四磺化酞菁钴在水溶液中二聚作用力的研究

采用发光光度法研究了四磺化酞菁钴（ＣｏＴＳＰｃ）在水、醇－水（ＭｅＯＨ、ＥｔＯＨ、ＰｒＯＨ）、胶束、微乳液、乙二胺、氨水、氰化钾的水溶液中的二聚现象，测定了ＣｏＴＳＰｃ的二聚常数ＫＤｏＴＳＰｃ与ｅｎ、ＮＨ３、ＣＮ形成配合物的稳定常数Ｋ和生成反应速率常数ｋ。     

CEL溶液中二磺酸基二邻苯二甲酰亚胺甲基酞菁锌的电子吸收和荧光光谱

两亲性金属酞菁配合物二磺酸基二邻苯二甲酰亚胺甲基酞菁锌（ＺｎＰｃＳ２Ｐ２）能有效选择地滞留在组织中,是一种新型的光动力治疗肿瘤的光敏剂。有关酞菁化合物治疗肿瘤的机制目前还不清楚,而对ＣＥＬ溶液中该光敏剂状态的研究对阐明其机制有重要意义,本文对不同浓度ＣＥＬ溶液中的二磺酸基二邻苯二甲酰胺甲基酞菁锌的吸收光谱和荧光光谱进行了研究,探讨了它在溶液中的聚集状态,通过分析确定其聚集态为二聚体,并获得其平衡常数和单体的摩尔吸光系数。     

用对分法计算二聚体系平衡常数

本文根据组合原理组成任意的三元代数方程组，经过一系列代数变换，获得关于二聚体系平衡常数k的一元代数方程，用单调函数的性质判定该方程是滞有解；对有解一元代数方程，用对分法等数值计算方法求得二聚体系平衡常数，并以拟合误差为判据确定最终二聚体系平衡常数，用本方法计算出的二磺化酞菁和三磺化酞菁的平衡常数分别为47973.4和30271.8，所得结果优于文献。     

可溶性钒氧酞菁在不同介质中的吸收光谱研究

研究了四丙基取代钒氧酞菁（Ｐｒ４ＶＯＰｃ）在不同介质中的吸收光谱。Ｐｒ４ＶＯＰｃ分子在不同介质中的吸收光谱差别很大：在稀溶液中以分子的单体吸收为主（λｍａｘ＝７０７ｎｍ），在浓溶液和ＰＭＭＡ薄膜中由于形成平行排列结构的二聚体而使分子单体的吸收峰发生蓝移（λｍａｘ＝６６０ｎｍ），在蒸发膜中则由于形成斜交结构的二聚体使得分子单体的吸收峰发生分裂形成红移和蓝移峰（λｍａｘ＝７２０ｎｍ，６６０ｎｍ），在溶液沉积的固态薄膜中由于形成结晶相Ｉ而表现出强烈的近红外吸收（λｍａｘ＝８２６．９ｎｍ）。造成这种差别的原因是四个丙基的引入加大了ＶＯＰｃ分子的空间位阻效应。通过热处理或溶剂蒸汽处理，可以使Ｐｒ４ＶＯＰｃ蒸发膜转变成具有强近红外吸收的结晶相Ｉ；而只有通过溶剂蒸汽处理才能使ＰＭＭＡ介质中的Ｐｒ４ＶＯＰｃ转变成结晶相ＩＩ。     

4，4′，4″，4－磺酸酞菁镓的二聚常数的测定

采用光度法测定了４，４′，４″，４－磺酸酞菁镓（ＴｓＰｃＧａ）的二聚平衡常数Ｋｄ，讨论了ｐＨ值、离子强度、水、温度等因素对Ｋｄ的影响。     

酞菁锌掺杂二氧化硅凝胶基质的光谱学特征

利用溶胶凝胶技术将四磺化酞菁锌 (ZnPcS4)成功地引入到了二氧化硅凝胶基质中 ,制备了均匀掺杂的有机 /无机复合干凝胶。研究ZnPcS4分子在溶胶凝胶过程中紫外可见吸收光谱的变化规律以探索其在复合体系中的存在状态。实验表明 ,在溶胶阶段 ,随着时间的延长 ,紫外可见吸收光谱中单体的吸收峰强度增大 ,说明凝胶中酞菁单体的浓度增大 ;而形成凝胶后 ,随着时间的延长 ,紫外可见吸收光谱中单体的吸收峰强度减小 ,二聚体的吸收峰强度增大 ,说明由于体系结构和微化学环境的变化 ,酞菁分子趋向于聚合。     

CdS薄膜的染料敏化

用ＬＢ方法在电沉积ＣｄＳ薄膜上修饰了ＰｃＣｕ单分子膜，并利用表面光电压谱对ＣｄＳ薄膜与ＰｃＣｕ修饰的ＣｄＳ薄膜进行了测试。结果表明，修饰后的ＣｄＳ薄膜其表面光电压值提高约５０倍，并且光电压响应由３００－５００ｎｍ扩展为３００－７００ｎｍ。紫外－可见偏振光谱测试表明，ＬＢ膜中酞菁环的取向角为４５度。     

