新型空间链取代四-(6-氨基己酸磺肽基)铝酞菁配合物的合成及其光物理性质

高锰酸钾降解2-萘酚-6-磺酸钠合成了"分子碎片"4-磺酸钾基邻苯二甲酸(1)。1在钼酸铵催化下,用固相法合成了四-磺酸铝酞菁(2)。采用氨基转化的方法,2经磺酰氯化和Hinsberg磺酰胺化反应分别合成了四-磺酰氯铝酞菁(3)和新型空间链取代四-(6-氨基己酸磺肽基)铝酞菁(4)。1～4结构经1HNMR,IR,MS和元素分析表征,并对4的光物理性质进行了初步研究。     

新型棒状磺酸液晶的合成与表征

以联苯为液晶基元,通过磺酸内酯的开环反应合成了新型磺酸基团位于分子末端的棒状分子——4-烷氧基-4’-丁氧烷磺酸基联苯(3a和3b),其结构经1H NMR和IR表征.偏光显微镜观察和差示扫描量热分析结果表明,3在高于180℃时表现出热致性近晶A相.     

单甲基化大豆苷元磺酸盐的合成、晶体结构及活性研究

以在豆苷元为原料合成出强水溶性异黄酮类化合物：7-甲氧基-4'-羟基异黄酮 -3'-磺酸钠（1）和7-甲氧基-4'-羟基异黄酮-3'-磺酸钴（2）。抗缺氧缺血活性试 验表明：化合物1和2的抗缺氧缺血活性比大豆苷元好。X-单晶衍射分析表明化合物 2晶体结构以Co~(2+)为对称中心，含6分子配位水和10分子结晶水，16个分子和7- 甲氧基-4'-羟基异黄酮-3'-磺酸根的羰基、羟基、磺酸基氧原子相互之间通过多个 氢键在晶体内部形成复杂的三维空间网络。     

243～263nm CH3COCH3 的多光子电离研究

在243～263 nm紫外光波段通过质量选择光电离激发谱研究了丙酮（CH3COCH3）的光化学反应通道。分析母体离子CH3COCH3+和碎片离子CH3CO+ 、 CH3+的光电离激发谱和质谱峰宽可以知道: 此光波段丙酮分子的光化学反应主要包括了丙酮分子经由(S1,T1)中间态产生母体离子的（1+1）双光子电离通道,母体离子进一步解离产生碎片离子CH3+的“光电离-光解离”通道和丙酮分子经由(S1,T1)中间态解离成中性自由基碎片CH3CO后再进一步被双光子电离的“光解离-光电离”通道。由母体离子光电离激发谱双光子阈值波长（255.67 nm）给出的丙酮电离势（IP）为（9.696±0.004）eV。     

双甲基化大豆苷元磺酸锂的合成及晶体结构

以大豆苷元为先导化合物,合成了水溶性异黄酮化合物4’,7-二甲氧基异黄酮磺酸锂．X射线单晶衍射分析表明：标题化合物属于三斜晶系,空间群Pi,晶胞参数为：a=0．7732（2）nm,b=1．874（5）nm,c=1．920（5）nm,α=111．224（4）°,β=90．21（5）°,γ=100．68（4）°Z=2．标题化合物的分子组成为[Li（H2O）4]2（C17H13O4SO3）2·4H2O,其中两种类型的锂离子均被4分子水所配位．[Li（H2O）4]^＋、C17H13O4SO3^-和H2O之间存在多种氢键作用;氢键作用以及阴阳离子之间的静电引力作用共同将标题化合物组装成具有三维网络结构的超分子．     

AA/AMPS共聚型吸水树脂反相悬浮合成工艺研究

以过硫酸铵－亚酸钠为引发剂，用反相悬浮法合成丙烯酸／2－丙烯酰胺基－2－甲基丙烷磺酸共聚型吸水树脂，最佳工艺条件为：N，N－亚基双丙烯酰胺浓度＝1．082mmol.L^-1，丙烯酸中和度为80％，2－丙烯酰胺基－2－甲基丙烷磺酸的质量分数w=0.30,OP4-PEG的质量分数w=0.003，双组分引发剂浓度＝22．64mmol.L^-1，反应温度50摄氏度，共聚物吸液率（水及生理盐水）A为：AH2O=1070mL.g^-1,Anormal aaline=220mL.g^-1，抗电解质能力高于聚丙烯酸钠或丙烯酸钠与丙烯酰胺的共聚物（反相悬浮法合成），140℃以上热稳定性低于聚丙烯酸钠，保水性与其相当。     

