A Unified Strategy to Access 2- and 4\u2011Deoxygenated Sugars Enabled by Manganese-Promoted 1,2-Radical Migration<\/p>\n
M. Carder, C. E. Suh, A. E. Wendlandt, J. Am. Chem. Soc<\/em>. 2021<\/strong>, 143<\/em>, 13798. doi: 10.1021\/jacs.1c05993.<\/a><\/p><\/blockquote>\n \u00a0\u00a0\u00a0\u00a0\u00a0\u00a0\u00a0 \u8131\u6c27\u7cd6\u4ee5\u53ca\u591a\u91cd\u5b98\u80fd\u56e2\u5316\u7684\u7cd6\u7c7b\u7ed3\u6784\u5355\u5143\u5e7f\u6cdb\u5b58\u5728\u4e8e\u4e00\u7cfb\u5217\u5177\u6709\u4f18\u826f\u751f\u7269\u6d3b\u6027\u7684\u5929\u7136\u4ea7\u7269\u5206\u5b50\u4e2d (Figure 1A)\u3002\u7136\u800c\uff0c\u76ee\u524d\u5bf9\u4e8e\u6784\u5efa\u5404\u7c7b\u8131\u6c27\u7cd6\u5206\u5b50\u534a\u5408\u6210\u7b56\u7565\u7684\u7814\u7a76\uff0c\u4ecd\u7136\u8f83\u5c11\u6709\u76f8\u5173\u7684\u6587\u732e\u62a5\u9053 (Figure 1B)[1]-[2]<\/sup>\u3002\u8fd9\u91cc\uff0c\u53d7\u5230\u524d\u671f\u5bf9\u4e8e\u751f\u7269\u5408\u6210\u4e2d\u91c7\u7528RNR (ribonucleotide reductase)\u50ac\u5316\u7684\u901a\u8fc7\u81ea\u7531\u57fa1,2-\u8fc1\u79fb\u6216SCS (spin center shift)\u673a\u7406\u8fdb\u884c\u7684\u7cd6\u5206\u5b50\u8131\u6c27\u53cd\u5e94\u8fc7\u7a0b (Figure 1C)[3]<\/sup>\u7684\u542f\u53d1\uff0c\u7f8e\u56fdMIT\u7684A. E. Wendlandt\u7814\u7a76\u56e2\u961f\u6210\u529f\u8bbe\u8ba1\u51fa\u4e00\u79cd\u5168\u65b0\u7684\u6784\u5efa2-\u4e0e4-\u8131\u6c27\u7cd6\u7c7b\u5206\u5b50\u7684\u7b80\u6d01\u534a\u5408\u6210\u7b56\u7565\uff0c\u53cd\u5e94\u8fc7\u7a0b\u4e2d\u7684\u5173\u952e\u6b65\u9aa4\u4e3b\u8981\u6d89\u53ca\u5421\u5583\u7cd6\u5206\u5b50\u7684\u6c27\u5316\u8fd8\u539f\u5f02\u6784\u5316 (Figure 1D)\u3002<\/p>\n \u9996\u5148\uff0c\u4f5c\u8005\u91c7\u7528L-\u03b1-methylrhamnoside (1<\/strong>) \u4f5c\u4e3a\u6a21\u677f\u5e95\u7269\uff0c\u8fdb\u884c\u76f8\u5173\u53cd\u5e94\u6761\u4ef6\u7684\u4f18\u5316\u7b5b\u9009 (Figure 2)\u3002\u8fdb\u800c\u786e\u5b9a\u6700\u4f73\u7684\u53cd\u5e94\u6761\u4ef6\u4e3a\uff1a\u91c7\u75284-CzIPN\u4f5c\u4e3a\u5149\u50ac\u5316\u5242\uff0cMn(OAc)2<\/sub>\u00b74H2<\/sub>O\u4f5c\u4e3a\u91d1\u5c5e\u50ac\u5316\u5242\uff0cquinuclidine\u4e0e(n-Bu)4<\/sub>NOAc\u4f5c\u4e3a\u6dfb\u52a0\u5242\uff0c\u9009\u62e9\u84dd\u5149LED\u8f90\u5c04 (blue LED Kessil lamp)\uff0cMeCN\/DMSO\u4f5c\u4e3a\u53cd\u5e94\u6eb6\u5242\uff0c\u53cd\u5e94\u6e29\u5ea6\u4e3a\u5ba4\u6e29\uff0c\u6700\u7ec8\u83b7\u5f97\u76f8\u5e94\u76842-\u8131\u6c27-3-\u916e\u5421\u5583\u7cd6\u82f7 (2-deoxyketopyranoside)\u4ea7\u7269 \u00a0(Figure 2A)\u3002\u540c\u65f6\uff0c\u8be5\u5c0f\u7ec4\u8fdb\u4e00\u6b65\u5bf9\u76f8\u5173\u7684\u53cd\u5e94\u673a\u7406\u8def\u5f84\u8fdb\u884c\u5408\u7406\u7684\u63a8\u6d4b (Figure 2B-D)\u3002<\/p>\n \u00a0 \u5728\u83b7\u5f97\u4e0a\u8ff0\u7684\u6700\u4f73\u53cd\u5e94\u6761\u4ef6\u4e4b\u540e\uff0c\u8be5\u5c0f\u7ec4\u8fdb\u4e00\u6b65\u5bf9\u4e00\u7cfb\u5217\u5355\u7cd6\u5e95\u7269\u7684\u5e94\u7528\u8303\u56f4 (Figure 3A-C)\u4ee5\u53ca\u5408\u6210\u5e94\u7528\u4ef7\u503c(\u5373\u8fdb\u4e00\u6b65\u76f8\u5e94\u7684\u7a00\u6709\u8131\u7cd6\u7cd6\u7c7b\u5206\u5b50\uff0cFigure 3D)\u8fdb\u884c\u6df1\u5165\u7814\u7a76\u3002 \u540c\u65f6\uff0c\u7814\u7a76\u53d1\u73b0\uff0c\u4ea7\u7269\u7684\u9009\u62e9\u6027\u53d7\u5230\u4e24\u65b9\u9762\u56e0\u7d20\uff0c\u5373\u8d77\u59cb\u7684HAA (H atom abstraction)\u4f4d\u70b9\u4ee5\u53ca\u540e\u7eed\u81ea\u7531\u57fa\u8fc1\u79fb\u6b65\u9aa4\u4e2d\u7684\u533a\u57df\u9009\u62e9\u6027\u7684\u63a7\u5236 (\u8be6\u89c1SI<\/a>)\u3002<\/p>\n \u4e4b\u540e\uff0c\u8be5\u5c0f\u7ec4\u901a\u8fc7\u4e00\u7cfb\u5217\u4ea4\u53c9\u5b9e\u9a8c\u7684\u76f8\u5173\u7814\u7a76\u8868\u660e\uff0c\u4ea7\u72692<\/strong>\u5728\u4e0a\u8ff0\u7684\u6c27\u5316\u8fd8\u539f\u5f02\u6784\u5316\u53cd\u5e94\u6761\u4ef6\u4e0b\uff0c\u65e0\u6cd5\u8fdb\u884c\u540e\u7eed\u7684\u5206\u89e3\u53cd\u5e94\u3002\u540c\u65f6\uff0c3-ketoglucoside 29<\/strong>\u5e76\u975e\u53cd\u5e94\u8fc7\u7a0b\u4e2d\u7684\u76f8\u5e94\u4e2d\u95f4\u4f53\uff0c\u5e76\u4e1429<\/strong>\u80fd\u591f\u5728\u4e0a\u8ff0\u7684\u6807\u51c6\u53cd\u5e94\u6761\u4ef6\u4e0b\u53d1\u751f\u5206\u89e3\u3002\u800c\u4e14\uff0c\u76f8\u5e94\u7684\u916e\u4e2d\u95f4\u4f53\u80fd\u591f\u5728\u4e0a\u8ff0\u7684\u6807\u51c6\u53cd\u5e94\u4f53\u7cfb\u4e2d\uff0c\u901a\u8fc74-CzIPN\u2022\u2212\u7684\u8fd8\u539f\uff0c\u5f62\u6210\u4ea7\u72692<\/strong> (Figure 