{"id":37229,"date":"2021-03-01T08:00:29","date_gmt":"2021-03-01T00:00:29","guid":{"rendered":"\/\/www.gsbet888.com\/?p=37229"},"modified":"2021-03-03T09:49:06","modified_gmt":"2021-03-03T01:49:06","slug":"%e5%8f%8d%e5%ba%94%e8%bf%87%e7%a8%8b%e5%8a%a8%e5%8a%9b%e5%ad%a6%e5%88%86%e6%9e%90%ef%bc%88reaction-progress-kinetic-analysis-%ef%bc%89%ef%bc%88%e4%b8%80%ef%bc%89","status":"publish","type":"post","link":"\/\/www.gsbet888.com\/%e5%8c%96%e5%ad%a6%e6%9d%82%e8%ae%b0\/2021\/03\/%e5%8f%8d%e5%ba%94%e8%bf%87%e7%a8%8b%e5%8a%a8%e5%8a%9b%e5%ad%a6%e5%88%86%e6%9e%90%ef%bc%88reaction-progress-kinetic-analysis-%ef%bc%89%ef%bc%88%e4%b8%80%ef%bc%89.html","title":{"rendered":"\u53cd\u5e94\u8fc7\u7a0b\u52a8\u529b\u5b66\u5206\u6790\uff08Reaction Progress Kinetic Analysis\u00a0\uff09\uff08\u4e00\uff09"},"content":{"rendered":"

\u672c\u6587\u4f5c\u8005<\/b><\/strong>:<\/b><\/strong>\u77f3\u6cb9\u919a<\/b><\/strong><\/p>\n

\u5bfc\u8bfb<\/h4>\n

\u5728\u5316\u5b66\u9886\u57df\u4e2d\uff0c\u53cd\u5e94\u8fc7\u7a0b\u52a8\u529b\u5b66\u5206\u6790\uff08RPKA\uff09\u662f\u4f17\u591a\u52a8\u529b\u5b66\u6280\u672f\u4e2d\u7684\u4e00\u4e2a\u5b50\u96c6\uff0c\u7528\u4e8e\u786e\u5b9a\u5316\u5b66\u53cd\u5e94\u7684\u901f\u7387\u89c4\u5f8b\u4e0e\u9610\u660e\u5316\u5b66\u53cd\u5e94\u7684\u673a\u7406\u3002\u867d\u7136\u6307\u5bfc\u53cd\u5e94\u8fc7\u7a0b\u52a8\u529b\u5b66\u5206\u6790\u7684\u76f8\u5173\u6982\u5ff5\u5e76\u4e0d\u65b0\u9c9c\uff0c\u7136\u800c\uff0c\u8fd9\u4e00\u52a8\u529b\u5b66\u5206\u6790\u6280\u672f\u76f4\u81f3\u572820\u4e16\u7eaa90\u5e74\u4ee3\u672b\u624d\u7531D.<\/u>\u00a0G.<\/u>\u00a0Blackmond<\/u><\/a>\u6559\u6388\uff08\u76ee\u524d\u5728Scripps\u7814\u7a76\u6240\u5de5\u4f5c\uff09\u6b63\u5f0f\u63d0\u51fa\u3002\uff0c\u5e76\u5728\u6b64\u540e\u83b7\u5f97\u8d8a\u6765\u8d8a\u5e7f\u6cdb\u7684\u5e94\u75281<\/sup>\u3002\u4e0e\u66f4\u5e38\u89c1\u7684\u62df\u4e00\u7ea7\u52a8\u529b\u5b66\u5206\u6790\uff08Pseudo-first-order analysis\uff09\u4e0d\u540c\uff0c \u7531\u4e8e\u53cd\u5e94\u673a\u7406\u53ef\u80fd\u56e0\u6240\u6d89\u53ca\u7269\u79cd\u7684\u76f8\u5bf9\u4e0e\u7edd\u5bf9\u6d53\u5ea6\u800c\u53d1\u751f\u6539\u53d8\uff0c\u56e0\u6b64\uff0c\u8fd9\u79cd\u65b9\u6cd5\u83b7\u5f97\u7684\u7ed3\u679c\u6bd4\u4f20\u7edf\u65b9\u6cd5\u66f4\u80fd\u4ee3\u8868\u76f8\u5173\u53cd\u5e94\u7269\u5728\u901a\u5e38\u5b9e\u9a8c\u6761\u4ef6\u4e0b\u7684\u53cd\u5e94\u884c\u4e3a\u3002\u6b64\u5916\uff0c\u901a\u8fc7\u89c2\u5bdf\u53cd\u5e94\u968f\u65f6\u95f4\u7684\u53d8\u5316\u800c\u83b7\u5f97\u7684\u76f8\u5173\u4fe1\u606f\uff0c\u80fd\u591f\u8fdb\u4e00\u6b65\u53d1\u73b0\u53cd\u5e94\u8fc7\u7a0b\u4e2d\u4e2d\u5b58\u5728\u7684\u8bf1\u5bfc\u671f\uff08induction periods\uff09\u3001\u50ac\u5316\u5242\u5931\u6d3b(catalyst deactivation)\u6216\u673a\u7406\u7a81\u53d8 (changes in mechanism) \u7b49\u5f02\u5e38\u884c\u4e3a\u3002<\/p>\n