新型薁磺酸镉配位聚合物的合成及其晶体结构

以薁磺酸钠为配体,通过溶液法合成了一种新型一维链状聚合物（1）,其结构和性能经IR, X-射线单晶衍射和热重分析表征。1属单斜晶系,空间群P2₁/c,晶胞参数a=2.349 6(7) nm, b=0.562 48(18) nm, c=1.148 7(4)nm。 1的中心Cd（Ⅱ）与4个薁磺酸阴离子的4个氧原子及两个水分子的两个氧原子配位,形成六配位八面体构型。配合物1通过磺酸基桥连作用将相邻的两个Cd（Ⅱ）形成一维链状结构。     

双活性磺酸基蔗渣木聚糖对羟基苯甲酸酯的合成及活性模拟

以蔗渣木聚糖(BX)为主要原料、氨基三磺酸钠为酯化剂,在一步酯化合成磺酸基蔗渣木聚糖酯的基础上,利用磺酸基蔗渣木聚糖酯和对羟基苯甲酸进行二步酯化反应,合成了磺酸基蔗渣木聚糖对羟基苯甲酸酯,并考察了反应条件对酯化反应的影响,通过单因素实验确定了第二步酯化反应较佳的合成工艺条件.蔗渣木聚糖酯化改性前后的样品分别用FT-IR,DG-DTG和XRD进行了表征,并对该双酯化衍生物的分子进行了优化与活性模拟.结果表明:FT-IR证明双酯化产物含有磺酸基团和对羟基苯甲酸酯基团,TG-DTG分析表明该双酯化衍生物的热稳定性提高,XRD说明发生双酯化改性后分子排列的规整性提高,结晶度增加;活性模拟实现了磺酸基蔗渣木聚糖对羟基苯甲酸酯与艾滋病毒的对接.     

等瓣性类似关系和金属有机化合物合成

CH_3,CH_2,CH,C等分子碎片是构成有机化合物的基本结构单元.金属和配体组成的分子碎片ML_n可以看作是构成金属有机化合物的基本结构单元.考查有机碎片和金属有机碎片的前线轨道(最高已占和最低未占)可以发现它们之间的类似性.在此基础上,如果以类似的金属有机碎片代替有机碎片,就可以按照已知有机分子的结构来设想未知金属有机化合物的结构,并进行合成,使新化合物的合成更有方向性.     

7-（4-安替吡啉偶氮）-8-羟基喹啉-5-磺酸的合成及其与铜的显色反应

7-（4-安替吡啉偶氮）-8-羟基喹啉为安替吡啉单偶氮类试剂中的一种，该试剂可与镓（Ⅲ）、铟（Ⅲ）、铋（Ⅲ）、钯（Ⅱ）、镍（Ⅱ）、钴（Ⅱ）、铜（Ⅱ）、铁（Ⅱ）等离子发生显色反应。本文在其5位引入磺酸基，合成了7-（4-安替吡啉偶氮）-8-羟基喹啉-5-磺酸（分子式为C20H17N5O5S）试剂。     

Oxygen dependence of two-photon activation of zinc and copper phthalocyanine tetrasulfonate in Jurkat cells

Abstract Photodynamic therapy (PDT), the use of light-activated drugs, is a promising treatment of cancer as well as several nonmalignant conditions. However, the efficacy of one-photon (1-gamma) PDT is limited by hypoxia, which can prevent the production of the cytotoxic singlet oxygen ((1)O(2)) species, leading to tumor resistance to PDT. To solve this problem, we propose an irradiation protocol based on a simultaneous, two-photon (2-gamma) excitation of the photosensitizer (Ps). Excitation of the Ps triplet state leads to an upper excited triplet state T(n) with distinct photochemical properties, which could inflict biologic damage independent of the presence of molecular oxygen. To determine the potential of a 2-gamma excitation process, Jurkat cells were incubated with zinc or copper phthalocyanine tetrasulfonate (ZnPcS(4) or CuPcS(4)). ZnPcS(4) is a potent (1)O(2) generator in 1-gamma PDT, while CuPcS(4) is inactive under these conditions. Jurkat cells incubated with either ZnPcS(4) or CuPcS(4) were exposed to a 670 nm continuous laser (1-gamma PDT), 532 nm pulsed-laser light (2-gamma PDT), or a combination of 532 and 670 nm (2-gamma PDT). The efficacy of ZnPcS(4) to photoinactivate the Jurkat cells decreased as the concentration of oxygen decreased for both the 1-gamma and 2-gamma protocols. In the case of CuPcS(4), cell phototoxicity was measured only following 2-gamma irradiation, and its efficacy also decreased at a lower oxygen concentration. Our results suggest that for CuPcS(4) the T(n) excited state can be populated after 2-gamma irradiation at 532 nm or the combination of 532 and 670 nm light. Dependency of phototoxicity upon aerobic conditions for both 1-gamma and 2-gamma PDT suggests that reactive oxygen species play an important role in 1-gamma and 2-gamma PDT.     

