新型光敏剂——系列尾式卟啉二肽的合成与光学性质研究

以5-(4-氨基苯基)-10,15,20-三苯基卟啉、叔丁氧羰基(Boc)保护的氨基酸为原料合成了系列新型尾式氨基酸卟啉和尾式卟啉二肽, 用核磁、质谱及元素分析对产物进行了表征, 并研究了其光学性质. 结果表明: 所合成的系列尾式卟啉二肽产率高达94%以上, 在可见光的红光部分有强烈的荧光发射.     

β-氢醌-四(对羟基苯基)卟啉的合成及其抗肿瘤活性

合成并初步研究了新型β-取代卟啉光敏剂2-氢醌-5,10,15,20-四(4-羟基苯基)卟啉锌(II)(Zn(II)P)、2-氢醌-5,10,15,20-四(4-羟基苯基)卟啉铜(II)(Cu(II)P)的抗肿瘤活性。结果表明,2-氢醌-5,10,15,20-四(4-羟基苯基)卟啉锌(II)的合成总产率60%,该光敏剂对慢性骨髓性白血病肿瘤细胞(K562)具有很好的光敏毒性,Zn(II)P的浓度为320mmol/L时,就能抑制90%以上的白血病肿瘤细胞的生长。     

新型β,β-桥连双卟啉的合成及其光敏活性研究

以1,6-二溴己烷为桥连试剂, 2-(1-羟基萘基)-5,10,15,20-四苯基卟啉及其Cu(Ⅱ), Ni(Ⅱ), Zn(Ⅱ)配合物为原料, 合成了4个新型β,β-桥连双卟啉. 以1,3-二苯基异苯并呋喃(DPBF)为猝灭剂, 测试了双卟啉及其Ni(Ⅱ), Zn(Ⅱ)配合物在光照条件下产生单线态氧的能力, 并研究了4个双卟啉化合物在光照和无光照条件下对pBR322质粒DNA的切割能力(用凝胶电泳)和对金黄色葡萄球菌(ATCC 25923)的光敏抑菌活性. 结果表明, 新型双卟啉光敏剂具有较好光敏活性, 产生的活性氧能有效杀灭金黄色葡萄球菌.     

二乙胺基尾式卟啉钴的合成及其载氧性质

合成了1种新的尾式卟啉钴--间-[邻-(4-二乙胺基丁酰胺基)苯基]三苯基卟啉合钴(Ⅱ)配合物,测定了电子光谱、红外光谱、质谱、电子自旋波谱,研究了这种尾式卟啉钴与有机碱和双原子小分子CO、NO的轴向反应及其可逆载氧性质.     

姜黄素桥连卟啉光敏剂的合成及表征

为了开发新的高效光动力治疗光敏剂, 以2-(2-羟基萘基)-5,10,15,20-四苯基卟啉及其Cu(Ⅱ), Ni(Ⅱ), Zn(Ⅱ)配合物为原料, 利用1,6-二溴己烷桥连具有抗癌活性的小分子姜黄素, 设计合成4个新型的天然产物桥连卟啉化合物. 通过UV, ¹H NMR, IR, MS及元素分析等手段对该新型光敏药剂进行了结构表征; 在此基础上, 采用凝胶电泳法考察了化合物在光照和无光照条件下对pBR322质粒DNA的切割能力. 作为潜在光敏剂与DNA相互作用的初步研究表明, 其与DNA结合能力较强, 具有明显的光敏切割效果.     

新型离子型尾式乙基咪唑基卟啉化合物的合成与表征

通过不对称的单羟基卟啉化合物、二溴烷烃、咪唑和溴乙烷反应,合成了一种新型的离子型尾式卟啉化合物——溴化5-对{4-[1-(3-乙基)-咪唑基]丁氧基}苯基-10,15,20-三苯基卟啉(Et-ImBPTPP)Br,并采用质谱、紫外光谱、红外光谱、热重分析、元素分析、能谱和核磁共振氢谱对该化合物进行了结构表征。     

二乙胺基尾式卟啉锰(Ⅲ)的性质研究——Ⅰ.合成与性质研究

本文合成了一种新型的二乙胺基尾式卟啉锰-氯化间一—[邻-(4-二乙胺基丁酰胺基)苯基]三苯基卟啉合锰(Ⅲ)[简称meso-MDBPTPPMn(Ⅲ)Cl],用分光光度法研究了meso-MDBPTPPMn(Ⅲ)Cl的氧化还原性及中心离子分别为二价和三价时与NO,CO等双原子小分子以及各种有机碱的轴向加合作用,并用循环伏安法研究了这种锰卟啉模型化合物的电化学性质。     

新型尾式组氨酸卟啉的合成及性质

设计并合成了新型尾式氨基酸卟啉5-(Trt-组氨酸酰胺基苯基)-10,15,20-三苯基卟啉(Trt-His-NH2-TPP,1)及其金属卟啉配合物(Zn,Co,Fe,Mn,分别标记为2～5).通过元素分析、核磁共振氨谱、质谱、紫外-可见光谱和红外光谱等对化合物进行了表征,研究了它们的荧光性质,并通过理论模拟研究了其最...     

