溴代酞菁铜衍生物薄膜的折射率和吸收特性

通过旋涂法在单晶硅片上制备了一系列含有不同数目溴取代基的酞菁铜衍生物：一溴代－四烷氧基酞菁铜（MBTAPcCu），二溴代－四烷氧基酞菁铜（DBTAPcCu），四溴代－四烷氧基酞菁岣（TBTAPcCu）和无溴代－四烷氧基酞菁铜（NBTAPcCu）薄膜，利用同步旋转起偏－检偏器（RAP）型的宽谱扫描全自动椭圆偏振光谱仪测定了上述薄膜的椭偏光谱，获得了该系列薄膜的复折射率、复介电常数和吸收系数，研究了溴取代基对酞菁铜衍生物薄膜光学性质的影响。     

固态和液态溶液中酞菁铜及其衍生物的光谱变化

研究了三种酞菁铜及其衍生物CuPc,tb-CuPc,oo-CuPc在不同环境状态下的吸收光谱的变化。讨论了三种被质子化前后在溶液中的吸收光谱Q带的红移机制,并与固体分散样品所产生的光谱进行了比较,研究了酞菁铜衍生物分散在聚合物薄膜样品分子间的相互作用导致的吸收光谱的改变。同时结合POM,DSC,XRD方法,进一步对薄膜材料的结构和物相进行了表征。结果表明在不同浓度酞菁铜衍生物掺杂的固体薄膜中,被分散的酞菁铜衍生物的分子之间仍然处于缔合或凝聚状态,降低酞菁铜衍生物掺杂浓度并不能解除缔合作用或改变固体薄膜样品中的吸收光谱。     

取代基对稀土夹心双酞菁铥荧光特性的影响

利用稳态荧光和时间分辨荧光方法研究了三明治型酞菁铥的荧光特性及其浓度、激发波长和取代基对荧光特性的影响。实验发现:3种双酞菁铥的氯仿溶液在700 nm处具有较强的荧光发射,给电子基-OC₈H₁₇的加入使得酞菁大环上π电子的离域性增强,降低了π分子轨道的能级差;同时,烷氧基上非成键电子能够和共轭体系中的π电子相互作用,形成p-π共轭,进一步降低了π-π^*之间的能级差,从而使荧光谱中发射峰的峰位发生红移,峰的强度也有变化。3种酞菁铥化合物在700 nm左右的荧光具有两个寿命,分别为单体和聚集体产生的,随着浓度的降低,单体成分逐渐增多。     

单异硫氰基3：1不对称酞菁锌的光谱性质研究

测定了三种含异硫氰基3：1不对称酞菁锌配合物（RO）6（NCS）PcZn（Ⅱ）（R=n-C4 H9；n-C5 H11;n-C10H21）在五种有机溶剂中的电子吸收光谱，研究了取代基和溶剂对吸收光谱的影响和规律。同时测定它们在有机溶剂中的荧光发射光谱，研究了外部取代基、溶剂和浓度对最大发射波长及荧光强度的影响规律，发现此类配合物具有特定的荧光效应，有望成为光动力诊断和治疗的有效光敏剂。     

新型八取代酞菁谱学性质研究

对1,4,8,11,15,18,22,25-八氧代正丁基酞菁铜、1,4,8,11,15,18,22,25-八氧代丁酸甲酯基酞菁锰、1,4,8,11,15,18,22,25-八氧代正丁酸甲酯基酞菁铜、1,4,8,11,15,18,22,25-八氧代正丁酸甲酯基酞菁锌这四种新型八取代酞菁的红外光谱、紫外光谱和荧光光谱的性质...     

酞菁铜衍生物在酞菁铜氧化铁纳米粒子交替LB膜中的分子取向

通过Langmuir Blodgett技术制备了酞菁铜 氧化铁纳米粒子交替LB膜 ,利用偏振紫外 可见光谱对酞菁铜衍生物在不同制膜条件下所制得的交替膜中的分子取向进行了研究。结果表明 ,在同一氧化铁溶胶亚相中 ,随着表面压的增大 ,或在相同的表面压下 ,随着亚相中氧化铁浓度的减小 ,酞菁铜分子在其复合LB膜中倾斜程度变大。     

单异硫氰基3∶1不对称酞菁锌的光谱性质研究

测定了三种含异硫氰基3∶1不对称酞菁锌配合物(RO)₆(NCS)PcZn(Ⅱ)(R=n-C₄H₉; n-C₅H₁₁; n-C₁₀H₂₁)在五种有机溶剂中的电子吸收光谱,研究了取代基和溶剂对吸收光谱的影响和规律。同时测定它们在有机溶剂中的荧光发射光谱,研究了外部取代基、溶剂和浓度对最大发射波长及荧光强度的影响规律,发现此类配合物具有特定的荧光效应,有望成为光动力诊断和治疗的有效光敏剂。     