Metal phthalocyanine as photosensitizer for photodynamic therapy (PDT)——Preparation,characterization and anticancer activities of an amphiphilic phthalocyanine ZnPcS_2P_2

A series of sulfonated (S) phthalimidomethyl (P) zinc phthalocyanines (Pc) was synthesized in a reaction, in which both kinds of substituents were introduced to ZnPc simultaneously. The products were separated by HPLC. The five different fractions obtained were further purified by a membrane separation method, and then characterized by UV/Vis, IR, element analysis and the abilities to generate singlet oxygen upon irradiation by light as well as a preliminary determination of in vitro antitumor activities. The results show that one of the five separating parts with formula of ZnPcS2P2 exhibited rather good PDT activity. The compound was further characterized by NMR, MS and thermal analysis. Studies on in vivo antitumor activities of ZnPcS2P2 as photosensi-tizer show that its inhibitory rate was up to 89.8% and 90.8% for S180 and U14 solid tumors transplanted in mice respectively when the dosage of drug was 2 mg/kg and the dosage of laser light with 670 nm wavelength was 72 J/cm2. Several structural factor     

Mineralization of 4-Chlorophenol under Visible Light Irradiation in the Presence of Aluminum and Zinc Phthalocyaninesulfonates

Photosensitized oxidation of 4-chlorophenol (4CP) by the title complexes (AIPcS and ZnPcS) in aerated aqueous solution uponvisible light irradiation(λ=450nm) has been investigated using methanol as a disassociating reagent.It is confirmed that the monomeric species of the sesitizer is more active than the corresponding dimer in singlet oxygen generation for 4CP oxidation.However,the monomer is also the main component found in the sensitlzer‘s photobleaching, In this reload, AIPcS is much more stable than ZnPcS, and the Dhotoble~hlno is observed to proceed via singlet and triplet oxygen, respectlvely.The final products of 4CP oxidation in alkaline solution are carbon dioxide and chloride ions.while at pH=7 and pH=3 the p-benzoquinone is the product.The temperature is found to have influence on both the photosensitized degradation of methyl orange and ZnPcS photobleaching,with an activation energy of 15.8 and 24.2kJ/mol,respectively.     

Investigated aerobic oxidation of aminochlorophenol catalyzed by phthalocyanine complexes

The synthesis of 9-Octadecenamide substituted Fe(II) phthalocyanine (ODAFePc) and Ni(II) phthalocyanine (ODANiPc) complexes from Fe(II) tetracarboxylic acid phthalocyanine (FeTcPc) and Ni(II) tetracarboxylic acid phthalocyanine (NiTcPc) with 9-Octadecenamide. These complexes have high molecular weight and soluble in organic solvents. The complexes have been confirmed by FTIR, Mass spectroscopy, UV–Visible X-ray diffraction, and thermogravimetric analysis. The synthesized complexes exhibit excellent stability and are catalytically active in 2-amino-4-chlorophenol (ACP) oxidation. The new method was used for the determination of the oxidation of phenol by applying different experimental parameters like concentration, catalytic quantity, temperature, and pH to get a good yield and catalytic activity of ODAFePc and ODANiPc were studied. ACP was oxidized by dissolved oxygen with ODAFePc and ODANiPc as a catalyst and immediately combined with 4-aminoantipyrine (4-AAP) to form a pink dye and was determined by appearance of absorption intensity at 580 ​nm. All the experimental results show that ODAFePc and ODANiPc complexes exhibit good catalytic behavior on oxidation of 2-amino-4-chlorophenol.     

A cobalt(II) phthalocyanine with indole substituents: formation,characterization and electrocatalytic studies

Herein, we report the formation of a new cobalt(II) phthalocyanine (CoPc) containing peripheral tetra-substituted indole (CoPc-ind, 2) moieties. The derivatized phthalonitrile, 4-(indole-4-oxy)phthalonitrile (1) as well its corresponding metal complex was characterized by NMR (for 1), IR– and UV–Vis spectroscopy as well as TOF mass spectrometry and elemental analysis (for 2). The electrochemical properties of the N₄-macrocyclic metal complex were investigated using cyclic- and square-wave voltammetry as well as corroborated by UV–Vis spectroelectrochemistry. The CoPc was electrodeposited onto the surface of a Pt working electrode followed by the immobilization of multiwalled carbon nanotubes (MWCNTs) onto the modified working electrode surface. The electrocatalytic activity of the resultant modified electrode toward dopamine revealed a lower ΔE value of 80?mV versus Ag|AgCl for the modified (2-MWCNTs) Pt electrode compared to the bare Pt electrode (ΔE?=?280?mV vs. Ag|AgCl). The diffusion- and convection-controlled electron-transfer kinetics of the chemically modified electrode were evaluated by chronoamperometry and rotating disk electrode techniques. Electrochemical impedance spectroscopic studies revealed that the 2-MWCNTs Pt electrode had a lower charge-transfer resistance and a higher apparent electron-transfer rate constant.     