二乙胺基尾式卟啉锰(Ⅲ)的性质研究(Ⅱ)——含氮有机碱与尾式卟啉锰(Ⅲ)配合物的轴向反应

采用光谱技术研究了一种新型尾式锰(Ⅲ)卟啉--氯化meso--[邻-(4-二乙胺基丁酰胺基)苯基]三苯基卟啉合锰(Ⅲ)[筒作PMn(Ⅲ)Cl]与有机碱的轴向反应,通过光谱滴定法测定了轴向反应在苯溶剂中的平衡常数.讨论了影响反应的因素.结果表明,这种尾式锰(Ⅲ)卟啉与脂肪胺的反应是氧化还原反应,与吡啶的反应是不完全的氧化还原反应,与咪唑的反应是轴向加合反应.     

meso-一〔邻-4-(二乙胺基)丁酰胺基苯基〕三苯基卟啉的合成和性质

本文报导了一个新的尾式卟啉——meso-一[邻-4-(二乙胺基)丁酰胺基苯基)三苯基卟啉的合成方法,并由元素分析UV、IR ~1HNMR、~(15)CNMR确认了它的结构,研究了它和过渡金属形成配合物的性质。     

酸敏变色记录材料的光谱特性及其光量子产率

本文研究了由偏二氯乙烯-丙烯酸甲酯共聚合物(VdCl₂-MA)和五甲氧基红指示剂组成的酸敏变色记录材料的光谱特性,测定了其光分解量子产率.通过添加光敏剂使原来只有在254nm紫外光下曝光才能发生光分解反应的酸敏变色材料在35nm紫外光下曝光也可发生光分解而变色.酸敏变色材料在254nm处紫外光曝光量子产率为0.032-0.020;在35nm处紫外光曝光量子产率为0.110-0.034.光敏剂的加入使酸敏变色材料量子产率提高了2-4倍.     

Influence of photosensitizer solvent on the mechanisms of photoactivated killing of Enterococcus faecalis

This study evaluated the mechanisms involved and the influence of photosensitizer solvent in the killing of Enterococcus faecalis using photodynamic therapy (PDT). Enterococcus faecalis cells incubated with 100 microm methylene blue dissolved in water and in MIX (a mixture of glycerol:ethanol:water) were irradiated with 664 nm diode laser (63.69 J cm(-2)). The effect of PDT on the viability of bacteria, and the functional integrity of cell wall, chromosomal DNA and membrane proteins were analyzed. The bactericidal action of PDT was significantly higher when a MIX-based photosensitizer solvent was used (P<0.001). Fluorimetric and fluorescence microscopy-based analysis showed the functional impairment of E. faecalis cell wall which was significantly higher when a MIX-based photosensitizer solvent was used (P<0.001). PDT with MIX-based photosensitizer solvent showed extensive damage to chromosomal DNA. However, both PDT conditions showed similar trend in the degradation of membrane proteins, although cross-linked proteins were evident only in PDT conducted with MIX-based photosensitizer solvent. The findings from our study showed that PDT destroyed the functional integrity of cell wall, DNA and membrane proteins of E. faecalis. The degrees of damage on these targets were influenced by the photosensitizer solvent used during PDT.     

A molecular light-driven water oxidation catalyst

Two mononuclear Ru(II) complexes, [Ru(ttbt)(pynap)(I)]I and [Ru(tpy)(Mepy)(2)(I)]I (tpy = 2,2';6,2"-terpyridine; ttbt = 4,4',4"-tri-tert-butyltpy; pynap = 2-(pyrid-2'-yl)-1,8-naphthyridine; and Mepy = 4-methylpyridine), are effective catalysts for the oxidation of water. This oxidation can be driven by a blue (λ(max) = 472 nm) LED light source using [Ru(bpy)(3)]Cl(2) (bpy = 2,2'-bipyridine) as the photosensitizer. Sodium persulfate acts as a sacrificial electron acceptor to oxidize the photosensitizer that in turn drives the catalysis. The presence of all four components, light, photosensitizer, sodium persulfate, and catalyst, are required for water oxidation. A dyad assembly has been prepared using a pyrazine-based linker to join a photosensitizer and catalyst moiety. Irradiation of this intramolecular system with blue light produces oxygen with a higher turnover number than the analogous intermolecular component system under the same conditions.     

