冠醚菁染料的研究 Ⅵ.含苯并咪唑环的冠醚菁染料的合成

关于冠醚硫碳菁染料的合成及其光谱增感作用的研究已有报道.这类含冠醚结构因子的新型菁染料被证明具有良好的增感性能和稳定性. 为了进一步研究冠醚结构对菁染料感光性能和理化性能的影响,合成了含苯并咪唑环的冠醚咪碳菁染料以及与菁有关的冠醚苯乙烯型染料. 新染料1—7的结构得到质谱、核磁共振谱、红外和紫外光谱的证实.染料中间体季铵盐8的合成已在前文报道.     

增感染料与卤化银微晶之间的作用及其聚集态的研究

本文研究了光谱增感染料的结构对立方体卤化银乳剂的感光性能的影响,并利用反射光谱和彩色分析荧光电镜研究了染料在卤化银微晶上的聚集态和Ｊ 聚集体的相对尺寸,通过测定乳剂离子电导率研究了染料的结构对乳剂离子电导率的影响．实验结果表明：本文中所用的九个染料不管是增感还是减感染料都能在立方体卤化银乳剂上形成Ｊ 聚集态;对噻碳菁染料而言,其５位上无论是吸电子基团还是推电子基团的染料形成的Ｊ 聚集体的平均尺寸皆较未取代染料的大,其增感效果也较好;苯环５位上吸电子基取代或平面性好的噻碳菁染料可提高立方体ＡｇＢｒＩ乳剂的离子电导率,证明它们的增感效果也好;６位硝基取代的吲哚碳菁染料是典型的减感染料,其在立方体乳剂上所形成的Ｊ 聚集体较小,但是对乳剂的离子电导无影响．此外,本文还试图对不对称插烯菁染料Ｄｙｅ９使立方体ＡｇＢｒＩ乳剂减感的作用进行了解释     

感绿增感染料电子能级和增感性能的研究

本文应用Hückel分子轨道理论,对一系列对称和不对称的噁碳菁、咪噁碳菁以及喹啉噻菁染料的电子能级进行了计算,测定了这些染料的激发能,极谱半波还原电位和在溴氯化银乳剂中的光谱增感性能,计算值与观测值取得了很好的一致性。     

新型吲哚碳菁染料的合成及表征

通过简单而有效的方法合成了14个二碳菁和三碳菁染料,其中大多数是新化合物,同时研究了染料的组成和性质之间的关系。     

不同取代基的噻碳菁和吲哚碳菁染料对其在溴化银微晶上吸附能力及形成J-聚集体尺寸分布的影响

本文研究了5-位不同取代基的噻碳菁和吲哚碳菁染料对其在立方型颗粒和T-颗粒溴化银微晶上吸附能力的影响,并采用ACFEM(Analytical Color Fluore scence Electron Microscopy)研究了上述结构染料对其吸附在溴化银微晶所形成的J-聚集体尺寸分布的影响。实验结果表明,对吲哚碳菁染料来说,立方体溴化银微晶表面的吸附能力较T-颗粒溴化银微晶表面的吸附能力强;但对噻碳菁染料来说则相反,它们在T-颗粒溴化银微晶表面的吸附能力较立方体溴化银微晶表面的吸附能力强。另外,对5-位不同取代基的噻碳菁染料而言,无论是在立方型颗粒或T-颗粒溴化银微晶上的吸附能力来说,含取代基(无论4-取代基是吸电子型还是推电子型)的噻碳菁染料较未取代的噻碳菁染料强;而5-位取代基是吸电子型的噻碳菁染料更有利于其吸附在T-颗粒溴化银微晶表面。此外,本文还进一步证明了溴化银微晶表面上染料J-聚集体的生长过程是符合奥斯瓦尔特成熟过程的。吲哚碳菁染料在T-颗粒溴化银微晶上形成的J-聚集体的平均尺寸明显大于在立方体溴化银微晶上形成的J-聚集体的平均尺寸。吸附在立方体溴化银微晶上的5-不同取代基的噻碳菁染料对其形成J-聚集体尺寸分布的影响的研究结果表明,含取代基(-CH₃,-Ph,-Cl)的噻碳菁染料形成的J-聚集体的尺寸分布几乎相同,但与未取代的噻碳菁染料形成的J-聚集体的尺寸分布明显不同;5-位含取代基的噻碳菁染料形成的J-聚集体平均尺寸大于未取代的噻碳菁染料的。     

