{"id":23559,"date":"2016-07-04T08:10:44","date_gmt":"2016-07-04T00:10:44","guid":{"rendered":"\/\/m.iemloyee.com\/?p=23559"},"modified":"2016-07-03T23:00:18","modified_gmt":"2016-07-03T15:00:18","slug":"nature%ef%bc%9a%e9%80%9a%e8%bf%87%e7%94%b5%e5%ad%90-%e8%b4%a8%e5%ad%90%e8%bd%ac%e7%a7%bb%e4%bb%8b%e8%b4%a8%e5%ae%9e%e7%8e%b0%e7%94%b5%e5%82%ac%e5%8c%96%e9%86%87%e6%b0%a7%e5%8c%96%e5%8f%8d%e5%ba%94","status":"publish","type":"post","link":"\/\/m.iemloyee.com\/?p=23559","title":{"rendered":"Nature\uff1a\u901a\u8fc7\u7535\u5b50-\u8d28\u5b50\u8f6c\u79fb\u4ecb\u8d28\u5b9e\u73b0\u7535\u50ac\u5316\u9187\u6c27\u5316\u53cd\u5e94"},"content":{"rendered":"

\u3010\u80cc\u666f\u7b80\u4ecb\u3011<\/strong>
\n\u968f\u7740\u71c3\u6599\u7535\u6c60\u3001\u751f\u7269\u8d28\u80fd\u7684\u5229\u7528\u53ca\u7cbe\u7ec6\u5316\u5b66\u5408\u6210\u8fd9\u4e9b\u6f5c\u5728\u5e94\u7528\u7684\u53d1\u5c55\uff0c\u9187\u7684\u7535\u5316\u5b66\u6c27\u5316\u5c06\u6210\u4e3a\u80fd\u6e90\u548c\u5316\u5b66\u8f6c\u5316\u5de5\u4f5c\u7684\u4e00\u5927\u91cd\u70b9\u3002<\/span><\/strong>\u954d\u50ac\u5316\u5242\u53ef\u7528\u4e8e\u7535\u5316\u5b66\u751f\u4ea7\u548c\u6c22\u7684\u6c27\u5316\u8fc7\u7a0b\uff0c\u4ece\u5176\u6700\u8fd1\u7684\u53d1\u5c55\u6765\u770b\uff0c\u9187\u7535\u5316\u5b66\u6c27\u5316\u8fc7\u7a0b\u4e2d\u7684\u5c0f\u5206\u5b50\u7535\u50ac\u5316\u5242\u4e5f\u5c06\u6210\u4e3a\u672a\u6765\u6df1\u5165\u53d1\u5c55\u8fc7\u7a0b\u4e2d\u7684\u9887\u5177\u524d\u666f\u7684\u76ee\u6807\u3002\u5177\u6709\u53ef\u5f62\u6210\u6c22\u5316\u6d3b\u6027\u70b9\u7684\u80fa\u7c7b\u914d\u5408\u7269\u4e0d\u4ec5\u53ef\u4ee5\u50ac\u5316\u5236\u6c22\u8fc7\u7a0b\u4e14\u5176\u901f\u7387\u8fdc\u9ad8\u4e8e\u9176\u7c7b\u50ac\u5316\uff1b\u6b64\u5916\uff0c\u5b83\u8fd8\u53ef\u4ee5\u8c03\u8282\u53ef\u9006\u7535\u50ac\u5316\u5236\u6c22\u548c\u53ca\u7528\u7c7b\u9176\u6c27\u5316\u65f6\u7684\u6027\u80fd\u3002\u7535\u50ac\u5316\u9187\u6c27\u5316\u7684\u53d1\u5c55\u4e00\u76f4\u8f83\u4e3a\u5e73\u7f13\u3002\u954d\u7edc\u5408\u7269\u4e0e\u4e4b\u524d\u7528\u4e8e\u6c22\u6c27\u5316\u7684\u50ac\u5316\u5242\u76f8\u4f3c\uff0c\u5df2\u7ecf\u5f97\u5230\u8bc1\u5b9e\u954d\u7edc\u5408\u7269\u57282.1\u5468\u8f6c\u7387\/s\u65f6\uff0c\u53ef\u4ee5\u8c03\u8282\u82ef\u7532\u9187\u6709\u6548\u7535\u5316\u5b66\u6c27\u5316\u3002\u7136\u800c\uff0c\u8fd9\u4e9b\u5316\u5408\u7269\u5728\u4e0e\u4e59\u9187\u548c\u7532\u9187\u53cd\u5e94\u65f6\u5177\u6709\u8f83\u5dee\u7684\u53cd\u5e94\u6d3b\u6027\u3002<\/p>\n