Oxidative biomacromolecular damage from novel phthalocyanine

Ｉｎｒｅｃｅｎｔｙｅａｒｓ,ｐｈｔｈａｌｏｃｙａｎｉｎｅｓａｒｅｗｉｄｅｌｙｕｓｅｄｉｎｐｈｏｔｏｄｙｎａｍｉｃｔｈｅｒａｐｙ(ＰＤＴ)ａｎｄｌｉｇｈｔｉｎｄｕｃｅｄｅｌｅｃｔｒｏｎｉｃｄｅｖｉｃｅｓ.Ｔｈｅｙｃａｎｂｅｐｏｔｅｎｔｉａｌｌｙｕｓｅｄｉｎｔｈｅｔｈｅｒａｐｙｏｆｃａｎｃｅｒａｎｄｉｎｔｈｅｒｅｓｔｒａｉｎｔｏｆｈｕｍａｎｉｍｍｕｎｏｌｏｇｙｖｉｒｕｓ(ＨＩＶ),ｅｔｃ.[1,2].Ｐｈｏｔｏｓｅｎｓｉｔｉｚｅｄｏｘｉｄａｔｉｏｎｉｓａｐｒｏｃｅｓｓｉｎｗｈｉｃｈｐｈｏｔｏｓｅｎｓｉｔｉｚｅｒｏ…     

Synthesis and photoactivity of pH-responsive amphiphilic block polymer photosensitizer bonded zinc phthalocyanine

A zinc tetraaminophthalocyanine derivative, zinc tetra(methacryloyl moiety)aminophthalocyanine (MeZnAPc) (with a double bond) was synthesized by the reaction between zinc tetraaminophthalocyanine (ZnTAPc) and methacryloyl chloride. Atom transfer radical polymerization (ATRP) was employed as the polymerization technique to obtain a novel pH-responsive polymeric photosensitizer (PEG110-b-P(DPAn-co-MeZnAPcm)) by copolymerizing of methoxypolyethylene glycols (MPEG) (as reducing agent), 2-(isopropylamino)ethyl methacrylate (DPA) and MeZnAPc. This photosensitizer was characterized by UV-vis spectroscopy, FTIR, H NMR, etc. The results indicated that the photosensitizer presented the well pH-responsive be 1 havior around the pH range 6.0-6.5 and the high photoactivity to 1,3-diphenylisobenzofuran (DPBF). The result of photocatalysis oxidation of L-tryptophan (L-Try) suggested that zinc phthalocyanine could present high photoactivity due to its dispersivity at pH 5.5 without formation of micelles, and its photoactivity decreased dramatically at pH 7.4 due to wrapping ZnTAPc into the micelles. Therefore, the novel pH-responsive polymeric photosensitizer has better application prospects in the field of photodynamic therapy.     

Photochemical reactivities of photosensitive polymers containing chalcone derivatives

Monomeric vinyl chalcone derivatives were prepared by the condensation reaction of p-hydroxybenzaldehyde with acetophenone derivatives in the presence of sodium ethoxide as a base, followed by esterification of their hydroxy groups with methacryloyl chloride. The monomers, 4-(methacryloyloxy)chalcone derivatives, have been polymerized by a free radical technique. Copolymers containing the chalcone groups with different ratios of p-nitrophenylmethacrylate as photosensitizer group have also been prepared. The photosensitivities of the polymeric chalcone derivatives were investigated through their photochemical reaction on exposure to UV light, and by measuring the changes in their UV spectra before and after irradiation. The results obtained from the disappearance rates of the C?C bonds indicate that the photoreactivities of the polymers are largely affected by the position of the substituent in the phenyl ring of the chalcone, the photosensitizer group ratio, and the irradiation time.     

