BODIPY类激光染料的合成及性能研究

BODIPY类染料以其光化学稳定性好、激光转换效率高、较大的激光发射和可调范围、溶解度好、激发态吸收截面小、三重态驰豫效率小等优点极大提升了光响应能力。在液体、固体聚合物介质中,BODIPY染料在泵浦脉冲下可以产生稳定的激光信号。通过染料分子结构和光物理性质研究,可以筛选出产生最优激光性能的结构和基质。主要介绍了染料共掺及改性聚合物基质固体染料激光的研究进展,同时对新型BODIPY类激光染料的研究现状进行了综述。     

不对称五氮齿镉和铟大环配合物的激发态性能研究

本文研究了不对称五氮齿镉和铟大环配合的的激发态性能及其光稳定性。结果表明：它们的三重态能量在１２０ｋＪ／ｍｏｌ左右,最低激发三重态敏化产生单重态氧的量子产率在０．６￣０．９,它们的分子一阶超极化率在￣１０＾－２８ｅｓｕ,在光照的条件下,配合物Ⅰ相当稳定,而配合Ⅱ则形成不稳定化合物导致光褪色。     

配位聚合物[Co(BZM)_2(TMBA)_2]_n的合成和表征

常温条件下在水和乙醇混合溶剂中,由苯并咪唑(BZM)、2,4,6-三甲基苯甲酸(HTMBA)与金属离子Co(Ⅱ)合成了1个新颖的三维超分子配合物[Co(BZM)2(TMBA)2]n,并通过X-射线单晶衍射、元素分析、红外光谱以及热稳定性分析等对其进行了结构测定和表征。分析表明,该配合物属正交晶系,Pbca空间群,中心金属离子Co(Ⅱ)是六配位,由4个氧原子和2个氮原子包围,氧原子分别来自2个2,4,6-三甲基苯甲酸分子,氮原子分别来自2个苯并咪唑分子。配合物通过范德华力形成3D网络结构。     

含二茂铁基偶氮染料的光稳定性研究

利用UV－Vis吸收光谱仪和光化学反应器研究了含二茂铁基偶氮染料及相应的偶氮染料溶液的光降解动力学。在溶液中，它们的光降解反应遵循零级动力学模型。与相应的偶氮染料相比，含二茂铁基的偶氮染料溶液具有较好的光稳定性。这表明，在其分子内存在着有效的从偶氮染料母体到二茂铁基团的分子内三重态－三重态能量传递，上述过程降低了偶氮染料激发三重态的生成，避免了染料的过早降解，提高了其稳定性。     

新水溶性卟啉试剂的合成及其与金属离子显色反应的研究

五种新的水溶性卤代苯磺酸卟啉化合物的合成和分离纯化方法。新卟啉试剂与 Cu(Ⅱ)、Zn(Ⅱ)、Pd(Ⅱ)、Ni(Ⅱ)、Co(Ⅱ)、Mn(Ⅱ)、Cd(Ⅱ)、Pb(Ⅱ)八种金属离子的显色反应。试剂结构的改变及各种取代基对试剂以及试剂与金属离子反应性能的影响。     

丙酮酸改性壳聚糖对金属离子的吸附性能研究

丙酮酸经Schiff碱反应对壳聚糖进行修饰 ,合成了高取代的水溶性丙酮酸缩壳聚糖 (PCTS) ,研究了PCTS、SCTS(水杨醛改性壳聚糖 )、CTS(壳聚糖 )对Cu(Ⅱ )、Zn(Ⅱ )、Co(Ⅱ )的静态吸附性能 ,并采用正交实验法考察了金属离子浓度、介质酸度、吸附量和吸附时间对吸附剂去除金属离子能力的影响。结果表明 ,PCTS的吸附性能优于SCTS与CTS ,对Cu(Ⅱ )、Zn(Ⅱ )、Co(Ⅱ )的吸附容量 (pH =7 0 )分别为 2 79 56、1 96 63、70 2 1mg/g ,金属离子浓度、介质酸度对吸附性能影响大 ,而吸附剂用量、吸附时间对吸附性能影响较小。     

高分子染料的光稳定性研究

光稳定性是衡量高分子染料的一个重要指标,而高分子染料的光稳定性主要与高分子骨架结构、染料母体结构及着色工艺等因素有关.本文详细分析了高分子染料光褪色的原因及机理,并针对影响高分子染料光稳定性的各因素,提出相应的改进措施.     