\"\"<\/a><\/p>\n

\u7b80\u4ecb<\/h4>\n

\u53cd\u5e94\u8fc7\u7a0b\u52a8\u529b\u5b66\u5206\u6790 (RPKA) \u53ef\u4ee5\u5728\u53cd\u5e94\u4f53\u7cfb\u4e2d\u5b58\u5728\u4e24\u79cd\u6216\u591a\u79cd\u53cd\u5e94\u7269\u7684\u6d53\u5ea6\u540c\u6b65\u6539\u53d8\u7684\u5408\u6210\u5b9e\u9a8c\u6761\u4ef6\u4e0b\uff0c\u901a\u8fc7\u51c6\u786e\u539f\u4f4d\u76d1\u6d4b\u6574\u4f53\u53cd\u5e94\u8fc7\u7a0b\uff0c\u4ece\u800c\u83b7\u5f97\u5927\u91cf\u6570\u636e\uff0c\u8fdb\u800c\u7b80\u5316\u52a8\u529b\u5b66\u7814\u7a76\uff0c\u4e8b\u5b9e\u4e0a\uff0c\u8fd9\u4e0e\u5b9e\u9645\u5408\u6210\u5b9e\u9a8c\u8fc7\u7a0b\u4e2d\uff0c\u53cd\u5e94\u53c2\u6570\u53d1\u751f\u6539\u53d8\u7684\u65b9\u5f0f\u4e00\u81f4\u3002RPKA \u65b9\u6cd5\u7684\u4e3b\u8981\u4f18\u52bf\u4fbf\u662f\u53ef\u4ee5\u5728\u65b0\u53cd\u5e94\u7684\u65e9\u671f\u7814\u7a76\u4e2d\uff0c\u5feb\u901f\u83b7\u53d6\u91cd\u8981\u7684\u52a8\u529b\u5b66\u4fe1\u606f\uff0c\u4ece\u800c\u6709\u5229\u4e8e\u6307\u5bfc\u540e\u7eed\u7684\u53cd\u5e94\u4f18\u5316\u4e0e\u628a\u63e1\u53cd\u5e94\u673a\u7406\u7814\u7a76\u7684\u65b9\u54111<\/sup>\u3002<\/p>\n