氯取代硫三碳菁染料的合成及性能

本文合成了七个硫三碳菁.其中四个具有桥环的菁染料。测定了它们的电子吸收光谱,讨论了结构对光稳定性的影响。并发现镍络合物能有效地抑制菁染料的光退色。     

含吲哚核端基多甲川菁染料的合成及性能

我们曾合成了具有桥环的硫三碳菁及多甲川苯乙烯菁,并测定了光学性能。本文报道吲哚环为端基的桥链三碳菁和四甲川苯乙烯菁的合成及在有机溶剂中电子吸收光谱及溶解性能的测定。所用仪器同前,7种多甲川菁染料的合成反应如下:     

吲哚二碳菁染料的合成

合成了五种N－烷基吲哚二碳菁染料，通过质谱、核磁共振氢谱及红外光谱确证了化合物结构。测定了化合物在溶液中的紫外吸收光谱和溶解度，讨论了溶解度、熔点与染料分子结构的关系。     

冠醚方酸碲碳菁染料的合成研究

合成了不对称冠醚方酸碲碳菁染料和对称冠醚方酸碲碳菁染料，并探讨了对称冠醚方酸碲碳菁的合成方法及反应条件，提出了其可能的反应机理。     

阴离子碳菁染料的合成与聚集动力学研究

自从1938年,Scheibe^[1]发现了菁染料聚集体中的能量传递现象,人们对菁染料的聚集行为展开了大量的研究^[2,3].由于菁染料聚集体对乳剂具有特殊的增感作用,人们主要研究聚集体在乳剂中的增感机理^[4,5]以及菁染料聚集的溶剂效应与浓度效应^[6]等,而对于菁染料聚集的动力学行为研究较少.     

Triphenylmethane dyes as fluorescent probes for G-quadruplex recognition

Triphenylmethane (TPM) dyes normally render rather weak fluorescence due to easy vibrational deexcitation. However, when they stack onto the two external G-quartets of a G-quadruplex (especially intramolecular G-quadruplex), such vibrations will be restricted, resulting in greatly enhanced fluorescence intensities. Thus, TPM dyes may be developed as sensitive G-quadruplex fluorescent probes. Here, fluorescence spectra and energy transfer spectra of five TPM dyes in the presence of G-quadruplexes, single- or double-stranded DNAs were compared. The results show that the fluorescence spectra of four TPM dyes can be used to discriminate intramolecular G-quadruplexes from intermolecular G-quadruplexes, single- and double-stranded DNAs. The energy transfer fluorescence spectra and energy transfer fluorescence titration can be used to distinguish G-quadruplexes (including intramolecular and intermolecular G-quadruplexes) from single- and double-stranded DNAs. Positive charges and substituent size in TPM dyes may be two important factors in influencing the binding stability of the dyes and G-quadruplexes.     

The fast atom bombardment mass spectra of xanthane dyes

The Fast Atom Bombardment mass spectra of a number of xanthane dyes are reported. These dyes are insufficiently volatile to give spectra by conventional electron impact ionization. Fragmentation pathways have been determined by metastable linked scan techniques and accurate masses obtained by peak matching. The xanthane dyes may be readily identified from their FAB spectra by the presence of characteristic ions.     

新型水溶性荧光标示剂吲哚方酸菁染料的合成及光谱性能

用方酸与不同的N烷基取代吲哚啉季铵盐缩合制备了一系列对称的水溶性方酸菁染料. 通过核磁共振氢谱和质谱对合成的染料结构进行了表征, 研究了它们在不同溶剂中的吸收和发射光谱. 结果表明, 随着溶剂极性的增大, 染料的吸收光谱发生蓝移, 表现为负向溶剂化效应, 在极性溶剂中的荧光量子产率比在水中的大. 考察了N位取代基对染料水溶液光稳定性的影响, 结果表明在吲哚环N原子上引入较大的苄基有助于提高光稳定性, 且随着苄基上取代基吸电子能力的增强, 染料的光稳定性增强.     

Azomethine and merocyanine dyes based on 3-arylbenzo[f]quinolinium salts and their spectral and electrophotographic properties

Azomethine dyes were obtained by reaction of 1-methyl- and 1,2-dimethyl-3-arylbenzo[f]quinolinium methiodides with 1-nitroso-2-naphthol. Merocyanine dyes were isolated by the action of KOH on 2-hydroxy-5,6-benzostyryl derivatives of 3-arylbenzo[f]quinolinium salts. The absorption spectra of the dyes in ethanol and chloroform are presented, and it is shown that, as compared with the spectra of the merocyanines, there is a bathochromic shift of the absorption bands in the spectra of the azomethine dyes. The azomethine and merocyanine dyes have solvatochromic properties and display photosensitivity in the UV and visible regions when they are introduced into a polymer matrix.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10, pp. 1343–1347, October, 1977.     