Synthesis,electrochemistry, and electrocatalytic activity of thiazole-substituted phthalocyanine complexes

Journal of Solid State Electrochemistry - We report the synthesis of non-peripheral metallophthalocyanines which carry four 4-(4-methoxyphenyl)-2-thiazole-2-thio units. 1H-NMR, FT-IR, UV–Vis,...     

Photodynamic activity of substituted zinc trisulfophthalocyanines: role of plasma membrane damage

We recently reported that variations in cellular phototoxicity among a series of alkynyl-substituted zinc trisulfophthalocyanines (ZnPcS3Cn) correlates with their hydrophobicity, with the most amphiphilic derivatives showing the highest cell uptake and phototoxicity. In this study we address the role of the plasma membrane in the photodynamic response as it relates to the overall hydrophobicity of the photosensitizer. The membrane tracker dye 1-[4(trimethylamino)phenyl]-6-phenylhexa-1,3,5-triene (TMA-DPH), which is incorporated into plasma membranes by endocytosis, was used to establish plasma membrane uptake by EMT-6 cells of the ZnPcS3C, by colocalization, and TMA-DPH membrane uptake rates after photodynamic therapy were used to quantify membrane damage. TMA-DPH colocalization patterns show plasma membrane uptake of the photosensitizers after short 1 h incubation periods. TMA-DPH plasma membrane uptake rates after illumination of the photosensitizer-treated cells show a parabolic relationship with photosensitizer hydrophobicity that correlates well with the phototoxicity of the ZnPcS3C,. After a 1 h incubation period, overall phototoxicity correlates closely with the postillumination rate of TMA-DPH incorporation into the cell membrane, suggesting a major role of plasma membrane damage in the overall PDT effect. In contrast, after a 24 h incubation, phototoxicity shows a stronger but imperfect correlation with total cellular photosensitizer uptake rather than TMA-DPH membrane uptake, suggesting a partial shift in the cellular damage responsible for photosensitization from the plasma membrane to intracellular targets. We conclude that plasma membrane localization of the amphiphilic ZnPcS3C6-C9 is a major factor in their overall photodynamic activity.     

Synthesis and photophysical properties of metal anthraquinone phthalocyanine

A novel anthraquinone phthalocyanine Al(Ⅲ) 4 and Co(Ⅱ) 5 were synthesized and characterized by elemental analysis, IR, UV/ vis, 1H NMR, HPLC and MS. The photophysical properties of the two metal complexes were studied and compared by ?uorescence spectrum method.     

Surface plasmon resonance on the LB monolayer of solvent-soluble silicon phthalocyanine

Thin films of bis-(p-chlorophenoxy) (tetra-4-nitrophthalocyaninato)silicon, TNPcSi(OPhCl-p)₂, were prepared by using Langmir-Blodgett techniques and the morphology of the film was investigated by AFM (atomic force microscope) analysis. It has been found that the LB films were successfully transferred onto substrates like mica, gold deposited glass, and pure glass with domains aggregated on the substrates. Surface plasmon resonance has been used to investigate the interaction between sulfur dioxide and a monolayer of TNPcSi(OPhCl-p)₂ LB film. It has been found that the monolayer of LB film transferred onto gold deposited glass gave a 0.55° shift of resonant angle and an additional 0.45° shift of resonant angle after exposion in sulfur dioxide\atomospheric ambient for twenty minute. The UV–visible absorption spectrum of the LB films of TNPcSi(OPhCl-p)₂ showed that there is chemical changes in the film after the exposure to the sulfur dioxide ambient. This work has shown a promising application as an optical gas sensor.     

Polymeric complex micelle loaded with axially substituted silicon（IV） phthalocyanine

A novel axially substituted silicon(IV) phthalocyanine, namely di-pyridyloxy axially substituted silicon(IV) phthalocyanine 2 was synthesized and characterized by UV/vis, IR, elemental analysis, MS as well as ¹H NMR spectroscopy. Hydrophobic 2 was encapsulated by amphiphilic triblock copolymer poly[N^ε-(benzyloxycarbonyl-lysine]-poly(ethylene glycol)-poly[N^ε-(benzyl oxycarbonyl) (PLL(Z)-b-PEG-b-PLL(Z)) to form hydrophobic 2-loaded polymeric complex micelle (PIC) (2-loaded PIC). Atom force microscopy (AFM) image showed that 2-loaded PIC formed a spherical nanocarrier with approximately 35-50 nm in diameter. The fluorescence intensity and lifetime of 2-loaded PIC was significantly enhanced by the incorporation 2 into PIC nanocarrier.