 <\/p>\n

\u76d1\u6d4b\u53cd\u5e94\u8fdb\u5ea6<\/b><\/strong><\/h4>\n

\u53cd\u5e94\u8fc7\u7a0b\u52a8\u529b\u5b66\u5206\u6790\u662f\u53d6\u51b3\u4e8e\u7cbe\u786e\u76d1\u6d4b\u53cd\u5e94\u8f6c\u5316\u7387\u968f\u65f6\u95f4\u53d8\u5316\u7684\u80fd\u529b\u3002\u8981\u5b9e\u73b0\u8fd9\u4e00\u76ee\u6807\uff0c\u5219\u9700\u8981\u4e00\u7cfb\u5217\u76d1\u6d4b\u6280\u672f\uff08\u6700\u4e3a\u5e38\u89c1\u7684\u76d1\u6d4b\u6280\u672f\u63a5\u4e0b\u6765\u5c0f\u7f16\u5c06\u4f5c\u8be6\u7ec6\u4ecb\u7ecd\uff09\u3002\u6709\u65f6\uff0c\u5316\u5b66\u5bb6\u8fd9\u4e9b\u6280\u672f\u5206\u4e3a\u5fae\u5206\u76d1\u6d4b\u6280\u672f\uff08\u76d1\u6d4b\u53cd\u5e94\u901f\u7387\u968f\u65f6\u95f4\u7684\u53d8\u5316\uff09\u6216\u79ef\u5206\u76d1\u6d4b\u6280\u672f\uff08\u76d1\u6d4b\u5e95\u7269\u4e0e\/\u6216\u4ea7\u7269\u542b\u91cf\u968f\u65f6\u95f4\u7684\u53d8\u5316\uff09\uff0c\u5e76\u4e14\uff0c\u901a\u8fc7\u7b80\u5355\u7684\u6570\u5b66\u53d8\u6362\uff08\u5fae\u5206\u6216\u79ef\u5206\uff09\uff0c\u80fd\u591f\u5c06\u901a\u8fc7\u4e24\u79cd\u65b9\u6cd5\u4e2d\u7684\u4efb\u610f\u4e00\u79cd\u6240\u83b7\u5f97\u7684\u6570\u636e\u8fdb\u884c\u76f8\u4e92\u8f6c\u6362\u3002\u4e8b\u5b9e\u4e0a\uff0c\u4e0d\u7ba1\u91c7\u7528\u54ea\u4e00\u79cd\u76d1\u6d4b\u6280\u672f\uff0c\u5747\u80fd\u591f\u901a\u8fc7\u9009\u62e9\u5176\u4ed6\u4e0d\u540c\u7684\u52a8\u529b\u5b66\u5206\u6790\u65b9\u6cd5\u8fdb\u4e00\u6b65\u8bc1\u5b9e\u4e0a\u8ff0\u76d1\u6d4b\u6280\u672f\u5728\u53cd\u5e94\u53c2\u6570\u5206\u6790\u4e2d\u7684\u6709\u6548\u60271<\/sup>\u3002<\/p>\n

1.\u53cd\u5e94\u8fdb\u7a0bN<\/b><\/strong>MR<\/b><\/strong>\u6280\u672f<\/b><\/strong><\/p>\n