\u6709\u673a\u785d\u9170\u57fa\uff0c\u5982TEMPO\uff082,2,6,6-\u56db\u7532\u57fa-1-\u54cc\u5576-N-\u6c27\u81ea\u7531\u57fa\uff09\uff0c\u662f\u9187\u6c27\u5316\u53cd\u5e94\u7814\u7a76\u4e2d\u4f7f\u7528\u6700\u5e7f\u6cdb\u7684\u7535\u50ac\u5316\u5242\u3002<\/strong><\/span>\u8fd9\u7c7b\u50ac\u5316\u5242\u53ef\u4e0e\u5927\u591a\u6570\u9187\u53cd\u5e94\u8868\u73b0\u51fa\u826f\u597d\u7684\u6d3b\u6027\uff081-2\u5468\u8f6c\u7387\/s\uff09\uff0c\u5e76\u4e14\u5728\u6709\u673a\u7535\u5316\u5b66\u5408\u6210\u65b9\u9762\u4e5f\u5927\u6709\u5e0c\u671b\u3002\u4f46\u662f\uff0c\u6709\u673a\u785d\u9170\u57fa\u7c7b\u7535\u50ac\u5316\u5242\u5728\u80fd\u91cf\u8f6c\u6362\u65b9\u9762\u7684\u4f7f\u7528\u4f1a\u53d7\u5230\u9ad8\u7535\u6781\u7535\u52bf\u9650\u5236\uff0c\u8fd9\u79cd\u9ad8\u7535\u6781\u7535\u52bf\u662f\u7528\u4e8e\u4ea7\u751f\u53cd\u5e94\u6027\u6c27\u5408\u6c28\u7684\u3002<\/p>\n

\u3010\u4e3b\u8981\u6210\u679c\u3011<\/strong>
\n\u4e0d\u4e45\u524d\uff0c\u5a01\u65af\u5eb7\u661f\u5927\u5b66\u9ea6\u8fea\u900a\u5206\u6821\u5316\u5b66\u7cfb\u7684Artavazd Badalyan\u548c Shannon S. Stahl\u62a5\u9053\u4e86\uff082,2′-\u8054\u5421\u5576\uff09\u94dc\/\u785d\u9170\u57fa<\/strong>\u5171\u50ac\u5316\u5242\u4f53\u7cfb<\/strong><\/span>\u53ef\u7528\u4e8e\u66f4\u5feb\u901f\u7684\u7535\u5316\u5b66\u9187\u6c27\u5316\u53cd\u5e94<\/strong><\/span>\uff0c\u800c\u4e14\u5728\u64cd\u4f5c\u8fc7\u7a0b\u4e2d\u6240\u7528\u7535\u6781\u7535\u52bf\u4f1a\u6bd4\u4ec5\u7528TEMPO\u4f5c\u50ac\u5316\u5242\u7684\u5316\u5b66\u8fc7\u7a0b\u8981\u4f4e\u534a\u4f0f<\/span><\/strong>\u3002\uff082,2′-\u8054\u5421\u5576\uff09\u94dc\uff08II\uff09\u548cTEMPO\u6c27\u5316\u8fd8\u539f\u5bf9\u8868\u73b0\u51fa\u534f\u540c\u53cd\u5e94\u6027\uff0c\u6b64\u5916\u8fd8\u4f7f\u7528\u4e86\u4f4e\u7535\u4f4d\uff0c\u5c5e\u4e8e\u8d28\u5b50\u5076\u8054TEMPO \/ TEMPOH\u6c27\u5316\u8fd8\u539f\u8fc7\u7a0b\uff0c\u800c\u4e0d\u662f\u9ad8\u7535\u4f4dTEMPO \/TEMPO+<\/sup>\u53cd\u5e94\u8fc7\u7a0b\u3002\u7814\u7a76\u8868\u660e\uff0c\u7535\u5b50\u8d28\u5b50\u8f6c\u79fb\u4ecb\u8d28\uff08\u5982TEMPO\uff09\u662f\u5982\u4f55\u4e0e\u7b2c\u4e00\u884c\u8fc7\u6e21\u91d1\u5c5e\uff08\u5982\u94dc\uff09\u7ed3\u5408\u4f7f\u7528\uff0c\u4ece\u800c\u5b9e\u73b0\u9ad8\u6548\u7684\u4e24\u7535\u5b50\u7535\u5316\u5b66\u8fc7\u7a0b\uff0c\u4e5f\u56e0\u6b64\u4e3a\u975e\u8d35\u91d1\u5c5e\u7535\u50ac\u5316\u5242\u7684\u53d1\u5c55\u5f15\u5165\u4e86\u4e00\u4e2a\u65b0\u7684\u6982\u5ff5\u3002<\/p>\n