4A-C)\u3002\u540c\u65f6\uff0c\u8be5\u5c0f\u7ec4\u901a\u8fc7\u5206\u5b50\u95f4\u7ade\u4e89\u5b9e\u9a8c\u7814\u7a76\u8868\u660e\uff0c29<\/strong>\u7684\u5206\u89e3\u901f\u7387\u5feb\u4e8e\u5316\u5408\u72699<\/strong>\u7684\u6d88\u8017\u901f\u7387 (\u8be6\u89c1SI<\/a>)\u3002<\/p>\n \u540c\u65f6\uff0c\u8be5\u5c0f\u7ec4\u8fdb\u4e00\u6b65\u901a\u8fc7ESR\u4ee5\u53caUV-vis\uff0c\u5bf9\u4e8e\u9530\u76d0\u5728\u81ea\u7531\u57fa\u8fc1\u79fb\u53cd\u5e94\u8fc7\u7a0b\u4e2d\u7684\u4f5c\u7528\u8fdb\u884c\u6df1\u5165\u7814\u7a76 (\u8be6\u89c1SI<\/a>)\u3002\u4f5c\u8005\u901a\u8fc7\u9759\u6001\u8367\u5149\u6dec\u706d (steady-state fluorescence quenching)\u5b9e\u9a8c\u7684\u76f8\u5173\u7814\u7a76\u8868\u660e\uff0c Mn3+<\/sup>\u80fd\u591f\u6709\u6548\u5730\u6dec\u706d\u6fc0\u53d1\u6001\u76844-CzIPN \uff0c\u5f62\u6210\u76f8\u5e94\u7684Mn2+<\/sup> (PC+\u2022<\/sup>\/PC* = \u22121.18 V vs SCE)\u3002\u4e4b\u540e\uff0c\u901a\u8fc7EPR\u8c31\u5b66\u7684\u7814\u7a76\uff0c\u8fdb\u800c\u8868\u660e\u524d\u50ac\u5316\u5242Mn3+<\/sup>\u80fd\u591f\u6781\u4e3a\u8fc5\u901f (\u65f6\u95f4<1 min)\u5e76\u5b9a\u91cf\u5730\u8f6c\u5316\u4e3a\u76f8\u5e94\u7684Mn2+<\/sup> (Figure 5B-C)\u3002\u5e76\u4e14\uff0c\u4f5c\u8005\u901a\u8fc7\u63a7\u5236\u5b9e\u9a8c\u7814\u7a76\uff0c\u8fdb\u4e00\u6b65\u89c2\u5bdf\u5230Mn3+<\/sup>\u7684\u5b9a\u91cf\u8fd8\u539f\u4ec5\u9700\u8981\u91c7\u7528\u5149\u50ac\u5316\u5242\u3001quinuclidine\u4ee5\u53ca\u5149\u7167\u7684\u53cd\u5e94\u6761\u4ef6\u5373\u53ef\u6709\u6548\u5730\u8fdb\u884c\u3002<\/p>\n \u00a0\u00a0\u00a0\u00a0\u00a0\u00a0\u00a0 \u76f8\u53cd\u5730\uff0c\u7814\u7a76\u8868\u660e\uff0c\u4e0e\u76f8\u5e94quinuclidine (Q\u2022+<\/sup>\/Q = +1.1 V vs SCE)\u5206\u5b50\u7684\u6c27\u5316 (\u5f62\u6210quinuclidinium\u81ea\u7531\u57fa)\u901f\u7387\u76f8\u6bd4\uff0cMn2+<\/sup>\u00a0(Mn3+<\/sup>\/Mn2+<\/sup>\u00a0= +1.4 V vs SCE) \u5bf9\u4e8e4-CzIPN* (PC*\/PC\u2022\u2013<\/sup>\u00a0= +1.43 V vs SCE)\u00a0\u7684\u9759\u6001\u8367\u5149\u6dec\u706d\u901f\u7387\u5219\u8f83\u4e3a\u7f13\u6162 (Figure 