氰桥化合物[cis-Fe(bpy)2(CN)2Mn(L)]2[PF6]4的合成及其对金属离子选择识别作用

将Mn(Ⅱ)离子、有机配体L(L=1,6-二苯基-2,5-双(2-甲基吡啶基)-2,5-二重氮己烷)和氰基化合物cis-FeⅡ(bpy)2(CN)2·3H2O(bpy=2,2′-联吡啶)在NH4PF6存在下制备一个四元环异核氰桥化合物即标题化合物,并对其结构进行表征。重金属离子对标题化合物的荧光响应研究表明,标题化合物对Cu(Ⅱ)和Fe(Ⅲ)有很好的选择性。随着金属离子Cu(Ⅱ)和Fe(Ⅲ)的加入,标题化合物的荧光强度逐渐降低至基本消失。随着金属离子Pb(Ⅱ)和Fe(Ⅱ)的加入,标题化合物的荧光强度逐渐降低,当金属离子加到一定浓度,标题化合物的荧光强度不随金属离子的变化而变化。对于Co(Ⅱ)、Cr(Ⅲ)、Mn(Ⅱ)、Cd(Ⅱ)、Ni(Ⅱ)、Zn(Ⅱ)等离子,随着金属离子的加入标题化合物的荧光强度改变甚微或不改变。     

亚氨基二乙醛肟树脂的合成及其性能的研究

介绍了苯乙烯二乙烯基苯为基体的亚氨基二乙醛肟树脂(IDAO)的合成,研究了树脂对金属离子的吸附性能,并讨论了pH对吸附的影响以及吸附的动力学效应。结果表明 IDAO 树脂对重金属离子(Cu(Ⅱ)、Co(Ⅱ)、Ni(Ⅱ)、Pb(Ⅱ)、Zn(Ⅱ)等),特别是高价重金属离子(Fe(Ⅲ)、Cr(Ⅳ)、V(Ⅴ))有很强的吸附作用,而对碱金属、碱土金属不吸附。     

一种新型水溶性花菁染料的制备与物性及应用研究

本文利用丙二烯醛缩二苯胺盐酸盐为缩合剂,以1,3-丙磺酸内酯和2,3,3-三甲基-3H-吲哚啉为原料设计并制备出一种1,1′-(磺酸基丙基)-3,3,3′,3′-四甲基-苯并吲哚五甲川花菁染料。利用IR、NMR和HRMS进行表征。通过UV和TG考察了染料的光、热稳定性,并探讨了不同金属离子对染料的紫外吸收和荧光光谱的影响。结果表明：菁染料在近红外区有较强吸收,且光热稳定性较好;同时金属离子的加入可以使染料的荧光猝灭,可以作为功能性染料进行使用。     

Removal of some hazardous materials from their solutions using active carbon‐filled poly vinyl alcohol/N‐vinyl pyrrolidone membrane subjected to freeze–thawing and gamma irradiation

Carbon membrane consisting of a mixture of powdered activated carbon and poly vinyl alcohol/N‐vinyl pyrrolidone was made by single freezing and thawing followed by gamma‐ray irradiation. The prepared membrane was characterized by X‐ray diffraction, scanning electron microscopy, and gel content. The membrane was applied for adsorption of some hazardous wastes (acid dye, basic dye, heavy metal ions such as Co and Ni, dichromate anion, and phenols) from their solutions. From the results, it was found that the prepared membrane possesses greater efficiency toward removal of heavy metal ions than powdered activated carbon, whereas their adsorption capacity toward dyes and phenol is almost the same as active carbon. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Photostability of Anthraquinone and Azo Dyes in N-Ethylacetamide (Nylon Model)

Measurements of the quantum yields of photodegradation of anthraquinone and azo dyes in N-ethylacetamide (nylon model) and triplet sensitisation of dye fading showed that the photochemical reactions are initiated by an upper excited n-π* triplet state. The primary photochemical reaction with both anthraquinone and azo dyes involves hydrogen abstraction from the amide so/vent. In some cases oxygen retards dye fading by reoxidation of the reduced structures. In other cases oxygen accelerates the photochemical reaction via free-radical initiated oxidation reactions. The quantum yields of dye fading are strongly wavelength dependent. On exposure to a simulated sunlight spectrum photodegradation is mostly caused by radiation in the region 300–400 nm. While unsubstituted anthraquinone is very photoreactive, amino-substituted anthraquinones are much more photostable in N-ethylacetam/de. Photostability of mono- and di-substituted anthraquinone derivatives increases with the electron-donating power of substituent groups. Azo dyes with increased conjugation such as diazo and naphthazo structures are more photostable than simple azobenzene derivatives. Certain electron-withdrawing substituents, which do not affect dye colour, improve the ‘oxidative’ photostability of both anthraquinone and azo dyes. A cobalt premetallised azo dye (C.I. Acid Red 182) is very photostable in N-ethylacetamide, showing the effect of metal chelates on photostability. The low values of quantum yields for the dye solutions are comparable with those of acid and disperse dyes in nylon films, indicating that N-ethylacetamide is a suitable nylon model for mechanistic studies of dye fading.     