\u3010\u56fe\u6587\u5bfc\u8bfb\u3011
\n\u56fe\u4e00\uff1a\u5206\u5b50\u7535\u50ac\u5316\u5242\u53ca\u76f8\u5173\u5747\u76f8\u548c\u9176\u50ac\u5316\u5242<\/strong>
\n\"nature1\"<\/p>\n

\u8bf4\u660e\uff1a<\/strong>
\na\uff1a\u5408\u6210\u80fd\u50ac\u5316\u5236\u6c22\u7684\u954d\u914d\u5408\u7269\uff08\u914d\u5408\u7269\u7684\u4fa7\u80fa\u4f5c\u4e3a\u8d28\u5b50\u7ee7\u7535\u5668\uff0c\u5e76\u4e14\u5177\u6709[FeFe]\u6c22\u5316\u6d3b\u6027\u4f4d\u70b9\u7684\u7c7b\u4f3c\u7ed3\u6784\uff09\uff1b
\nb\uff1aTEMPO\u7684\u6c27\u5316\u8fd8\u539f\u53cd\u5e94\u8fc7\u7a0b\uff1b
\nc\u3001d\uff1a\u6c27\u5408\u6c28\u548c\uff08(bpy)Cu\/TEMPO\u57fa\u4e24\u79cd\u50ac\u5316\u5242\u50ac\u5316\u9187\u6c27\u5316\u53cd\u5e94\u7684\u7b80\u5355\u5faa\u73af\u56fe\uff1b
\ne\uff1a\u534a\u4e73\u7cd6\u6c27\u5316\u9176\u7684\u6c27\u5316\u6d3b\u6027\u4f4d\u70b9\u3002<\/p>\n

\u56fe\u4e8c\uff1a(bpy)Cu(OTf)\u548cTEMPO\u6eb6\u6db2\u7684\u5faa\u73af\u4f0f\u5b89\u56fe\u548c\u538c\u6c27\u6761\u4ef6\u4e0b(bpy)Cu(II) -\u50ac\u5316\u6c27\u5316TEMPOH\uff08\u548c\u82ef\u7532\u9187\uff09\u7684\u5206\u5149\u5149\u5ea6\u66f2\u7ebf\u3002<\/strong><\/p>\n

\"nature2\"<\/p>\n

\u8bf4\u660e\uff1a<\/strong>
\na\u6761\u4ef6\uff1a1 mM (bpy)Cu(OTf)\uff0c1mM TEMPO\uff0c10 mV s\u22121,\u73bb\u7483\u78b3\u5de5\u4f5c\u7535\u6781\uff0c0.1M Bu4NClO4\/ CH3CN\uff1b
\nb\u6761\u4ef6\uff1a1 mM Cu(II)(OTf)2\uff0c1mM bpy\uff0c0.1mM TEMPO\uff0c50mM 2,6-\u4e8c\u7532\u57fa\u5421\u5576\uff0c100mM PhCH2OH\uff0c2mL\uff0c25\u2103\uff0c0.1M Bu4NClO4\/ CH3CN\uff0c\u53cd\u5e94\u65f6\u95f4\u4e3a20\u5206\u949f\u3002
\n\u6211\u4eec\u53ef\u4ee5\u6ce8\u610f\u5230\uff0ca\u4e2d\u5bf9\u4e8e(bpy)Cu\u548cTEMPO\u4e24\u7c7b\u50ac\u5316\u5242\u4e2d\u7684\u5cf0\u503c\u7535\u6d41\u7684\u5dee\u522b\u53cd\u6620\u4e86\u5b83\u4eec\u6269\u6563\u6027\u8d28\u7684\u5dee\u5f02\u3002b\u4e2d\u6700\u7ec8\u5149\u8c31\u5bf9\u5e94\u4e8e1 mM (bpy)Cu\uff08I\uff09(OTf)\u5355\u72ec\u5236\u5907\u6eb6\u6db2\u7684\u5149\u8c31\u3002\u5728\u65e9\u671f\u65f6\u95f4\u70b9\u7b49\u5438\u6536\u884c\u4e3a\u7684\u7f3a\u4e4f\u5219\u53cd\u6620\u5728\u53cd\u5e94\u6761\u4ef6\u4e0bCu(II)\/Cu(I)\/bpy\u5f62\u6001\u7684\u53d8\u5316\u3002<\/p>\n

