钯酞菁配合物的荧光光谱与单线态氧的生成速率

分别测定了四-α-(2,2,4-三甲基-3-戊氧基)酞菁钯(锌)和四-α-(2,4-二叔丁基苯氧基)酞菁钯(锌)配合物的紫外-可见电子吸收光谱,荧光发射光谱和单线态氧生成速率,结果表明虽然酞菁钯的中心金属离子为开壳层电子结构,但其生成单线态氧(1O₂)的能力与中心金属为闭壳层结构的相应取代酞菁锌相近,这可能是与其荧光发射很弱,系间串跃很强相关。     

四取代酞菁金属配合物的紫外-可见吸收光谱和荧光发射光谱研究

报道了16种含哌嗪或含哌啶四取代酞菁金属配合物{R4PcM,R=2-[4-(2-磺基乙基)哌嗪-1-基]乙氧基(SPEO—)、2-(哌啶-1-基)乙氧基(PEO—);取代位置分别在α位和β位;M=Zn(Ⅱ),Ni(Ⅱ),Co(Ⅱ), Cu(Ⅱ)}的UV-Vis吸收光谱和荧光发射光谱的测定,探讨了中心金属离子、取代基种类及其取代位置、溶剂等因素对酞菁金属配合物UV-Vis吸收光谱和荧光发射光谱性质的影响。结果表明:R4PcM的Q带λ_max落在681～718 nm范围内,与相同中心金属离子的无取代酞菁金属配合物(669～671 nm)比较都发生了不同程度的红移,荧光发射光谱与UV-Vis吸收光谱呈镜像关系,特别的是两种β位取代中心金属离子为Zn(Ⅱ)的酞菁金属配合物[β-(SPEO)₄PcZn,β-(PEO)₄PcZn]具有极高的摩尔消光系数、较大的荧光量子产率和较长的荧光寿命,有望开发成新型的光动力诊疗用光敏剂。     

四氮杂芳氧基取代酞菁金属配合物的UV-Vis吸收光谱研究

测定了6个系列18种四氮杂芳氧基取代酞菁金属配合物(R₄PcM, R=4-吡啶氧基、8-喹啉氧基、2-甲基-8-喹啉氧基;取代位置分别为：α位及β位;M=Ni(Ⅱ), Cu(Ⅱ), Zn(Ⅱ))的UV-Vis吸收光谱。探讨了中心金属、取代基种类及取代位置、溶剂对酞菁金属配合物UV-Vis吸收光谱中Q带最大吸收波长(λ_max)的影响,实验结果表明：标题配合物的Q带λ_max在680 nm左右;与相同中心金属无取代酞菁金属配合物(669～671 nm)比较,标题配合物的Q带λ_max都发生了不同程度的红移;当取代基在α位时其种类对标题配合物Q带λ_max的影响较在β位时显著,且相同取代基及中心金属的α位取代配合物的Q带λ_max较β位取代配合物的红移更为明显;中心金属、溶剂对标题配合物的Q带λ_max影响不明显。     

轴向嘧啶衍生物修饰硅酞菁的光谱性质、光动力抗癌活性及与白蛋白相互作用的研究

研究了一种新型轴向修饰硅酞菁,即二(2-氨基-6-三氟甲基-4-嘧啶氧基)硅酞菁(SiPcF)的光物理光化学性质、离体光动力抗癌活性以及与白蛋白的相互作用。结果表明,SiPcF的Q带最大吸收峰波长686 nm,摩尔吸光系数为2.3×105 mol-1·L ·cm-1,荧光发射峰694 nm,荧光量子产率为0.46,光敏化产生单线态氧的量子产率为0.38,是有效的1O₂光敏剂。SiPcF与牛血清白蛋白(BSA)具有较强的相互作用,两者的结合常数为4.33×105mol·L-1,结合位点数为1。离体细胞实验表明,SiPcF具有较高的光动力抗癌活性,对人肝癌细胞HepG2的IC₅₀值为5×10-7mol·L-1。     

