CN110396092B - 含噻吩基钌配合物作为高效单线态氧产生光敏剂 - Google Patents

含噻吩基钌配合物作为高效单线态氧产生光敏剂 Download PDF

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CN110396092B
CN110396092B CN201910612879.8A CN201910612879A CN110396092B CN 110396092 B CN110396092 B CN 110396092B CN 201910612879 A CN201910612879 A CN 201910612879A CN 110396092 B CN110396092 B CN 110396092B
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ruthenium complex
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王克志
张思琪
李羽佳
傅英焕
尹郅涵
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Abstract

本发明公布了一种含噻吩基钌配合物[Ru(dtdpq)3](ClO4)以及制备方法。该配合物可作为水溶液中高效单线态氧产生光敏剂。

Description

含噻吩基钌配合物作为高效单线态氧产生光敏剂
技术领域
本专利涉及钌配合物在作为高效单线态氧产生光敏材料等相关领域中的应用。
背景技术
当光照射具有光活性的材料即光敏剂时，将产生具有强氧化性及生物毒性作用的单线态氧(1O2)。目前广泛研究的光敏材料种类繁多，涉及有机小分子、金属配合物、纳米材料及蛋白质等。然而，受自身水溶性的限制，以及水分子可淬灭产生的1O2，大多数光敏剂仅研究其在有机溶剂中的单线态氧产率，在水溶液中产率并不理想。大量研究表明，光敏剂通过单线态氧机理在光动力学治疗肿瘤、水环境中污染物的氧化降解、害虫防治等方面有重要应用价值(Mostafa S, Rosario-Ortiz,F.L,Environ.Sci.Technol.2013,47,8179-8186；Zheng Y,He L,Zhang DY.Dalton Trans.2017,46,11395-11407；Lari M,Martinez-Alonso M,Busto N. Inorganic Chemistry.2018,57,14322-14336；Arora K,Herroon M,Al-Afyouni MH,J. Am.Chem.Soc.14367-14380)。因此，研发水溶液中高效单线态氧敏化剂具有重要意义。钌配合物因其具有较大的消光系数、光稳定性强、并在光照条件下能够有效形成激发三重态从而转化分子氧(3O2)为单线态氧(1O2)，因此，近年来人们对钌配合物作为光敏剂产生单线态氧的能力颇为关注。本专利公开的的含噻吩基钌配合物，在水溶液中具有高的1O2产生能力。
发明内容
本发明的目的是制备一种含噻吩基钌配合物[Ru(dtdpq)3](ClO4)2，采用 APDA(9,10-蒽二丙酸二钠盐)法研究其在水溶液中的1O2产生能力。钌配合物光照后产生1O2，ADPA与溶液中产生的1O2反应引起其吸光度降低。以ADPA作为单线态氧捕获剂，玫瑰红作为标准光敏剂，通过监测反应液在378nm处吸光值变化计算钌配合物的单线态氧产率。研究结果表明，光照条件下 [Ru(dtdpq)3](ClO4)2在磷酸盐缓冲液(PBS)中单线态氧产率为0.23。因此，钌配合物[Ru(dtdpq)3](ClO4)2可以作为一种高效的单线态氧产生光敏剂。
本发明的技术方案如下：
钌配合物的合成途径如下式所示：
Figure RE-GDA0002206008450000021
与现有技术相比，本发明的有益效果在于：
目前广泛研究的光敏剂在有机溶剂中具有较高单线态氧产率，但在水溶液中受自身溶解度及周围水分子淬灭等影响，水溶液中单线态氧产率并不理想。由于单线态氧产生光敏剂在光动力学治疗肿瘤、水中污染物氧化降解、抗菌、病虫害防治等方面具有广阔研究前景，因此，迫切需要开发出水溶液中具有较高单线态氧产生能力的光敏材料。本发明合成的钌配合物在水溶液中具有较高光稳定性，光照条件下单线态氧产率为0.23。以上性质表明，该钌配合物可作为一种高效单线态氧产生光敏剂。
附图说明
图1可见光照射下ADPA与钌配合物的混合PBS溶液吸光度随光照时间的变化
图2可见光照射下ADPA与玫瑰红的混合PBS溶液吸光度随光照时间的变化