2-巯基吡啶金属络合物的制备及热稳定性

制备了以2-巯基吡啶为配体的铅(Ⅱ)、钴(Ⅱ)、锰(Ⅱ)、锌(Ⅱ)、镉(Ⅱ)、铜(Ⅱ)和镍(Ⅱ)7种络合物,通过EDTA络合滴定分析、电导测定、紫外光谱和红外谱表征,确定络合物的结构。同时,利用热重分析对络合物的热稳定性进行了研究,得出其稳定性次序为:铅(Ⅱ)络合物>锌(Ⅱ)络合物>镉(Ⅱ)络合物>镍(Ⅱ)络合物>钴(Ⅱ)络合物>锰(Ⅱ)络合物>铜(Ⅱ)络合物。     

The influence of metal ions on the aggregation and hydrophobicity of dyes in solutions

The effect of the addition of metal ions to dye solutions in promoting dye aggregation and in changing dye association in solution has been studied. Experimental findings indicate that the promoting effects of calcium and magnesium ions are greater than that of sodium ions. It is expected that any change in dye hydrophobicity would have a direct influence on the extent of dye aggregation. Under acid conditions, a higher concentration of metal ions would result in an increase in dye aggregation with a reduction in dye hydrophobicity. On the other hand, while the dye aggregation is increased under alkaline conditions under the influence of metal ions, hydrophobicity was shown to increase. These changes in dye hydrophobicity could be used to explain the dyeing behaviour of reactive dyes in the dyeing of silk.     

Poly(N-vinylcaprolactam) gel/organic dye complexes as sensors for metal ions in aqueous salt solutions

The complex formation of organogels based on poly(N-vinylcaprolactam) (PVCa) and organic dyes [5-(4-dimethylaminobenzylidene) rhodanine, α-nitroso-β-naftol, and dithizone] and the properties of the complexes in salt aqueous solutions were studied. PVCa gels absorbed these dyes in organic media (ethanol and chloroform). Our main focus was the behavior of the gel/dye complex immersed in a salt aqueous solution if the dye was the chelating ligand for metal ions. The behavior of the PVCa/dithizone (Dz)/chloroform system was studied in AgNO₃ aqueous solutions. The absorption spectra of gel/dye and gel/dye/metal ion systems were investigated. The results obtained indicate that Ag⁺ ions penetrate the gel phase and that the Dz/silver complexes are indeed formed inside the gel. The dependence of the optical density of the gel/dye/metal ion systems on the AgNO₃ concentration was observed. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 3238–3243, 2001     

稀土改性尼龙66染色机理的研究

<正>近几年来,稀土化合物在纤维染色过程中的应用取得了良好效果.随着稀土染色的推广和应用,对稀土染色机理的研究也愈加引起人们的关注.有人在研究锦纶和涤纶稀土染色时提出了分子络合理论,认为在染色过程中,稀土化合物的加入会生成纤维大分子-稀土离子-染料分子复杂的配位体,从而改善了染色效果.     

Dyeing of polyester and its blends with some disazo dyes derived from the disodium salt of chromotropic acid and their chelates with transition metal ions

Disazo dyes derived from the disodium salt of chromotropic acid and their chelates with metal ions were applied on polyester, polyester/cotton and polyester/wool blend fibres as disperse dyes. The fastness to washing, perspiration, rubbing and light of the resultant dyeings were measured. The bonding of dye or its complexes to the fibre and the effect of substituent groups on the colour fastness of the dyes are discussed.     

氯化钠-硫氰酸钾-溴化十六烷基三甲基铵体系浮选分离铂

研究了氯化钠-硫氰酸钾-溴化十六烷基三甲基铵体系浮选分离铂的行为及其与常见金属离子的分离条件。结果表明,当NaCl用量为1 g,0.1 mol/L硫氰酸钾(KSCN)溶液为2.0 mL,10 mmol/L溴化十六烷基三甲基铵溶液为2.0 mL,pH=4.0时,Pt(Ⅳ)能被定量浮选,而Al(Ⅲ),Co(Ⅱ),Ni(Ⅱ),Mn(Ⅱ)离子不被浮选,实现了Pt(Ⅳ)与这些离子完全分离。对合成水样进行了浮选分离测定。     

Evidence for the Participation of Singlet Oxygen in the Vat–dye Photosensitized Degradation of Cellulose

A study has been made of the vat–dye photosensitized degradation of cellulose. Whilst the part played by the dyes in direct hydrogen abstraction from a cellulose substrate cannot be overlooked, it is apparent that the role played by singlet oxygen is important. The ability of a dye to produce singlet oxygen has been studied by measuring the amount of tetraphenylcyclopentadienone the dye can photo–oxidize. It would appear that the singlet oxygen is initially formed in its high energy g state by energy transfer from the triplet state of the dye to ground state molecular oxygen. Luminescence spectroscopy has been employed in order to gain information about the excited state energies of the dye molecules, and an electron spin resonance study of the dyes in rigid media has been carried out in order to obtain information about the triplet state.