Study of photopolymer. XVII. Synthesis of novel photosensitive polymers with pendant photosensitive group and photosensitizer groups

Novel photosensitive polymers with pendant photosensitive group, such as cinnamic ester, and photosensitizer groups, such as N-carbamoyl-p-nitroaniline and N-carbamoly-4-nitro-1-naphthylamine, were synthesized from radical copolymerizations of (2-cinnamoyloxy)ethylmethacrylate with photosensitizer monomers, such as p-nitrophenylmethacrylamide and 4-nitro-1-na-phthylmethacrylamide, by using asobisisobutyronitrile (AIBN) in benzene and from the copolymerizations of (2-hydroxy)ethylmethacrylate or (2-hydroxy)ethylacrylate with photosensitizer monomers by using AIBN in DMF. This procedure was followed by condensation reactions of the copolymers with cinnamoyl chloride with pyridine as HCL acceptor in the same reaction flask. The photoreactivities of the polymers obtained were influenced by the concentration of photosensitive group and photosensitizer groups and their ratio in the polymer matrix. In addition, the photosensitivity of cinnamic ester groups attached to a soft polymer segment was higher than that of cinnamic ester group attached to a hard polymer segment when these polymers had the same pendant N-carbamoyl-p-nitroaniline group as photosensitizer. Furthermore, the spacer length between the polymer chain and photosensitizer group was important for increasing the photoreactivity of the photosensitive group in the polymers with pendant cinnamic ester and N-carbamoyl-p-nitroaniline groups.     

pH响应两亲嵌段锌酞菁聚合物光敏剂的制备及光活性

将氨基锌酞菁（ZnTAPc）与甲基丙烯酰氯反应制备出含有不饱和双键的取代锌酞菁衍生物（MeZnAPc）,采用ATRP法将聚乙二醇单甲醚大分子引发剂（mPEG110-Br）与甲基丙烯酸（2-异丙胺基）乙酯（DPA）和MeZnAPc共聚,制得一种新型pH响应两亲嵌段锌酞菁聚合物光敏剂（PEG110-b-P（DPAn-co-MeZnAPcm））.用1HNMR,FTIR对MeZnAPc和聚合物光敏剂进行表征.UV-vis测试表明该聚合物光敏剂在pH6.0～6.5具有较好的pH响应性.以1,3-二苯基苯并呋喃（DPBF）为底物研究了该聚合物光敏剂的光催化氧化效率,结果表明其具有较高光活性.利用该聚合物光敏剂在不同pH的水溶液中对L-色氨酸进行光催化氧化实验,结果发现在pH5.5不存在胶束时,锌酞菁可以较好地分散在溶液中,并能维持较高光活性,而在pH7.4形成胶束时可以将锌酞菁很好地包裹在其内部,使其光活性大大降低.因此,这种pH响应两亲嵌段锌酞菁聚合物作为一种新型光敏剂,在光动力学治疗领域有较好的应用前景.     

Electronic excitation spectra of the [Ir(ppy)2(bpy)]+ photosensitizer bound to small silver clusters Ag(n) (n = 1-6)

The changes in nature and order of the excited electronic states of the photosensitizer [Ir(ppy)(2)(bpy)](+) upon binding to small silver clusters, Ag(n) (n = 1-6), were studied theoretically using the linear response TDDFT method with the range-separated LC-BLYP functional. Binding energies and localization of HOMO and LUMO orbitals are found to oscillate with the number of silver atoms. Special emphasis is put on the discussion of long-range charge transfer transitions between the photosensitizer and the silver cluster. The energies of these transitions were found to be only slightly dependent on the relative orientations of both fragments, but strongly dependent on the intermolecular distance. The absorption spectrum of the combined system does not show a systematic trend with respect to cluster size, but it is strongly modified by the charge transfer transitions. Possible photophysical processes of the systems containing larger clusters are discussed.     

Photodynamic effects of mTHPC on human colon adenocarcinoma cells: photocytotoxicity,subcellular localization and apoptosis

The photodynamic properties of meta-tetra(hydroxyphenyl)chlorin (mTHPC), a promising second-generation photosensitizer, were investigated using a human colon adenocarcinoma cell line (Colo 201 cells). The study on photocytotoxicity using 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide reduction assay showed that mTHPC was an effective photosensitizer on Colo 201 cells. The photocytotoxicity of mTHPC showed both drug and light dose-dependent characteristics. To reach LD50, namely, the dose at which 50% of the cells were killed, only 0.45+/-0.15 microg/mL of mTHPC and 3 J/cm2 of light dose were required. The presence of 10% fetal calf serum in culture medium significantly decreased the incorporation of mTHPC into cells and resulted in the reduction of photodynamic efficacy. Using confocal laser scanning microscopy, mTHPC was first shown to localize in lysosomes rather than in mitochondria. Furthermore, nuclear stainings demonstrated that photodynamic therapy with mTHPC induced apoptosis in Colo 201 cells.