锌酞菁配合物的线性与非线性光学性质研究

利用UV-Vis吸收光谱、荧光光谱及开孔Z扫描技术对五种锌酞菁配合物的DMF溶液进行了线性与非线性光学性质的表征;并以无取代锌酞菁为例,研究了酞菁溶液线性与非线性光学性能的浓度效应。结果表明五种酞菁均具有显著的荧光和非线性光学效应,其非线性吸收系数在10-9 cm·W-1数量级范围。且随酞菁浓度的改变,其荧光和非线性吸收明显改变,表现出强烈的浓度效应。     

1,11,15,25-四羟基-4,8,18,22-二（桥联二丙羧基）酞菁铜的合成及性质研究

对新型取代基酞菁和酞菁晶体合成和性质进行了研究。因为酞菁在信息、医疗、化工等众多领域有很广泛的应用,所以近百年来一直是科学家研究的热点课题。酞菁经过近百年的研究,科学家已经合成了上万种酞菁衍生物,但是,随着科技的不断进步,人类社会不断发展的需求,具有新特性的新型酞菁的获得仍是相关科技工作者孜孜以求的目标。为此,在本论文中,我们改进了合成方法,合成了新型的桥联酞菁材料：1,11,15,25-四羟基-4,8,18,22-二（桥联二丙羧基）酞菁铜,表征其结构。并研究电化学性质。首先以丙二酸和3,6-二羟基邻苯二腈为起始原料,以水为溶剂,加入浓硫酸作为催化剂,先合成前体,即丙二酸3,3′-二(6–羟基邻苯二腈)脂。然后再用丙二酸 3,3′-二(6-羟基邻苯二腈)脂与一水合乙酸铜,以正戊醇为溶剂,以DBU为催化剂,合成了1,11,15,25-四羟基-4,8,18,22-二（桥联二丙羧基）酞菁铜,其分子式是C₃₈H₁₆N₈O₁₂Cu。对1,11,15,25-四羟基-4,8,18,22–二（桥联二丙羧基）酞菁铜进行紫外吸收及荧光光谱测定,证明合成产物是目标产物,并研究了1,11,15,25-四羟基-4,8,18,22-二（桥联二丙羧基）酞菁铜的电化学性质。     

酯基取代的吲哚衍生物的红外和荧光光谱研究（英文）

色氨酸衍生物长期以来一直被用作位点特异性的非天然氨基酸红外和荧光探针.其中,4-氰基色氨酸的荧光在可见光范围,是目前已知的最小的非天然氨基酸蓝色荧光探针.本研究组致力于发展其它小型的基于吲哚或色氨酸衍生物的蓝色、绿色和红色荧光探针.本文利用傅立叶红外光谱、紫外可见吸收光谱、稳态和时间分辨荧光光谱系统测量了酯基取代的六种吲哚衍生物在不同溶剂中的光谱.发现吲哚-4-甲酸甲酯的荧光在450 nm,并且具有较长的荧光寿命,有望被用作新型的非天然氨基酸荧光探针.本文的研究不仅为选择合适的吲哚衍生物进行实际应用提供了指导,并且为计算吲哚不同位置的取代对电子跃迁的影响提供了实验数据.     

某些金属酞菁配合物的单体电子吸收光谱和荧光光谱

研究了某些金属酞菁配合物在单体状态下的电子吸收光谱和荧光光谱,并探讨了溶剂、中心离子和取代基的影响效应。     

Substitution effect on the adlayer formation of tetrachloroperylene bisimides on HOPG surface

Di-perylene-3,4,9,10-tetracarboxylic acid bisimides (diPBI) is an n-type graphene molecule with nonplanar conformation. The controllable assembly and molecular adlayer structures of tetrachlorinated diPBI derivatives with different alkyl chains substitutions on highly oriented pyrolytic graphite were studied by scanning tunneling microscopy. When the molecule was substituted by butyl, the formation of multilayer or monolayer can be regulated by the solution concentration. When the molecule was substituted by 2-ethylhexyl, however, it can only form monolayer assembly. The unit cell of 2-ethylhexyl substituted diPBI adlayer was expanded to a rectangular shape compared to that of the butyl substituted diPBI. The steric repulsion of the alkyl chains (straight or branched) substitution is proposed as the key factor to control the adlayer structures of diPBI derivatives. The result is helpful to the design and fabrication of the organic film of chemically synthesized graphene type materials.     

水溶性酞菁类光敏剂的合成及其光谱性质研究

以3-硝基邻苯二甲腈与3-巯基-1-丙磺酸钠为原料,在醋酸盐存在下通过四环化合成了三种带四个3-磺基丙基磺酰基的水溶性酞菁。利用紫外-可见吸收光谱,荧光光谱等对其光谱性质进行了测量,并计算了其荧光量子产率和单线态氧量子产率。引入吸电子基团所合成的水溶性酞菁与ZnPc相比,其荧光发射光谱的形状并未改变,但其最大荧光发射波长均发生10 nm以上的红移。三种水溶性酞菁中锌酞菁的荧光量子产率最高,铜酞菁的荧光量子产率最低;它们在水溶液中的荧光呈双指数衰减,这可归结为激发态质子化或去质子化的结果。单线态氧量子产率锌酞菁最大,空心酞菁次之,铜酞菁最小。光谱分析结果表明,合成的锌酞菁和空心酞菁具有高的单线态氧量子产率和高的光稳定性,有望用作光动力治疗和光免疫治疗的光敏剂。     