两亲性光敏剂Al(OH)PcSP在醇水和水溶液中的分子光谱和存在状态

研究了具有光动力抗癌活性的两亲性光敏剂磺基邻苯二甲酰亚胺甲基酞菁羟基铝 (Al(OH)PcSP)在醇水和在水中的电子吸收光谱 ,并探讨了其聚集状态。研究表明 ,Al(OH)PcSP在醇水溶液中以单体形式存在 ,醇的碳链和羟基数对Al(OH)PcSP的单体吸收光谱没有显著的影响。但在水中 ,Al(OH)PcSP存在单体 二聚体平衡 ,二聚平衡常数为 5 730 7× 10 4 mol·L-1。Al(OH)PcSP在水中所形成的二聚体的Q带特征吸收峰位于 740 5nm ,相对于其单体特征吸收峰 (6 76 5nm)红移 ,而一般金属酞菁在水中所形成的聚集体Q带特征吸收光谱均相对于单体兰移至位于 6 30nm附近。研究了Al(OH)PcSP的荧光光谱 ,结果说明 ,二聚体的荧光很弱。     

SnPc多晶薄膜的结构、光谱与线性二向色研究

真空升华获得了两种晶态结构的酞菁锡（ＳｎＰｃ）多品薄膜．用常规吸收光谱和Ｘ射线衍射谱进行了表征和分析．观察到激子谱带的Ｂｅｔｈｅ分裂和Ｄａｖｙｄｏｖ分裂对异向性衬底上生长的ａ－ＳｎＰｃ和β－ＳｎＰｃ薄膜分别测量了偏振吸收光谱．发现其中β－ＳｎＰｃ异向膜具有明显的光学二向色性，并且当测试波长从Ｑ激子谱带的蓝侧向红侧变化时，二向色吸收轴发生９０°旋转．在５３０ｎｍ附近观察到一个新的吸收带，认为属于ＳｎＰｃ分子间电荷转移激子谱带。 关键词：     

酞菁锌参杂二氧化硅凝胶基质的光谱学特征

利用溶胶-凝胶技术将四磺化酞菁锌（ZnPcS4）成功地引入到了二氧化硅凝胶基质中，制备了均匀掺杂的有机/无机复合干凝胶。研究ZnPcS4分子在溶胶-凝胶过程中紫外-可见吸收光谱的变化规律以探索其在复合体系中的存在状态。实验表明，在溶胶阶段，随着时间的延长，紫外-可见吸收光谱中单体的吸收峰强度增大，说明凝胶中酞菁单体的浓度增大；而形成凝胶后，随着时间的延长，紫外-可见吸收光谱中单体的吸收峰强度减小，二聚体的吸收峰强度增大，说明由于体系结构和微化学环境的变化，酞菁分子趋向于聚合。     

LB薄膜中四新戊氧基酞菁锌和四壬基酞菁铜分子聚集体的吸收光谱的温度特性

本文制备了四新戊氧基酞菁锌(Tetra-neopentoxy phthalocyanine zine)(TNPPeZn)和四壬基酞菁铜(Tetra-nonyl phthalocyanine copper)(TNPeCu)两种酞菁衍生物的Langmuir-Blodgett(LB)薄膜.通过测量10～473K温度下的吸收光谱,研究了两种薄膜的分子聚集状态.TNPPeZn的LB薄膜中,存在着分子单体和分子二聚体,在吸收光谱中分别表现为680nm和620nm的吸收峰.随着温度的升高,分子单体逐渐转变为分子二聚体,这个过程是不可逆的.TNPeCu的LB薄膜中,除了分子单体和分子二聚体以外,还有吸收为740nm的分子J聚集体存在.随着温度的变化,J聚集体发生可逆变化.     

Photochemistry of tetrasulphonated magnesium phthalocyanine in water and DMSO solutions by Raman, femtosecond transient absorption, and stationary absorption spectroscopies

Photochemical and photophysical behavior of the tetrasulphonated magnesium phthalocyanine MgPcS₄ has been studied by Raman spectroscopy, femtosecond transient absorption, and stationary UV–VIS absorption spectroscopies. It has been shown also that the dimerization equilibrium constant K for the tetrasulfonated magnesium phthalocyanine is strongly shifted towards monomeric form in DMSO solutions compared to aqueous systems. The Raman and emission spectra recorded in the range of 294–77 K combined with the femtosecond transient absorption reveal spectral features that provide unique information about the primary photochemical and photophysical events of magnesium phthalocyanines in liquid solutions as well as in the crystal frozen matrices.     

