

萘酞菁衍生物在光动力疗法中的研究进展

光动力治疗作为一种非侵入性治疗方式,具有微创、毒副作用小、可重复治疗等优点。光敏剂是光动力治疗的关键因素之一,萘酞菁作为第二代光敏剂,扩展的π-共轭体系使其在750～900 nm具有强吸收,该近红外光有较深的组织穿透性,且能量足够激发光敏剂,也能避免可见光区吸收带来的皮肤光毒性。但萘酞菁具有较强的聚集倾向,影响其光化学性质及光动力疗效。综述了通过合成萘酞菁衍生物和纳米载体包封来改善其光学性质或增强光动力疗效的进展。     

光动力治疗用酞菁类光敏剂的合成研究进展

本介绍了光动力治疗原理、酞菁类光敏剂的合成方法及其近年来得到的研究进展，并介绍了酞菁在光动力治疗中的光化学生物过程和光漂白现象，还对其存在的缺点和今后的研究方向进行了讨论。     

磺化酞菁类染料光敏氧化胆固醇及L-半胱氨酸的反应

本文合成了磺化酞菁、磺化酞菁镓和磺化酞菁铝,研究了它们光敏氧化胆固醇及L-半胱氨酸的反应。染料的聚集态和溶液的pH值对反应速率有不同程度的影响。D_2O加速反应而NaN_3猝灭反应的结果表明,光敏氧化反应主要通过Ⅱ型(涉及~1O_2)机制进行。     

磺化金属酞菁的溶剂效应

文章测试了5种磺化金属酞菁在7种不同极性溶剂中的吸收光谱,用N icol理论研究了金属酞菁染料的溶剂效应。实验和理论结果表明,此类化合物最大吸收峰的波数与函数f(n,ε)存在良好的线性关系,线性相关系数都在0.93以上;而Bayliss函数项(n2-1)/(2n2+1)决定了最大吸收波长(λm ax)的位移变化,λm ax总体上随着溶剂折射率的增大而蓝移,随着溶剂极性的增强而红移。基于此结果,提出了通过选择合适的溶剂调节酞菁染料吸收峰的有效方法,从而使酞菁染料更好地应用于激光防护。     

光致变色化合物螺萘并吡喃的合成及光谱性能

以2-萘酚、苯肼和3-甲基-2-丁酮为原料,设计并合成了一种含萘环螺吡喃类光致变色化合物:1,3,3-三甲基吲哚啉螺萘并吡喃,通过1HNMR、IR和元素分析表征了它的分子结构,利用紫外光谱和荧光光谱对目标化合物的吸收光谱和光致发光光谱进行了研究,初步探索了目标产物的光致变色性能。吸收光谱结果表明,目标分子(闭环体)的二氯甲烷溶液(1×10-4mol/L)在可见光区基本无吸收而呈现无色,但经254 nm的紫外光照射后其开环体在480 nm处有较强的吸收而呈现红色(A=1.1),停止紫外光照射溶液恢复为无色,显示了良好的光致变色性能;发光光谱结果显示,目标分子经紫外光激发后其开环体在433 nm处有较强的蓝光发射。     

Synthesis, optical properties and ultrafast dynamics of a 2,1,3-benzothiadiazole-based red emitter with intense fluorescence and large two-photon absorption cross-section

A new 2,1,3-benzothiadiazole-based red fluorescent compound with a D-A-D type structure was synthesized and characterized. The central 2,1,3-benzothiadiazole core was symmetrically connected via the 4,7-positions with two donor groups in which the 7-position of a fluorenyl ring was substituted with a carbazol-9-yl moiety and the 2-position was substituted by a 5-thienyl moiety. The carbazol moieties were further derivatized by two 2-naphthyl moieties at the 3,6-positions. Femtosecond laser spectroscopic techniques including excited state fluorescence and pump-probe technique investigations, together with steady state absorption and one-photon fluorescence spectra, were employed to systematically investigate the optical properties and ultrafast dynamics of the new compound in tetrahydrofuran solution. It shows a large two-photon absorption cross-section and high fluorescence quantum yield, indicating potential application in two-photon fluorescence imaging field. The ultrafast dynamics results reveal competition between a pure excited state relaxation process and stimulated radiation in the red wavelength region.     

The tautomeric and acid-base equilibria of p-methyl red in aqueous solutions

The UV-visible spectra of p-methyl red were examined at 25°C in water at various acidities and the variations in the spectra were correlated with the structures of the several forms of the compound. The monoprotonated form gives aggregates at concentrations exceeding 1.50 × 10⁻⁵ mol dm⁻³ p-methyl red. In 0.1–1.0 mol dm⁻³ HCl, p-methyl red is present as a tautomeric equilibrium mixture with an equilibrium constant of 4.0. The microscopic acid dissociation constants that describe the acid-base equilibria involving the cationic form were calculated. The partition coefficient that describes the distribution of p-methyl red between di-n-butyl ether and water attains a maximum value of 49.0 at pH 3.5.     