\u56fe\u4e09\uff1a(bpy)Cu\/TEMPO \u548cTEMPO \u50ac\u5316\u65f6\uff0c\u82ef\u7532\u9187\u7684\u7535\u5316\u5b66\u6c27\u5316\u6027\u80fd\uff0c\u5176\u5faa\u73af\u4f0f\u5b89\u56fe\uff0c\u52a8\u529b\u5b66\u6570\u636e\u548c\u6027\u80fd\u6bd4\u8f83\u3002<\/strong><\/p>\n

\"nature3\"<\/p>\n

\u8bf4\u660e\uff1a<\/strong>
\na\uff1a(bpy)Cu\/TEMPO\u6eb6\u6db2\u7684\u5faa\u73af\u4f0f\u5b89\u56fe\u3002\u5176\u4e2d1 mM Cu(I)OTf\uff0c1 mM bpy\uff0c5 mM TEMPO (\u9ed1\u8272)\uff0c\u52a0\u516550mM\u7684 Et3N\uff08\u7ea2\u8272\uff09\uff0c\u7136\u540e\u518d\u52a0\u5165\u7684100mM PhCH2OH\uff08\u84dd\u8272\uff09\uff1b
\nb\uff1a\u7535\u6d41icat\uff08\u03bcA\uff09\u4e0e(bpy) Cu(I)OTf\u6d53\u5ea6\uff08mM\uff09\u6240\u5bf9\u5e94\u7684\u51fd\u6570\u56fe\uff1b
\n\u6761\u4ef6\uff1a5 mM TEMPO, 50 mM Et3N, 100 mM PhCH2OH\u3002
\nc\uff1a\u7535\u6d41icat\uff08\u03bcA\uff09\u4e0e[PhCH2OH]0.5\uff08M0.5\uff09\u6d53\u5ea6\u6240\u5bf9\u5e94\u7684\u51fd\u6570\u56fe\uff1b
\n\u6761\u4ef6\uff1a1 mM (bpy)Cu(I), 5 mM TEMPO, 50 mM Et3N\u3002
\nd\uff1aTEMPO\u6eb6\u6db2\u7684\u5faa\u73af\u4f0f\u5b89\u56fe\u3002\u5176\u4e2d1 mM TEMPO (\u9ed1\u8272), \u52a0\u5165450 mM NMI (\u7ea2\u8272), \u518d\u52a0\u5165 100 mM PhCH2OH (\u84dd\u8272)\u3002
\ne\uff1a\u7535\u6d41icat\uff08\u03bcA\uff09\u4e0e[TEMPO]\uff08mM\uff09\u6d53\u5ea6\u6240\u5bf9\u5e94\u7684\u51fd\u6570\u56fe\uff1b
\n\u6761\u4ef6: 450 mM NMI, 100 mM PhCH2OH.
\nf\uff1a\u7535\u6d41icat\uff08\u03bcA\uff09\u4e0e[PhCH2OH]0.5\uff08M0.5\uff09\u6d53\u5ea6\u6240\u5bf9\u5e94\u7684\u51fd\u6570\u56fe\uff1b
\n\u6761\u4ef6: 1 mM TEMPO, 450 mM NMI.
\ng\uff1a(bpy)Cu\/TEMPO- \u548cTEMPO-\u7535\u50ac\u5316\u6c27\u5316\u82ef\u7532\u9187\u7684\u6027\u80fd\u6bd4\u8f83.
\n\u6240\u6709\u7684\u5b9e\u9a8c\u5747\u57280.1 M Bu4NClO4\/CH3CN, (bpy)Cu\/TEMPO\u7528150 mVs\u22121 \uff0c\u53ea\u6709TEMPO\u65f6\u7528100 mV s\u22121\u6761\u4ef6\u4e0b\u53cd\u5e94\u3002<\/p>\n