图3可见光照射下ADPA、钌配合物、及二者混合PBS溶液吸光度变化与光照时间的关系
图4光照射后钌配合物对ADPA的光降解率常数测定图
图5光照射后玫瑰红对ADPA的光降解率常数测定图
具体实施方式
实施例1：配体及钌配合物的制备
1.2,3-二噻吩吡嗪[1,10]邻菲咯啉的合成：将0.1mmol的1,2-双(噻吩-2-基) 乙烷-1，2-二酮溶于冰醋酸(5mL)中，向其中加入0.15mmol的1，10- 邻菲啰啉-5，6-二胺(42.2mg，0.2mmol)的冰醋酸溶液(2.5mL)，并不断搅拌。反应混合物在氮气保护下回流90分钟后，真空干燥，除去醋酸。沉淀溶于二氯甲烷的水溶液，有机相用饱和的碳酸氢钠溶液和水洗涤。加入无水硫酸钠干燥，过滤，干燥。滤渣进行硅胶柱层析纯化(展开剂：二氯甲烷/甲醇＝40/1，体积比)，得到淡黄色粉末产物。1H NMR (CDCl3)δ7.08～7.10(2H,m),7.46(2H,d,J＝5.0Hz),7.56(2H,d,J＝3.1 Hz),7.75～7.78(2H,m),9.24～9.26(2H,m),9.41～9.43(2H,m).
2.钌配合物的合成：将RuCl3·3H2O(14.3mg,0.05mmol)与2,3-二噻吩吡嗪 [1,10]邻菲咯啉(59.4mg,0.15mmol)混合到3ml乙二醇中，氮气保护下反应10小时。反应结束后冷却至室温，过滤。将滤液进行柱层析分离(展开剂：二氯甲烷/甲醇/N,N-二甲基甲酰胺＝5/1/0.5，体积比)。减压蒸馏除去大部分溶剂后，加入乙醚扩散重结晶，得到红色产物0.052g，产率 63％。1H NMR(400MHz,CDCl3):δ9.40(t,2H),8.53(m,4H), 8.19(d,4H),8.09(t,2H),8.02–7.92(m,4H),7.80(t,2H), 7.67(t,2H),7.57-7.51(m,4H),7.32(t,2H),7.24-7.19(m, 2H).m/z:计算值：909.3([M-ClO4]+),实测值：909.14(15.3％)；计算值：405.0([M-2ClO4]2+),实测值：405.08(100％).
实施例2：ADPA法检测水溶液中[Ru(dtdpq)3]2+的单线态氧产率
向3mL含有一定浓度钌配合物的PBS溶液中加入10μL ADPA，使378nm 处的吸光值～0.2，并记录光照前吸光值。将上述溶液用26mW/cm2可见光照射10 分钟，每两分钟测一次紫外-可见吸收光谱，并记录378nm处吸光值。同样的方法测定标准光敏剂玫瑰红光照不同时间的光谱变化，通过下面公式求得单线态氧产率：
Figure RE-GDA0002206008450000031
其中，下角标Ru和RB分别代表钌配合物和玫瑰红，K为ADPA在378nm 处的光降解率常数，A代表400-700nm吸收峰积分面积，ΦRB为RB在水溶液中的单线态氧产率(0.75)。
如图1和图2所示，当钌配合物或玫瑰红存在时，随光照时间延长(0-10 min)，ADPA的吸光度不断降低，表明钌配合物和玫瑰红在光照条件下均能有效产生1O2将ADPA逐渐降解。为排除钌配合物或ADPA自身光稳定性的干扰，实验测定了不同光照时间(0-10min)378nm处的相对吸光度变化(图3)。结果表明，当溶液中仅存在钌配合物或ADPA时，该光照条件下二者的吸光度几乎不变，表明钌配合物和ADPA具有较高的光稳定性，从而进一步说明混合溶液中 ADPA吸光度的变化是由于光照下钌配合物产生的1O2将其氧化降解所致。根据图4和图5计算得到光照射后钌配合物和玫瑰红对ADPA的光降解率常数(K)，从而求得水溶液中[Ru(dtdpq)3](ClO4)2的单线态氧产率为0.23。

Claims (3)

1.一种含噻吩基钌配合物[Ru(dtdpq)3](ClO4)2，由阳离子和阴离子组成，其特征在于，所述阳离子为[Ru(dtdpq)3]2+，结构如下式所示：
Figure FDA0002492181430000011
2.权利要求1所述的含噻吩基钌配合物的制备方法，其特征在于，先制备dtdpq，然后按照计量摩尔比称取RuCl3·3H2O与dtdpq于乙二醇中，氮气保护下加热回流反应10小时，反应结束后冷却至室温，沉淀为高氯酸盐后，过滤，将滤液进行柱层析分离，展开剂为体积比为5:1:0.5的二氯甲烷-甲醇-N,N-二甲基甲酰胺混合溶剂，减压蒸馏除去大部分溶剂后，加入乙醚扩散重结晶，得到目标产物。
3.光照条件下，含噻吩基钌配合物[Ru(dtdpq)3](ClO4)2在水溶液中具有较高的单线态氧产率，可作为高效单线态氧产生光敏剂。
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