衍生于三苯基吡啶的pH探针的制备及其光谱性质

由4-氯苯甲醛、苯乙酮和氨在氢氧化钠溶液中一锅法合成了化合物4-(4-氯苯)-2,6-二苯基吡啶(Ⅰ),用1HNMR、13CNMR和FTIR对化合物Ⅰ进行了结构表征。pH滴定实验表明,化合物Ⅰ的紫外吸收和荧光发射光谱均对溶液的pH具有较强的敏感性,当溶液pH=4.70～4.22,化合物Ⅰ在256 nm的紫外吸收强度随着pH的减小而降低,在312 nm的紫外吸收强度及在403 nm的荧光强度随着pH的减小而增强。此外,热分析结果表明,化合物Ⅰ具有优良的热稳定性。     

Photophysics of the phenoxazine dyes resazurin and resorufin in direct and reverse micelles

The photophysics of the phenoxazin-3-one dyes resazurin and resorufin was studied in a micellar solution of cetyltrimethylammonium chloride and in reverse micelles of 1,4-bis(2-ethylhexyl)sulfosuccinate and benzylhexadecyldimethylammonium chloride. Absorption and fluorescence emission spectra, as well as fluorescence lifetimes and T–T transient absorption spectra were determined as a function of surfactant concentration. In the presence of direct micelles of cetyltrimethylammonium chloride, both dyes displayed red shifts in the absorption and fluorescence spectra together with a simultaneous fluorescence lifetime increase. The electrostatic attraction between the anionic dyes and the positive micellar interface favors the location of the dyes closer to the head groups of the surfactant molecules. In reverse micellar systems the spectral properties depended upon the charge of the surfactant and water content. In the case of 1,4-bis(2-ethylhexyl)sulfosuccinate, at low water content both dyes were incorporated into the interface; as the water content increased their spectral properties tended to those in pure water. In contrast, in the case of cationic surfactant, the dyes were located in the interfacial pseudophase as a result of electrostatic interactions.     

1,1-双(1H-苯并咪唑-2-基)-1-十三碳烯的合成及其性能

以邻苯二胺和丙二酸为原料,在3 mol/L盐酸催化下合成双(1H-苯并咪唑-2-基)甲烷中间体,然后与月桂醛通过Knoevenagel缩合反应合成了双苯并咪唑衍生物——1,1-双(1H-苯并咪唑-2-基)-1-十三碳烯。利用元素分析、FTIR和~1HNMR对合成产物的结构进行了表征,考察了常规碱催化剂对目标产物收率的影响,并通过UVVis和荧光光谱(FL)测定了目标化合物的光学性能。结果表明:六氢吡啶催化效果最好,产物收率可达76.33%。目标化合物在243、315和361 nm 3处有紫外吸收峰,可有效覆盖日光紫外线UVA和UVB波段;目标化合物溶液在λem=464.5 nm处有蓝紫色荧光,固体薄膜在λ_(em)=476.5 nm处有蓝紫色荧光,荧光量子产率为0.47。标题化合物荧光增白效果与常用荧光增白剂VBL相当。     

Problems of spectrophotometry of glass-forming melts: II. A technique for measuring the absorption spectra of glasses and melts in the red and near-infrared ranges at temperatures from 20 to 1500°C

A technique for measuring the absorption spectra of glasses and glass-forming melts in the red visible and near IR ranges, the experimental setup, and the measuring cell intended for use over a wide range of temperatures are described. The main problems concerning the acquisition of reliable data on the absorption spectra of glass-forming melts at high temperatures and the basic sources of errors in measurements of the spectra are considered.     

Perylene derivative sensitized multi-walled carbon nanotube thin film

Perylene-sensitized multi-walled carbon nanotubes (PV-MWNT) have been prepared by a π-stacking between nanotubes and perylene derivatives, N,N′-diphenyl glyoxaline-3,4,9,10-perylene tetracarboxylic acid diacidamide (PV). The resultant nanocomposites have been characterized by transmission electron microscope (TEM), UV-vis absorption, photoluminescence (PL) and photocurrent spectra. Long range ordering can be observed in the form of PV-MWNT via π-stacking by TEM. Red-shift in the optical spectra consisting of the UV-vis absorption and PL spectra with the attraction of PV on the surface of the MWNTs were observed. The evident quenching in PL spectra of PV-MWNT was ascribed to the absorption and transfer of recombination energy by MWNT. Photosensitivity spectra demonstrated an increasing photocurrent in the ultraviolet region and a broadening photosensitivity in the red spectral region for solar cells based on PV-MWNT.