\u56fe\u56db\uff1a\u4e0d\u540c\u9187\u4e0d\u540c\u50ac\u5316\u5242\u4f53\u7cfb\u7684\u7535\u5b50\u6548\u5e94\u53ca\u76f8\u5bf9\u53cd\u5e94\u6d3b\u6027\u3002<\/strong><\/p>\n

\"nature4\"<\/p>\n

\u8bf4\u660e\uff1a<\/strong>
\n\u4e0d\u540c\u7535\u50ac\u5316\u5242\u4e0e\u53d6\u4ee3\u82c4\u9187\u53cd\u5e94\u65f6\u7684Hammett\u51fd\u6570\u56fe\uff0c\u5176\u4e2d (a)\uff1a (bpy)Cu\/TEMPO\uff0c(b)\uff1a TEMPO\uff1b\u53cd\u5e94\u6761\u4ef6\u5982\u56fe\u4e09\u6240\u793a\u3002
\nc\uff1a(bpy)Cu\/TEMPO-\u50ac\u5316\u9187\u6c27\u5316\u7684\u673a\u5236\uff1b
\nd\uff1a\u4e09\u79cd\u4e0d\u5bf9\u50ac\u5316\u4f53\u7cfb\uff08Cu\/TEMPO\u3001Cu\/ABNO\u548c\u53ea\u542bTEMPO\uff09\u4e0e\u516d\u79cd\u4e0d\u540c\u82c4\u9187\u3001\u8102\u80aa\u65cf\u9187\u3001\u4f2f\u9187\u548c\u4ef2\u9187\u7684\u76f8\u5bf9\u50ac\u5316\u6d3b\u6027\u3002
\n\u6761\u4ef6\u5747\u4e3a\uff1a100 mM \u9187\u30010.1 M Bu4NClO4 \u6eb6\u4e8eCH3CN\u3002
\nCu\/TEMPO: 1 mM (bpy)Cu(I)(OTf), 5 mM TEMPO, 50 mM Et3N;
\nCu\/ABNO: 1 mM (bpy)Cu(I)(OTf), 1 mM ABNO, 50 mM Et3N\u3002
\nTEMPO:1 mM TEMPO, 450 mM NMI\uff0c\u5176\u4e2d\u901f\u7387\u5e38\u6570\u53ef\u6839\u636e\u76f8\u5173\u516c\u5f0f\u5f97\u51fa\u3002<\/p>\n

\u7ed3\u8bed<\/strong>
\nBr\u00f8nsted\u78b1\u5728\u63d0\u9ad8\u8d28\u5b50\u8026\u5408\u7535\u5b50\u8f6c\u79fb\u6b65\u9aa4\u4e2d\u8d77\u5230\u5173\u952e\u6027\u4f5c\u7528\u3002\u7efc\u5408\u5168\u6587\u6765\u770b\uff0c(bpy)Cu\/nitroxyl-\u50ac\u5316\u4f53\u7cfb\u4e2d\u7684\u785d\u9170\u57fa\u4f5c\u4e3a\u7535\u5b50-\u8d28\u5b50\u8f6c\u79fb\u7684\u4ecb\u8d28\u8d77\u5230\u4e86\u7c7b\u4f3c\u4e8e\u5176\u4ed6\u50ac\u5316\u53cd\u5e94\u4e2dBr\u00f8nsted\u78b1\u7684\u4f5c\u7528\u3002\u901a\u8fc7\u4e0e\u7b2c\u4e00\u884c\u8fc7\u6e21\u91d1\u5c5e\u5f62\u6210\u914d\u5408\u7269\uff0c\u7535\u5b50-\u8d28\u5b50\u8f6c\u79fb\u4ecb\u8d28\u5c06\u4e3a\u8d28\u5b50\u8026\u5408\u4e24\u7535\u5b50\u53cd\u5e94\u6d3b\u6027\u63d0\u4f9b\u6709\u6548\u7684\u57fa\u7840\u3002\u56e0\u6b64\uff0c\u4e0a\u8ff0\u7814\u7a76\u5bf9\u975e\u8d35\u91cd\u91d1\u5c5e\u7ec4\u6210\u7684\u7535\u50ac\u5316\u5242\u7684\u53d1\u5c55\u6709\u7740\u91cd\u8981\u7684\u5f71\u54cd\u3002<\/p>\n

\u6587\u732e\u94fe\u63a5\uff1aCooperative electrocatalytic alcohol oxidation with electron-proton-transfer mediators<\/a><\/p>\n","protected":false},"excerpt":{"rendered":"

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