5A)\u3002\u8fdb\u800c\u8fdb\u4e00\u6b65\u652f\u6301\u5728\u7a33\u6001\u6761\u4ef6\u4e0b\uff0c\u901a\u8fc7quinuclidine\u5206\u5b50\u7684\u4f18\u5148\u6c27\u5316\u800c\u8fdb\u884c\u7684\u8fd8\u539f\u6dec\u706d\u8fc7\u7a0b(Figure 5C)\u3002\u8fd9\u79cdMn3+<\/sup>\u4e0eMn2+<\/sup>\u00a0\u5728\u6c27\u5316\u6dec\u706d\u4e0e\u8fd8\u539f\u6dec\u706d\u5faa\u73af\u4e2d\uff0c\u53cd\u5e94\u901f\u7387\u7684\u8f83\u5927\u5dee\u5f02\uff0c\u4f7f\u5f97Mn2+<\/sup>\u00a0\u80fd\u591f\u5728\u5176\u4ed6\u5f3a\u6c27\u5316\u5242\u5b58\u5728\u7684\u6761\u4ef6\u4e0b\u6301\u4e45\u5b58\u5728\u3002\u63a5\u4e0b\u6765\uff0c\u4f5c\u8005\u901a\u8fc7\u6838\u78c1\u6ef4\u5b9a\u5b9e\u9a8c (NMR titration experiment)\u7814\u7a76\u8868\u660e\uff0cmethylrhamnoside 1<\/strong>\u4e0eMn(OAc)2<\/sub>\u00b74H2<\/sub>O\u4e4b\u95f4\u5b58\u5728\u4e2d\u7b49\u5f3a\u5ea6\u7684\u6210\u952e\u76f8\u4e92\u4f5c\u7528 (145 M\u20131<\/sup>)\uff0c\u800c1<\/strong>\u4e0eMn(OAc)3<\/sub>\u00b72H2<\/sub>O\u4e4b\u95f4\u5219\u4e0d\u5b58\u5728\u8f83\u4e3a\u663e\u8457\u7684\u76f8\u4e92\u4f5c\u7528 (\u8be6\u89c1SI<\/a>)\u3002\u7efc\u5408\u4e0a\u8ff0\u7684\u5b9e\u9a8c\u7814\u7a76\uff0c\u4f5c\u8005\u63d0\u51fa\u5982\u4e0b\u5408\u7406\u7684\u53cd\u5e94\u673a\u7406 (Figure 5D)\u3002<\/p>\n \u7f8e\u56fdMIT\u7684A. E. Wendlandt\u7814\u7a76\u56e2\u961f\u6210\u529f\u5f00\u53d1\u51fa\u4e00\u79cd\u5168\u65b0\u7684\u6784\u5efa2-\u4e0e4-\u8131\u6c27\u7cd6\u7c7b\u5316\u5408\u7269\u7684\u7b80\u6d01\u534a\u5408\u6210\u7b56\u7565\u3002\u8fd9\u4e00\u5168\u65b0\u7684\u534a\u5408\u6210\u7b56\u7565\u5177\u6709\u4f18\u826f\u7684\u533a\u57df\u9009\u62e9\u6027\u3001\u65e0\u9700\u5f15\u5165\u76f8\u5e94\u7684\u4fdd\u62a4\u57fa\u56e2\u3001\u8d77\u59cb\u539f\u6599\u5ec9\u4ef7\u6613\u5f97\u4ee5\u53ca\u826f\u597d\u7684\u5408\u6210\u5e94\u7528\u4ef7\u503c\u7b49\u4f18\u52bf\u3002<\/p>\n <\/p>\n","protected":false},"excerpt":{"rendered":"\u672c\u6587\u4f5c\u8005:\u6653\u6653 \u5bfc\u8bfb \u00a0\u00a0 \u8fd1\u671f\uff0c\u7f8e\u56fdMIT\u7684A. E. Wendlandt\u7814\u7a76\u56e2\u961f\u6210\u529f\u5f00\u53d1\u51fa\u4e00\u79cd\u5168\u65b0\u7684\u6784\u5efa2-\u4e0e4-\u8131\u6c27\u7cd6\u7c7b\u5316\u5408\u7269\u7684\u7b80\u6d01\u534a\u5408\u6210\u7b56\u7565\u3002\u8fd9\u4e00\u5168\u65b0\u7684\u534a\u5408\u6210\u7b56\u7565\u8868\u73b0\u51fa\u4f18\u826f\u7684\u533a\u57df\u9009\u62e9\u6027\u3002\u540c\u65f6\uff0c\u53cd\u5e94\u8fc7\u7a0b\u4e2d\u65e0\u9700\u5f15\u5165\u4efb\u4f55\u76f8\u5173\u7684\u4fdd\u62a4\u57fa\u56e2\u3002\u5e76\u4e14\uff0c\u8fd9\u4e00\u7b56\u7565\u4e2d\u7684\u5173\u952e\u53cd\u5e94\u6b65\u9aa4\u4e3b\u8981\u6d89\u53ca\u5728\u53ef\u89c1\u5149\u5a92\u4ecb\u7684\u5149\u6c27\u5316\u8fd8\u539f\u6761\u4ef6\u4e0b\uff0c\u901a\u8fc7\u9530 (II)\u4fc3\u8fdb\u7684\u4e2d\u6027\u6c22\u539f\u5b50\u652b\u53d6(hydrogen atom abstraction, HAA)\u8fc7\u7a0b\u5f62\u6210\u7684\u7cd6\u81ea\u7531\u57fa\u4e2d\u95f4\u4f53 (sugar radical intermediate)\u53c2\u4e0e\u7684\u6c27\u5316\u8fd8\u539f\u5f02\u6784\u5316(redox isomerization)\u8fc7\u7a0b\u3002 A Unified Strategy to Access 2- and 4\u2011Deoxygenated Sugars Enabled by Manganese-Promoted 1,2-Radical Migration M. Carder, C. E. Suh, A. E. Wendlandt, J. Am. Chem. Soc. 2021, 143, 13798. doi: 10.1021\/jacs.1c05993. \u6b63\u6587 \u00a0\u00a0\u00a0\u00a0\u00a0\u00a0\u00a0 \u8131\u6c27\u7cd6\u4ee5\u53ca\u591a\u91cd\u5b98\u80fd\u56e2\u5316\u7684\u7cd6\u7c7b\u7ed3\u6784\u5355\u5143\u5e7f\u6cdb\u5b58\u5728\u4e8e\u4e00\u7cfb\u5217\u5177\u6709\u4f18\u826f\u751f\u7269\u6d3b\u6027\u7684\u5929\u7136\u4ea7\u7269\u5206\u5b50\u4e2d (Figure 1A)\u3002\u7136\u800c\uff0c\u76ee\u524d\u5bf9\u4e8e\u6784\u5efa\u5404\u7c7b\u8131\u6c27\u7cd6\u5206\u5b50\u534a\u5408\u6210\u7b56\u7565\u7684\u7814\u7a76\uff0c\u4ecd\u7136\u8f83\u5c11\u6709\u76f8\u5173\u7684\u6587\u732e\u62a5\u9053 (Figure 1B)[1]-[2]\u3002\u8fd9\u91cc\uff0c\u53d7\u5230\u524d\u671f\u5bf9\u4e8e\u751f\u7269\u5408\u6210\u4e2d\u91c7\u7528RNR (ribonucleotide reductase)\u50ac\u5316\u7684\u901a\u8fc7\u81ea\u7531\u57fa1,2-\u8fc1\u79fb\u6216SCS (spin center shift)\u673a\u7406\u8fdb\u884c\u7684\u7cd6\u5206\u5b50\u8131\u6c27\u53cd\u5e94\u8fc7\u7a0b (Figure 1C)[3]\u7684\u542f\u53d1\uff0c\u7f8e\u56fdMIT\u7684A. E. Wendlandt\u7814\u7a76\u56e2\u961f\u6210\u529f\u8bbe\u8ba1\u51fa\u4e00\u79cd\u5168\u65b0\u7684\u6784\u5efa2-\u4e0e4-\u8131\u6c27\u7cd6\u7c7b\u5206\u5b50\u7684\u7b80\u6d01\u534a\u5408\u6210\u7b56\u7565\uff0c\u53cd\u5e94\u8fc7\u7a0b\u4e2d\u7684\u5173\u952e\u6b65\u9aa4\u4e3b\u8981\u6d89\u53ca\u5421\u5583\u7cd6\u5206\u5b50\u7684\u6c27\u5316\u8fd8\u539f\u5f02\u6784\u5316 (Figure 1D)\u3002 \u9996\u5148\uff0c\u4f5c\u8005\u91c7\u7528L-\u03b1-methylrhamnoside (1) \u4f5c\u4e3a\u6a21\u677f\u5e95\u7269\uff0c\u8fdb\u884c\u76f8\u5173\u53cd\u5e94\u6761\u4ef6\u7684\u4f18\u5316\u7b5b\u9009 (Figure 2)\u3002\u8fdb\u800c\u786e\u5b9a\u6700\u4f73\u7684\u53cd\u5e94\u6761\u4ef6\u4e3a\uff1a\u91c7\u75284-CzIPN\u4f5c\u4e3a\u5149\u50ac\u5316\u5242\uff0cMn(OAc)2\u00b74H2O\u4f5c\u4e3a\u91d1\u5c5e\u50ac\u5316\u5242\uff0cquinuclidine\u4e0e(n-Bu)4NOAc\u4f5c\u4e3a\u6dfb\u52a0\u5242\uff0c\u9009\u62e9\u84dd\u5149LED\u8f90\u5c04 (blue LED Kessil lamp)\uff0cMeCN\/DMSO\u4f5c\u4e3a\u53cd\u5e94\u6eb6\u5242\uff0c\u53cd\u5e94\u6e29\u5ea6\u4e3a\u5ba4\u6e29\uff0c\u6700\u7ec8\u83b7\u5f97\u76f8\u5e94\u76842-\u8131\u6c27-3-\u916e\u5421\u5583\u7cd6\u82f7 (2-deoxyketopyranoside)\u4ea7\u7269 \u00a0(Figure 2A)\u3002\u540c\u65f6\uff0c\u8be5\u5c0f\u7ec4\u8fdb\u4e00\u6b65\u5bf9\u76f8\u5173\u7684\u53cd\u5e94\u673a\u7406\u8def\u5f84\u8fdb\u884c\u5408\u7406\u7684\u63a8\u6d4b (Figure 2B-D)\u3002 \u00a0 \u5728\u83b7\u5f97\u4e0a\u8ff0\u7684\u6700\u4f73\u53cd\u5e94\u6761\u4ef6\u4e4b\u540e\uff0c\u8be5\u5c0f\u7ec4\u8fdb\u4e00\u6b65\u5bf9\u4e00\u7cfb\u5217\u5355\u7cd6\u5e95\u7269\u7684\u5e94\u7528\u8303\u56f4 (Figure 3A-C)\u4ee5\u53ca\u5408\u6210\u5e94\u7528\u4ef7\u503c(\u5373\u8fdb\u4e00\u6b65\u76f8\u5e94\u7684\u7a00\u6709\u8131\u7cd6\u7cd6\u7c7b\u5206\u5b50\uff0cFigure 3D)\u8fdb\u884c\u6df1\u5165\u7814\u7a76\u3002 \u540c\u65f6\uff0c\u7814\u7a76\u53d1\u73b0\uff0c\u4ea7\u7269\u7684\u9009\u62e9\u6027\u53d7\u5230\u4e24\u65b9\u9762\u56e0\u7d20\uff0c\u5373\u8d77\u59cb\u7684HAA (H atom abstraction)\u4f4d\u70b9\u4ee5\u53ca\u540e\u7eed\u81ea\u7531\u57fa\u8fc1\u79fb\u6b65\u9aa4\u4e2d\u7684\u533a\u57df\u9009\u62e9\u6027\u7684\u63a7\u5236 (\u8be6\u89c1SI)\u3002 \u4e4b\u540e\uff0c\u8be5\u5c0f\u7ec4\u901a\u8fc7\u4e00\u7cfb\u5217\u4ea4\u53c9\u5b9e\u9a8c\u7684\u76f8\u5173\u7814\u7a76\u8868\u660e\uff0c\u4ea7\u72692\u5728\u4e0a\u8ff0\u7684\u6c27\u5316\u8fd8\u539f\u5f02\u6784\u5316\u53cd\u5e94\u6761\u4ef6\u4e0b\uff0c\u65e0\u6cd5\u8fdb\u884c\u540e\u7eed\u7684\u5206\u89e3\u53cd\u5e94\u3002\u540c\u65f6\uff0c3-ketoglucoside 