两个发光铽(Ⅲ)配合物的晶体结构和荧光性质

采用水热法合成了两个稀土配合物[Tb(3-SBA)(IP)OH(H₂O)]·H₂O (1)和[Tb(dpdc)_1.5(IP)(H₂O)]_n(2)(3-SBA=3-羧基苯磺酸根,dpdc=2,2′-联苯二甲酸根,IP=1H-咪唑[4,5-f][1,10]-邻菲啰啉),并用X-ray单晶衍射仪测定了它们的晶体结构。配合物1是由3-羧基苯磺酸根和羟基交替连接Tb(Ⅲ)离子形成的一维链。配合物2是由2,2′-联苯二甲酸根桥联Tb(Ⅲ)离子形成的一维链。配合物1与2在紫外灯下均发出强的绿色荧光,其荧光光谱中有四个发射峰,位于492,544,584和619 nm,分别对应于Tb(Ⅲ)离子的5D₄→7F_J(J=6-3)跃迁,其发射光谱中均不存在配体荧光。配体吸收紫外光,有效地转移能量给Tb(Ⅲ)离子。配合物1与2中Tb(Ⅲ)离子的5D₄发光显示了单指数衰减,寿命分别为0.287和0.439 ms,发光量子产率分别为9.28%和7.07%。     

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。     

二氢沉香呋喃倍半萜的2D NMR研究

利用¹H-¹³C相关(¹H-¹³C COSY)谱对1β-乙酰氧基-2β(α-甲基丁酰氧基)-6α-羟基-8β,9α-二苯甲酰氧基-β-二氢沉香呋喃(A),和1β-乙酰氧基-2β(α-甲基丁酰氧基)-6α-羟基-8β(β-呋喃甲酰氧基)-9α-苯甲酰氧基-β-二氢沉香呋喃(B)的¹³C NMR谱化学位移进行了全指定,利用¹H-¹H远程相关(¹H-¹H COSYLR)谱确定了化合物A和B中6-Ha和7-He,8-He和9-He的弱偶合,以及7-He和9-He的弱W型远程偶合.     

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。     

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。     

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。     

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。     

Photofunctional Polyurethane Nanofabrics Doped by Zinc Tetraphenylporphyrin and Zinc Phthalocyanine Photosensitizers

Polymeric polyurethane nanofabrics doped by zinc tetraphenylporphyrin (ZnTPP) and/or zinc phthalocyanine (ZnPc) photosensitizers were prepared by the electrospinning method and characterized by microscopic methods, steady-state and time-resolved fluorescence, and absorption spectroscopy. Nanofabrics doped by both ZnTPP and ZnPc efficiently harvest visible light to generate triplet states and singlet oxygen O₂(¹Δ_g) with a lifetime of about 15 μs in air atmosphere. The energy transfer between the excited singlet states of ZnTPP and ground states of ZnPc is described in details. All nanofabrics have bactericidal surfaces and photooxidize inorganic and organic substrates. ZnTPP and ZnPc in the polyurethane nanofabrics are less photostable than incorporated free-base tetraphenylporphyrin (TPP).     

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。     

Charge Transfer Photophysics of Tetra(α-amino) Zinc Phthalocyanine

The absorption, fluorescence, and transient absorption spectra of Tetra(α-amino) zinc phthalocyanine, ZnPc(α-NH₂)₄, have been measured in polar solvents and compared with that of ZnPc(α-R)₄ (R?=?H, NO₂, OCH(CH₃)₂). While the latter three showed the typical photophysics of phthalocyanines, ZnPc(α-NH₂)₄ exhibits distinct spectral properties, a very low fluorescence quantum yield and a relatively long fluorescence lifetime. These observations are explained by the substantial charge transfer characters in the absorption and fluorescence spectra of ZnPc(α-NH₂)₄. NMR indicates that intramolecular H-bonding makes atoms in NH₂ actually coplanar with other elements of ZnPc(α-NH₂)₄. The local excited state is non emissive and the weak emission is assigned to its charge transfer state. The transient absorption bands from laser flash photolysis located at 630 nm, 645 nm is assigned to the mono-charge transfer state, while that at 545 nm is assigned to the di-charge transfer state.     

Fluorescence Properties of Phenol-Modified Zinc Phthalocyanine that Tuned by Photoinduced Intra-Molecular Electron Transfer and pH Values

