目的寻找一种新型光动力学疗法光敏剂。方法采用从光合细菌中分离纯化的脱镁细菌叶绿素为配体,与金属盐在有机溶剂中反应,合成了Cu,Zn,Co,N i 4种金属细菌叶绿素,并对其紫外可见光谱和荧光光谱进行研究。此外还研究了4种金属细菌叶绿素对K562和HL60两种白血病细胞生长的影响。结果4种金属细菌叶绿素的光谱图都有可预见的漂移,证明金属已配位到细菌叶绿素的卟啉大环上。同时,4种金属细菌叶绿素都有很强的抑瘤作用,光照可以明显提高其抑瘤率。结论金属细菌叶绿素作为一种新型光敏剂具有优良的性质,是新一代光敏剂发展的一个方向。
Rhodobacter sphaeroide as a new biocatalysts were investigated in the asymmetric reduction of ketones to chiral alcohols. The cells were used in an aqueous system for the asymmetric reduction of acetophenone to prepare (S)-1-phenyl-ethanol by photo-electron-transfer reactions. It is found that higher product yield and product enantiomeric excess could be achieved. The results show that the enantiomer excess of the chiral alcohols was up to 99%(e.e.) and the yield is more than 90%. The effects of DCMU and the optimal reaction conditions on the reaction were investigated. The results show that the reaction was controlled by light completely, the optimal substrate concentration is 17.0 mmol/L, the optimal cell mass concentration is \{0.2 g/mL,\} the optimal pH is 7—8, the optimal reaction time was 72 h.
Treatment of the lithium β-diketiminate [Li{N(R)C(NMe2)C(H)C(NMe2)N(R)}]2 (1) (R=SiMe3) with KOBut, KOH·H2O and CoCl2 in tetrahydrofuran gave in good yields the RO bridged β-diketiminato Co complex [Co{N(H)C(NMe2)C(H)C(NMe2)N(R)-( μ-OR)}]2 (2) at ambient condition. The crystal data of (2) are as follows: crystal system, monoclinic; space group, P121/n1; a=0.963 9(3) nm, b=1.077 2(3) nm, c=2.025 0(6) nm, V=2.102 5(10) nm3, Z=2, Dc=1.186 g·cm-3, F(000)=804, μ(Mo Kα)=0.934 mm-1, R1=0.047 8, wR2=0.097 9. In solid state, complex (2) is a dimer bridged by RO (R=SiMe3) group and the two Co2+ are in distorted tetrahedron. CCDC: 249253.