Pressure-induced dimerization of C60 fullerene

The dimerization of C₆₀ fullerene under conditions of quasi-hydrostatic compression at temperatures above 293 K is investigated by IR spectroscopy, Raman scattering (RS) spectroscopy, and x-ray diffraction. The measured dimer (C₆₀)₂ content in the products of the polymerization of fullerite as a function of the pressure, temperature, and treatment time shows that dimerization occurs even at room temperature in the entire pressure range above ∼1.0 GPa. However, at least at temperatures above 400 K dimerization does not result in the formation of a dimer phase as a stable modification of the system, since the dimer is an intermediate product of the transformation. It is shown that increasing the holding time at 423 K decreases the content of the dimer fraction in the samples and results in the formation of linear (at 1.5 GPa) and two-dimensional (at 6.0 GPa) polymers, which are structure-forming elements of the orthorhombic and rhombohedral polymerized phases. Pis'ma Zh. éksp. Teor. Fiz. 68, No. 12, 881–886 (25 December 1998)     

Branching ratio and L2 + L3 intensities of 3d-transition metals in phthalocyanines and the amine complexes

L(2,3) inner-shell excitation spectra were obtained by electron energy-loss spectroscopy (EELS) for the divalent first transition series metals in phthalocyanine complexes (MPc) such as titanium oxide phthalocyanine (TiOPc), fluoro-chromium phthalocyanine (CrFPc), manganese phthalocyanine (MnPc), iron phthalocyanine (FePc), cobalt phthalocyanine (CoPc), nickel phthalocyanine (NiPc) and copper phthalocyanine (CuPc). It was found that the value of normalized total intensity of I(L2 + L3) was nearly proportional to the formal electron vacancies of each 3d-state, and the values of the branching ratio, I(L3)/I((L2 + L3), represented a high-spin-state rather than low-spin-state for MnPc, FePc and NiPc. EELS was also applied to charge-transfer complexes of FePc with an amine such as pyridine or gamma-picoline. It was concluded that their I(L2 + L3) intensity of Fe showed the decrease in vacancies of 3d-states on the formation of the charge-transfer complex with these amines, which suggests some electron transfer from the amine to Fe in phthalocyanine. The EELS study provides beneficial information for investigating the electronic states of the specific metal sites in organic materials.     

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...     

Density-matrix renormalization group study of the spin-Peierls instability in the antiferromagnetic Heisenberg ladder

The columnar dimerized antiferromagnetic S?=?1/2 spin ladder is numerically studied by the density-matrix renormalization-group (DMRG) method. The elastic lattice with spin-phonon coupling ?? and lattice elastic force k is introduced into the system. Thus the S?=?1?/?2 Heisenberg spin chain is unstable towards dimerization (the spin-Peierls transition). However, the dimerization should be suppressed if the rung coupling J _?? is sufficiently large, and a Columnar dimer to Rung singlet phase transition takes place. After a self-consistent calculation of the dimerization, we determine the quantum phase diagram by numerically computing the singlet-triplet gap, the dimerization amplitude, the order parameters, the rung spin correlation and quantum entropies. Our results show that the phase boundary between the Columnar dimer phase and Rung singlet phase is approximately of the form J _?? ~ \hbox{$(\frac{k}{\alpha^{2}})^{-\frac{5}{4}}$} ( k ?? 2 ) ? 5 4.     

The synthesis and photophysical properties of novel cationic tetra pyridiloxy substituted aluminium, silicon and titanium phthalocyanines in water

This work reports on the synthesis, characterisation and photophysical properties of new unquaternized β-2,(3)-tetra-(2 pyridiloxy) aluminium(III) (3a), silicon(IV) (3b), titanium(IV) (3c) phthalocyanines and their water-soluble quaternized counterparts, 4a, 4b and 4c, respectively. The water-soluble silicon(IV) (4b) and titanium(IV) (4c) phthalocyanine derivatives were found to be aggregated in aqueous media but were partially or fully disaggregated in the presence of a surfactant Cremophor^® EL (CEL). The photophysical properties of aggregated complexes were investigated both in the presence of CEL and in pH 11 alone. Low triplet and fluorescence yield were obtained in pH 11 but an improvement was achieved upon addition of CEL for the aggregated complexes. The unquaternized silicon(IV) phthalocyanine complex (3b) gave the highest triplet quantum yield of 0.77 in DMF followed by its quaternized derivative (4b) with triplet yield of 0.73 in pH 11 plus CEL. The highest triplet lifetime of 220 μs was obtained for 4b in the presence of CEL. Higher fluorescence yields of 0.23 were obtained for quaternized water-soluble aluminium(III) phthalocyanine derivative (4a) in the presence of CEL.     

IR Study of the Pressure Induced Solid State DI- and Polymerization in 1,3-butadiene

The pressure induced chemical reaction of butadiene was studied in the crystal phase by means of FTIR spectroscopy using a Membrane Diamond Anvil Cell (DAC). Two different reaction products, vinylcyclohexene (dimerization) and trans-polybutadiene (polymerization), were obtained. The phase diagram of butadiene was investigated and the existence of an orientationally disordered phase, between the liquid and the ordered solid phase, was identified. The analysis of the time evolution of the integrated absorption of the product bands provides information on the reaction mechanisms. Distinct models are necessary to explain the polymer and the dimer formation.