29\u5e76\u975e\u53cd\u5e94\u8fc7\u7a0b\u4e2d\u7684\u76f8\u5e94\u4e2d\u95f4\u4f53\uff0c\u5e76\u4e1429\u80fd\u591f\u5728\u4e0a\u8ff0\u7684\u6807\u51c6\u53cd\u5e94\u6761\u4ef6\u4e0b\u53d1\u751f\u5206\u89e3\u3002\u800c\u4e14\uff0c\u76f8\u5e94\u7684\u916e\u4e2d\u95f4\u4f53\u80fd\u591f\u5728\u4e0a\u8ff0\u7684\u6807\u51c6\u53cd\u5e94\u4f53\u7cfb\u4e2d\uff0c\u901a\u8fc74-CzIPN\u2022\u2212\u7684\u8fd8\u539f\uff0c\u5f62\u6210\u4ea7\u72692 (Figure 4A-C)\u3002\u540c\u65f6\uff0c\u8be5\u5c0f\u7ec4\u901a\u8fc7\u5206\u5b50\u95f4\u7ade\u4e89\u5b9e\u9a8c\u7814\u7a76\u8868\u660e\uff0c29\u7684\u5206\u89e3\u901f\u7387\u5feb\u4e8e\u5316\u5408\u72699\u7684\u6d88\u8017\u901f\u7387 (\u8be6\u89c1SI)\u3002 \u540c\u65f6\uff0c\u8be5\u5c0f\u7ec4\u8fdb\u4e00\u6b65\u901a\u8fc7ESR\u4ee5\u53caUV-vis\uff0c\u5bf9\u4e8e\u9530\u76d0\u5728\u81ea\u7531\u57fa\u8fc1\u79fb\u53cd\u5e94\u8fc7\u7a0b\u4e2d\u7684\u4f5c\u7528\u8fdb\u884c\u6df1\u5165\u7814\u7a76 (\u8be6\u89c1SI)\u3002\u4f5c\u8005\u901a\u8fc7\u9759\u6001\u8367\u5149\u6dec\u706d (steady-state fluorescence quenching)\u5b9e\u9a8c\u7684\u76f8\u5173\u7814\u7a76\u8868\u660e\uff0c Mn3+\u80fd\u591f\u6709\u6548\u5730\u6dec\u706d\u6fc0\u53d1\u6001\u76844-CzIPN \uff0c\u5f62\u6210\u76f8\u5e94\u7684Mn2+ (PC+\u2022\/PC* = \u22121.18 V vs SCE)\u3002\u4e4b\u540e\uff0c\u901a\u8fc7EPR\u8c31\u5b66\u7684\u7814\u7a76\uff0c\u8fdb\u800c\u8868\u660e\u524d\u50ac\u5316\u5242Mn3+\u80fd\u591f\u6781\u4e3a\u8fc5\u901f (\u65f6\u95f4<1 min)\u5e76\u5b9a\u91cf\u5730\u8f6c\u5316\u4e3a\u76f8\u5e94\u7684Mn2+ (Figure 5B-C)\u3002\u5e76\u4e14\uff0c\u4f5c\u8005\u901a\u8fc7\u63a7\u5236\u5b9e\u9a8c\u7814\u7a76\uff0c\u8fdb\u4e00\u6b65\u89c2\u5bdf\u5230Mn3+\u7684\u5b9a\u91cf\u8fd8\u539f\u4ec5\u9700\u8981\u91c7\u7528\u5149\u50ac\u5316\u5242\u3001quinuclidine\u4ee5\u53ca\u5149\u7167\u7684\u53cd\u5e94\u6761\u4ef6\u5373\u53ef\u6709\u6548\u5730\u8fdb\u884c\u3002 \u00a0\u00a0\u00a0\u00a0\u00a0\u00a0\u00a0 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