Study of fluorescent aggregates of polymethine dyes

Absorption, fluorescence, and fluorescence excitation spectra have been studied for a number of anionic, cationic, and cationic-anionic polymethine dyes in low-polar and nonpolar solvents, as well as in binary mixtures of solvents differing in polarity. For most of the dyes studied, fluorescent aggregates have been found to form. Their broad fluorescence bands are located in the long-wave region with respect to those of the initial dyes. The quantum yield of the aggregate fluorescence is normally higher than that of the initial dyes. Fluorescence excitation spectra of some cationic-anionic dyes in nonpolar solvents disagree with their absorption spectra because of contact and solvent-separated ion pairs simultaneously present in the solution.Translated fromIzvestiya Akademii Nauk, Seriya Khimicheskaya, No. 1, pp. 69–75, January, 1993.     

Absorption spectra of 2,3-dihydrothionaphthen-3-one and its derivatives

A number of new thioindigoid dyes have been synthesized. They have been subjected to photochemical isomerization. The absorption spectra of the dyes synthesized have been compared with the absorption spectra of analogous dyes not containing bromine. The spectra of the cis forms are less sensitive to the introduction of a bromine atom than those of the trans forms.For Communication XI, see [1].Translated from Khimiya Geterotsiklicheskikh Soedinenii, Vol. 6, No. 8, pp. 1031–1033, August, 1970.     

Fluorescent properties of cationic-anionic polymethine dyes

The fluorescence spectra were studied and the quantum yields of the fluorescence of a number of cationic-anionic polymethine dyes were measured in polar, low-polarity, and nonpolar solvents. It was shown that the fluorescence spectra of cationic-anionic dyes in polar solvents, like the absorption spectra, represent the sum of the fluorescence spectra of the corresponding cationic and anionic dyes. For dyes in which the absorption bands of the anion and cation are close and a new short-wave band arises in the ion pairs, excitation into this band virtually does not lead to fluorescence, which is a consequence of the forbidden nature of the long-wave transition that arises as a result of the interaction of the chromophores. For a number of cationic-anionic dyes in ion pairs an energy transfer is observed: When an ion possessing short-wave absorption is excited, an ion with long-wave absorption fluoresces.N. N. Semenov Institute of Chemical Physics, Russian Academy of Sciences, 117977 Moscow. Translated fromIzvestiya Akademii Nauk, Seriya Khimicheskaya, No. 11, pp. 2532–2539, November, 1992.     

含吡喃鎓端基的苯乙烯染料合成及电子吸收光谱

多甲川染料已广泛用于银盐感光材料、电子照相、染料激光器、光记录介质及太阳能转换体系等方面。其中苯乙烯多甲川染料具有宽的吸收光谱,引起人们的重视。我们曾合成了含吡喃鎓多甲川染料,它们与含氮杂环的多甲川染料相比,吸收波长红移,并具有极好的光化学稳定性。本文合成了含吡喃鎓端基的二甲川及四甲川苯乙烯染料,测定了电子吸收光谱。     

Bischromophoric styrylpyridinium dyes. Spectroscopic properties of 1,3-bis-[4-(p-N,N-dialkylaminostyryl)pyridinyl]propane dibromides

The photophysical properties of newly synthesized bischromophoric solvatochromic stilbazolium dyes, 1,3-bis-[4-(p-N,N-dialkylaminostyryl)pyridinyl]propane dibromides (C1-C9), were studied in a series of solvents and their spectroscopic properties were compared with structurally related, monochromophoric styrylpyridinium dyes (SP1-SP9). The position of the UV-vis absorption spectra maximum of novel dyes is only slightly solvent polarity dependent in contrast to the fluorescence spectra that show pronounced solvatochromic effect demonstrated by a large Stokes shifts. The influence of the solvent on absorption and emission spectra, and the solvatochromic properties observed for both ground and first excited states for all the dyes were used for the evaluation of their excited state dipole moments. The ground state dipole moments of both mono- and bischromophoric dyes were established by applying ab initio calculations. The calculations and measurements unexpectedly show that the bischromophoric dyes are characterized by ground state dipole moments being equal to about half of that characterizing their monomeric equivalents, while the excited state dipole moments of bischromophoric dyes are about 10-25% higher in comparison to their monomeric equivalents.