钆(Ⅲ)仿叶绿素配合物的合成、表征以及作为光磁双模式诊疗探针的应用  

Gadolinium(Ⅲ) Complex of Chlorophyll Mimics: Synthesis,Characterization and Potential Application as Photo-Magnetic Bimodal Theranostic Agent

作　　者：杨字舒 宁莹莹[1] 张俊龙[1] 

机构地区：[1]北京大学化学与分子工程学院,北京分子科学国家实验室(筹),稀土材料化学及应用国家重点实验室,北京100871

出　　处：《中国稀土学报》2016年第6期764-772,共9页Journal of the Chinese Society of Rare Earths

基　　金：国家自然基金面上项目(20971007,21101169,21571007,21271013和21321001)资助

摘　　要：模拟自然界对四吡咯染料的β位调节方式,结合卟吩内酯近红外吸收和三线态能级可调、且易于修饰的优点,设计并合成了Gd(Ⅲ)卟吩内半缩醛配合物,并通过水溶性铵基修饰,使之具有两亲性质。该类配合物能较好地敏化O_2,单线态氧量子产率约0.75,且可应用于光毒性治疗,即使在红光(600~700 nm)激发下,其对He La细胞的半数致死浓度(IC50)仍低至1.5μmol·L^(-1)。同时,Gd-4的纵向弛豫率(r1)为1.1 mmol·L^(-1)·s^(-1)(0.5 T,37℃),表明配合物具有磁共振成像造影能力。因此,这类化合物具有光、磁双功能诊疗的潜在应用价值。Gadolinium （III） complexes are potential bimodal theranostic probes for photodynamic cancer therapy （PDT） and magnetic resonance imaging （MRI）. For the feasible modification of β-substituents, tunable triplet state and strong NIR absorption of porpholactones, we designed and synthesized the Gd（III） porpholactol complex （Gd-4） , inspired by natural tetrapyrrole pigments such as chlorophylles. Through modified with hydrophilic ammonium （ NMe3^＋ ） , the complex became water soluble and biocompatible. Importantly, as Gd-4 is a good O2 photo- sensitizer with ^1O2 quantum yield of 0.75, it can be applied in PDT towards HeLa cells. Even under the irradiation of red light （600 -700 nm） , the IC50 was as low as 1.5 μmol·L^-1. More significantly, due to seven unpaired f electrons of Gd^3＋ ion, this complex can be further applied in MRI with the longitudinal relaxivity of 1.1 mmol·L^-1 ·s^ -1 in water （0.5 T, 37 ℃ ）. These results herein showed that Gd-4 is a potential photo-magnetic bifunctional theranostic agent and revealed the importance of bioinspired approach in the design of functional lanthanide complexes.

关 键 词：卟吩内酯 钆(Ⅲ) 单线态氧 光毒性 磁共振成像 

分 类 号：O6[理学—化学]