Cation-mediated optical resolution and anticancer activity of chiral polyoxometalates built from entirely achiral building blocks.
Cation-mediated optical resolution and anticancer activity of chiral polyoxometalates built from entirely achiral building blocks.
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DOI：
10.1039/c5sc04408a
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发表时间：
2016-07-01
期刊：
影响因子：
8.4
通讯作者：
Lin W
中科院分区：
文献类型：
--
作者：
Zhang ZM;Duan X;Yao S;Wang Z;Lin Z;Li YG;Long LS;Wang EB;Lin W
同手性聚氧杂环丁烷酸酯通过反阳离子介导的手性对称性破坏而被光学拆分，并且通过激活凋亡途径对各种癌细胞显示出有效的细胞毒性。本文报道了同手性聚氧乙烯酸盐（POM）大阴离子{CoSb 6 O 4（H2O）3[Co（H2O）SbW 8 O31]3}15-（1，H2O =六亚甲基四胺）通过反阳离子介导的手性对称性破缺和不对称自催化过程的结晶。在低Co2+浓度存在下，在反应中形成1的Δ-和Λ-对映体，结晶成外消旋晶体rac-1。在高Co2+浓度下，多氧阴离子对映体通过氢键相互作用表现出高水平的手性识别，结晶为对映体纯的Δ-或Λ-[Co（H2O）6{CoSb 6 O 4（H2O）3[Co（H2O）SbW 8 O31]3}]13-晶体。在结晶过程中，微尺度的非对称性破坏事件和非线性不对称自催化过程使对映体在不同批次中结晶，这为分离纯手性块体材料提供了机会。因此，外消旋和纯手性晶体的定义的结构提供了一个分子水平的说明，氢键相互作用是负责这种高水平的手性识别，在一个类似的过程中经常观察到的超分子手性在生物学。这些POM大阴离子显示出对各种癌细胞，特别是卵巢癌细胞的高细胞毒性。这些化合物的抗肿瘤活性至少部分地由细胞凋亡途径的激活引起，如通过流式细胞术、膜联蛋白V染色、DNA梯和TUNEL测定所示，可能通过阻断细胞周期和与细胞中的蛋白质复合。本文报道的POM大阴离子为各种癌症的潜在治疗提供了有希望的和新的抗肿瘤剂。
Homochiral polyoxometalates were optically resolved via the counter cation-mediated breaking of chiral symmetry, and showed potent cytotoxicity against various cancer cells by activating apoptotic pathways. We report the crystallization of homochiral polyoxometalate (POM) macroanions {CoSb6O4(H2O)3[Co(hmta)SbW8O31]3}15– (1, hmta = hexamethylenetetramine) via the counter cation-mediated chiral symmetry breaking and asymmetric autocatalytic processes. In the presence of low Co2+ concentrations both Δ- and Λ-enantiomers of 1 formed in the reaction, crystallizing into the racemic crystal rac-1. At a high Co2+ concentration, the polyoxoanion enantiomers showed a high level of chiral recognition via H-bonding interactions to crystallize into enantiopure crystals of Δ- or Λ-[Co(H2O)6{CoSb6O4(H2O)3[Co(hmta)SbW8O31]3}]13–. During crystallization, a microscale symmetry-breaking event and a nonlinear asymmetric autocatalysis process make the enantiomers crystallize in different batches, which provides an opportunity to isolate the homochiral bulk materials. The defined structures of the racemic and homochiral crystals thus provide a molecular-level illustration that H-bonding interactions are responsible for such high-level chiral recognition, in a process similar to the supramolecular chirality frequently observed in biology. These POM macroanions showed a high cytotoxicity against various cancer cells, particularly ovarian cancer cells. The antitumor activity of these compounds resulted at least in part from the activation of the apoptotic pathways, as shown by the flow cytometry, Annexin V staining, DNA ladder, and TUNEL assay, likely by blocking the cell cycle and complexing with proteins in cells. The POM macroanions reported herein provide promising and novel antitumor agents for the potential treatment of various cancers.
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影响因子：
56.9
作者：
KONDEPUDI, DK;KAUFMAN, RJ;SINGH, N
通讯作者：
SINGH, N
影响因子：
4.6
作者：
GARVEY, JF;POPE, MT
通讯作者：
POPE, MT
影响因子：
64.8
作者：
Chin, J;Lee, SS;Kim, DH
通讯作者：
Kim, DH
DOI：
10.1016/j.jphotobiol.2012.04.001
发表时间：
2012-07-02
影响因子：
5.4
作者：
Hu, Yan-Jun;Yue, Hua-Li;Zhang, Li-Ping
通讯作者：
Zhang, Li-Ping
影响因子：
16.6
作者：
Fang, XK;Anderson, TM;Hill, CL
通讯作者：
Hill, CL