卟啉修饰的壳聚糖光敏新材料的制备与表征
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摘要
目的合成卟啉修饰的壳聚糖光敏新材料,对其进行表征,并优化其合成工艺。方法以溴己烷苯基卟啉衍生物和壳聚糖为原料,以K_2CO_3为碱,采用四丁基溴化铵为相转移催化剂,合成卟啉-壳聚糖复合物,采用茚三酮法测定卟啉接枝率。通过单因素实验研究反应温度、反应时间、混合溶剂比例、催化剂当量等对接枝率的影响,采用正交实验法优化获得最佳制备工艺条件。结果最佳合成条件为温度55℃、反应时间为5.5 h、混合溶剂中水和氯仿的比例为1∶2、催化剂为1当量、无机碱使用K_2CO_3,卟啉的平均接枝率为41.30%。结论通过共价偶联合成卟啉修饰壳聚糖光敏新材料的方法可行。
OBJECTIVE To synthesis and characterize the chitosan-porphyrin complexes(CS-BHP), and to optimize the experimental condition. METHODS CS-BHP was synthesized from 5-p-(6-bromohexylaminophenyl)-10,15,20-triphenyl porphyrin(BHP) and chitosan by using K_2CO_3 as a base and tetrabutylammonium bromide as a phase transfer catalyst. The porphyrin grafting rate of CS-BHP was detected with ninhydrin by UV-Vis. In the single factor analysis, the effect of temperature, reaction time, the volume ratio of water to chloroform in the component solvent, equivalent of the catalyst were investigated. The orthogonal test was used to optimize the condition of synthesis. RESULTS The optimized condition of the reaction was as follows: the temperature was 55 ℃, the reaction time was 5.5 h, the volume ratio of water to chloroform in the component solvent was 1∶2, catalyst was 1 equivalent, and K_2CO_3 was used as base, the average porphyrin grafting rate of CS-BHP was 41.30%. CONCLUSION It is feasible to synthesize CS-BHP by the method of covalent coupling.
OBJECTIVE To synthesis and characterize the chitosan-porphyrin complexes(CS-BHP), and to optimize the experimental condition. METHODS CS-BHP was synthesized from 5-p-(6-bromohexylaminophenyl)-10,15,20-triphenyl porphyrin(BHP) and chitosan by using K_2CO_3 as a base and tetrabutylammonium bromide as a phase transfer catalyst. The porphyrin grafting rate of CS-BHP was detected with ninhydrin by UV-Vis. In the single factor analysis, the effect of temperature, reaction time, the volume ratio of water to chloroform in the component solvent, equivalent of the catalyst were investigated. The orthogonal test was used to optimize the condition of synthesis. RESULTS The optimized condition of the reaction was as follows: the temperature was 55 ℃, the reaction time was 5.5 h, the volume ratio of water to chloroform in the component solvent was 1∶2, catalyst was 1 equivalent, and K_2CO_3 was used as base, the average porphyrin grafting rate of CS-BHP was 41.30%. CONCLUSION It is feasible to synthesize CS-BHP by the method of covalent coupling.
引文
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[2]LI D H,LIU L M,TIAN K L,et al.Synthesis,biodegradability and cytotoxicity of water-soluble isobutylchitosan[J].Carbohydr Polym,2007,67(1):40-45.
[3]SHI L,HU L P,PU J B,et al.A study on safety in animal of chttosan[J].Chin J Mar Drug(中国海洋药物),2000,19(1):25-28.
[4]王爱勤.甲壳素化学[M].北京:北京科学出版社,2008:244-256.
[5]SONG Q P,WANG Y,DING C M.Preparation of highly deacetylated chitosan in alcohol[J].Chem World(化学世界),2005,46(7):422-423.
[6]OKHAMAFE A O,AMSDEN B,CHU W,et al.Modulation of protein release from chitosan-alginate microcapsules using the pH-sensitive polymer hydroxypropyl methyl cellulose acetate succinate[J].J Microencapsul,1996,13(5):497-508.
[7]LEE K Y,KWON I C,KIM Y H,et al.Preparation of chitosan self-aggregates as a gene delivery system[J].J Control Release,1998,51(2/3):213-220.
[8]ANTONI P M,NAIK A,ALBERT I,et al.(Metallo)porphyrins as potent phototoxic anti-cancer agents after irradiation with red light[J].Chemistry,2015,21(3):1178-1183.
[9]ZHANG D D,LI W N,Mei W J,et al.Studies on the target of photodynamic therapy with porphyrin derivatives as photosensitizer[J].Chin J Mod Appl Pharm(中国现代应用药学),2013,30(4):445-449.
[10]GU C Z,MENG S X,FENG Y Q.The progress of porphyrin sensitizers for dye-sensitized solar cells[J].Chin J Org Chem(有机化学),2015,35(6):1229-1237.
[11]BARATA J F,ZAMARRóN A,NEVES M G,et al.Photodynamic effects induced by meso-tris(pentafluorophenyl)corrole and its cyclodextrin conjugates on cytoskeletal components of HeLa cells[J].Eur J Med Chem,2015(92):135-144
[12]ZHANG Z,WEN J Y,LV B B,et al.Photocytotoxicity and G-quadruplex DNA interaction of water-soluble gallium(III)tris(N-methyl-4-pyridyl)corrole complex[J].Appl Organometal Chem,2016,30(3):132-139.
[13]NAIK A,RUBBIANI R,GASSER G,et al.Visible‐light‐induced annihilation of tumor cells with platinum-porphyrin conjugates[J].Angew Chem Int Ed Engl,2014,53(27):6938-6941.
[14]GIANFERRARA T,SPAGNUL C,ALBERTO R,et al.Towards matched pairs of porphyrin-Re(I)/(99m)Tc(I)conjugates that combine photodynamic activity with fluorescence and radio imaging[J].Chem Med Chem,2014,9(6):1231-1237.
[15]YU D J,LI M Z,HUANG X Z,et al.Preparation of and study on magnetic resonance imaging performance of metal porphyrin modified by low molecular weight chitosan[J].Spectrosc Spect Anal(光谱与光谱分析),2013,33(10):2736-2739.
[16]LUO W F,SONG X Y,MAO L Y,et al.Study on detection of toluene content with metalloporphyrins[J].Chem Bioengineer,2012,29(7):89-91
[17]HE J,LIU W H,HE L M,et al.Synthesis and photodynamic antitumor activity of new metalloporphyrin-Ara-C compounds[J].Chem J Chin Univ(高等学校化学学报),2013,34(10):2308-2312.