Tetra[α-(4-hydroxyphenoxy)] zinc phthalocyanine, ZnPc(α-OPhOH)₄, was synthesized and its photophysics was found to be sharply pH dependent. Dual fluorescence emission around 700 nm was observed when it is dissolved in basic solution. The fluorescence of the phthalocyanine can be sharply switched off at pH 9.1 due to the intramolecular photoinduced electron transfer (PET) in ZnPc(α-OPhONa)₄, formed by the deprotonation of ZnPc(α-OPhOH)₄. The photophysics of both ZnPc(α-OPhOH)₄ and ZnPc(α-OPhONa)₄ were studied in detail by UV-vis absorption, steady state and time-resolved fluorescence and transient absorption (TA) to reveal the fluorescence quenching mechanism. Intra-molecular PET in ZnPc(α-OPhONa)₄ from the donor, PhONa subunits, to the acceptor, ZnPc moiety, was characterized by the much smaller fluorescence quantum yield (0.003) and lifetime (<0.20 ns). PET was further evidenced by the occurrence of charge separation state (CSS) in TA spectra, i.e. the bands due to anion radical of ZnPc and phenol radical. The lifetime of the charge separation state is ca. 3 ns, the efficiency of PET is ca. 99% and the rate constant of PET is 2.3 × 10¹⁰ s⁻¹.     

十六羧酸基酞菁锌光敏剂与白蛋白相互作用的光谱研究及复合物的制备

利用光谱法研究了光敏剂分子2,3,9,10,16,17,23,24-八(3,5-二羧酸基苯氧基)酞菁锌(ZnPc(COOH)₁₆)与白蛋白(BSA和HSA)的相互作用,结果表明,ZnPc(COOH)₁₆与BSA,HSA存在较强的相互作用,结合常数为2.25～2.94×106 L·mol-1。同时,通过温育摩尔比为2∶1的ZnPc(COOH)₁₆和白蛋白混合物,进而凝胶色谱分离纯化,得到了摩尔比为1∶1的ZnPc(COOH)₁₆-BSA和ZnPc(COOH)₁₆-HSA复合物。光谱研究表明,ZnPc(COOH)₁₆在复合物中以单体形式存在,Q带最大吸收峰和发射峰均较单纯的ZnPc(COOH)₁₆有所红移。     

The effect of annulation of benzene rings on the photophysics and electronic structure of tetraazachlorin molecules

The photophysics and electronic structure of tribenzotetraazachlorins (H₂, Zn, and Mg), which are novel analogues of phtalocyanines, have been studied experimentally and theoretically. At 293 K, the electronic absorption, fluorescence, and fluorescence excitation spectra are recorded and the fluorescence quantum yield and lifetime, as well as the quantum yield of singlet oxygen generation, are measured; at 77 K, the fluorescence, fluorescence excitation, and fluorescence polarization spectra are recorded and the fluorescence lifetime values are measured. The dependences of the absorption spectra and photophysical parameters on the structure variation are analyzed in detail. Quantum-chemical calculations of the electronic structure and absorption spectra of tribenzotetraazachlorins (H₂, Mg) are performed using the INDO/Sm method (modified INDO/S method) based on molecular-geometry optimization by the DFT PBE/TZVP method. The results of quantum-chemical calculations of the electronic absorption spectra are in very good agreement with the experimental data for the transitions to two lower electronic states.     

Encapsulation of Photosensitizers and Upconversion Nanocrystals in Lipid Micelles for Photodynamic Therapy

Photodynamic therapy (PDT) is a promising method for cancer therapy. However, it is constrained by limited penetration depth of visible light, hydrophobicity of photosensitizers, and lack of tumor targeting. In this work, the photosensitizer zinc phthalocyanine (ZnPc) and upconversion nanocrystals (UCNs) are encapsulated into OQPGA‐PEG/RGD/TAT lipid micelles. The UCNs acting as a nanotransducer convert deep‐penetrating near‐infrared (NIR) light to visible light for activating the photosensitizer. OQPGA‐PEG/RGD/TAT lipid micelles are used as a carrier for the photosensitizer, with improved biocompatibility and cancer‐targeting ability. The results show that the photosensitizer ZnPc‐ and UCNs‐loaded OQPGA‐PEG/RGD/TAT lipid micelles are nanoparticles with an average size of 25 nm. The lipid micelle nanoparticles are stable in water with low leakage of photosensitizer. The absorption peak of the photosensitizer overlaps with the emission peak of UCNs, so the visible fluorescence emitted from the UCNs upon excitation by the NIR laser at 980 nm can activate the photosensitizer to produce singlet oxygen for PDT. The targeting RGD peptide and cell‐penetrating TAT peptide on the surface help the nanoparticles getting into cancer cells. The OQPGA‐PEG/RGD/TAT lipid micelles encapsulated with both the photosensitizer ZnPc and UCNs could be used for targeted PDT by using deep‐penetrating NIR light as the light source.