稳态荧光探针法研究槐糖脂生物表面活性剂的胶束化行为

应用稳态荧光探针法测定了非离子生物表面活性剂槐糖内脂临界胶束浓度(CMC)和胶束聚集数(N_agg),并考察了添加无机电解质和短链脂肪醇对槐糖内酯CMC的影响。结果表明,槐糖内酯的CMC为1.3×10-4 mol·L-1,并随加入电解质浓度的升高而略有降低,外加短链脂肪则使其CMC值升高;在4~8倍的CMC浓度范围内,槐糖内酯溶液N_agg随其浓度增大而增大,但胶束聚集数较小,为4~8个;激光纳米粒径结果显示槐糖内酯胶束动态直径较大且分布较为集中,平均约为90 nm。槐糖内酯胶束具有聚集数小而直径大的特点,表明该生物表面活性剂所形成的胶束排列较为松弛。     

Optical characterization of bromo-alkoxyl-substituted copper phthalocyanine derivative thin films

A series of thin films of copper phthalocyanine derivatives with bromine and alkoxyl substituents [CuPc(OC₈H₁₇)₄Br_m, m=0,1,2,4] were prepared on single-crystal silicon substrates by spin coating. The ellipsometric spectra of the films have been studied on a rotating analyzer–polarizer type of scanning ellipsometer. The optical, dielectric constants and absorption coefficients of the films in 500–800 nm wavelength region were obtained. The results show that the complex refractive index, dielectric constants and absorption coefficient of these thin films are influenced regularly by bromine substituent on conjugated macrocycle. It was found that there are approximately linear relationships between the resonance absorption wavelengths of the films and the average number of bromine atoms substituted on the phthalocyanine ring.     

Denaturation Mechanism of BSA by Urea Derivatives: Evidence for Hydrogen-Bonding Mode from Fluorescence Tools

Urea and alkyl urea derivatives, which posses a free N-H moiety in the urea molecular framework is responsible for the fluorescence quenching of BSA. Fluorescence quenching accompanied with a blue initially and subsequently a red shift in the emission maximum of BSA is observed on the addition of urea derivatives containing N-H moieties. On the contrary, a fluorescence enhancement accompanied with a shift in the emission maximum towards the blue region is observed on the addition of tetramethylurea (TMU). Urea derivatives, which posses a free N-H moiety acts as a perfect denaturant by direct hydrogen-bonding interaction with BSA resulting in the unfolding process. The unfolding of the buried tryptophan moieties to the aqueous phase does not occur, when all the N-H moieties in the urea are methyl substituted (TMU). Fluorescence spectral techniques reveal that the direct hydrogen-bonding interaction of the N-H moiety of urea molecular framework with the carbonyl oxygen moieties of BSA results in the unfolding of the tryptophan moieties to the aqueous phase, while that of the carbonyl oxygen of urea with the N-H moieties of BSA is definitely not involved in the denaturation process. Steady state and time-resolved fluorescence studies illustrate that the extent of protein folding occurs at a relatively lower concentration of unsymmetrical alkyl urea derivatives (butyl urea (BU) and ethyl urea (EU)), compared to that of urea.     

基于共振瑞利散射法的人血清蛋白浓度的研究

文章针对人标准血清总蛋白浓度的定量测定, 建立了以四羧基金属酞菁锌为光谱探针检测蛋白质的共振光散射的新方法。该方法的实质是将人标准血清总蛋白和酞菁锌溶液混合, 当光源照射到样品池中的混合液时, 将激发出强烈的共振瑞利散射荧光信号, 根据信号强度的强弱, 计算血清蛋白浓度的大小。自行设计的测试装置采用了薄壁试管的样品皿, 减小了激光光波穿过溶液时的光程, 可得到更强的探测信号。测试结果表明: 根据数字示波器显示的探测器信号, 可得出电压的峰峰值, 体现了荧光的大小, 从而可以进一步计算出血清蛋白的浓度。     

Determination of the aggregation degree of zinc-phthalocyanines derivatives into polymeric films via the characterization of the linear-optical absorption

We investigated the aggregation effects in films composed by zinc-phtalocyanine and its derivative, dispersed into a poly(methyl methacrylate) matrix, by analyzing the absorption coefficient at an increasing concentration. The ratio by weight of the compound to the host polymer was varied within two different ranges in order to extrapolate the solubility limit for both molecules. Measurements performed by spectroscopic analysis, allowed the calculation of the linear-optical absorption coefficient. Experimental data were interpolated by adopting a set of three Lorentzian oscillators characterized by three different sets of parameters, i.e., the intensity factor, resonance frequency, and line width, respectively. With the obtained data, the degree of monomer and dimer concentration in the films was evaluated. Within the investigated concentration range, the maximum solubility was found to be very different for the two investigated molecules, where the substituted phthalocyanine was very efficient in reducing the aggregation tendency.