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\"\"<\/a><\/p>\n

\u56fe1 \u53cd\u5e94\u8fdb\u7a0bNMR<\/p>\n

2.\u539f\u4f4d\u7ea2\u5916\u6280\u672f<\/strong><\/p>\n

\u539f\u4f4d\u7ea2\u5916\u5149\u8c31\u6cd5(in situ FT-IR)\u53ef\u7528\u4e8e\u76d1\u6d4b\u53cd\u5e94\u8fc7\u7a0b\uff0c\u524d\u63d0\u662f\u8bd5\u5242\u6216\u4ea7\u54c1\u5728\u7ea2\u5916\u5149\u8c31\u533a\u57df\u5b58\u5728\u7279\u5f81\u7684IR\u5438\u6536\u3002\u53cd\u5e94\u7269\u6d88\u8017\u901f\u7387\u6216\u4ea7\u7269\u751f\u6210\u901f\u7387\u53ef\u4ee5\u901a\u8fc7\u5438\u5149\u5ea6\u968f\u53cd\u5e94\u65f6\u95f4\u7684\u6539\u53d8\u800c\u83b7\u53d6\uff08\u5e94\u7528Beer\u5b9a\u5f8b\uff09\u3002\u5373\u4f7f\u53cd\u5e94\u7269\u4e0e\u4ea7\u7269\u7684\u5438\u6536\u5149\u8c31\u663e\u793a\u51fa\u4e00\u5b9a\u7a0b\u5ea6\u7684\u91cd\u53e0\uff0c\u53ea\u8981\u6240\u7814\u7a76\u7684IR\u5438\u6536\u5cf0\u7684\u7edd\u5bf9\u5438\u5149\u5ea6\u968f\u65f6\u95f4\u80fd\u591f\u53d1\u751f\u663e\u8457\u53d8\u5316\uff0c\u73b0\u4ee3\u4eea\u5668\u82b3\u9999\u8f6f\u4ef6\u901a\u5e38\u53ef\u4ee5\u51c6\u786e\u5730\u5bf9\u91cd\u53e0\u90e8\u5206\u7684\u76f8\u5bf9\u8d21\u732e\u8fdb\u884c\u53bb\u5377\u79ef(deconvolution)\u5206\u67902<\/sup>\u3002\u7531\u4e8e\u6536\u96c6\u7684\u539f\u59cb\u6570\u636e\u4e0e\u6d53\u5ea6\u4ee5\u53ca\u65f6\u95f4\u6210\u6b63\u6bd4\uff0c\u56e0\u6b64\uff0c\u539f\u4f4d\u7ea2\u5916\u5149\u8c31\u5c5e\u4e8e\u79ef\u5206\u76d1\u6d4b\u6280\u672f1<\/sup>\u3002\u6839\u636e\u4e0a\u8ff0\u6570\u636e\uff0c\u53ef\u4ee5\u901a\u8fc7\u7b80\u5355\u5730\u5bf9\u5b9e\u9a8c\u66f2\u7ebf\u8fdb\u884c\u591a\u9879\u5f0f\u79ef\u5206\u62df\u5408\u7684\u65b9\u5f0f\u83b7\u5f97\u539f\u6599\u6216\u4ea7\u7269\u6d53\u5ea6\u968f\u65f6\u95f4\u53d8\u5316\u7684\u4fe1\u606f\u3002\u968f\u7740\u539f\u4f4d\u7ea2\u5916\u5149\u8c31\u4eea\u76d1\u63a7\u53ef\u9760\u6027\u7684\u589e\u52a0\uff0c\u8fd1\u5e74\u6765\uff0cFT-IR\u7684\u5e94\u7528\u8d8a\u6765\u8d8a\u5e7f\u6cdb\u3002\u5177\u6709\u4ee3\u8868\u6027\u7684\u5b9e\u4f8b\u4e3b\u8981\u6d89\u53ca\u6c28\u57fa\u786b\u8132\u50ac\u5316\u7684\u975e\u5929\u7136\u6c28\u57fa\u9178\u7684\u4e0d\u5bf9\u79f0Strecker\u5408\u6210\u4e0eLewis\u78b1\u50ac\u5316\u7684\u5364\u5185\u916f\u5316\uff08halolactonization<\/a>\uff09\u4e0e\u73af\u919a\u5316\uff08cycloetherification<\/a>\uff09\u00a0\u7684\u673a\u7406\u7814\u7a764,5<\/sup>\u3002\uff08\u56fe2\uff09<\/p>\n

\"\"<\/a><\/p>\n

\u56fe2 \u539f\u4f4d\u7ea2\u5916\u5149\u8c31<\/p>\n

3.\u539f\u4f4d<\/b><\/strong>\u7d2b\u5916-\u53ef\u89c1\u5149\u8c31<\/b><\/strong><\/p>\n

\u4e0e\u539f\u4f4d\u7ea2\u5916\u5b9e\u9a8c\u7c7b\u4f3c\uff0c\u53ea\u8981\u8bd5\u5242\u6216\u4ea7\u7269\u5728\u7d2b\u5916-\u53ef\u89c1\u533a\u57df\u663e\u793a\u51fa\u7279\u5f81\u7684\u5438\u6536\u5cf0\uff0c\u5c31\u80fd\u591f\u9009\u7528\u539f\u4f4d\u7d2b\u5916-\u53ef\u89c1\u5438\u6536\u5149\u8c31\u6cd5\uff08in situ<\/i><\/em>\u00a0UV-visible<\/u><\/a>\u00a0absorbance spectroscopy<\/u><\/a>\u00a0\uff09\u76d1\u6d4b\u53cd\u5e94\u8fdb\u7a0b\u3002\u7531\u4e8e\u53cd\u5e94\u7269\u6d88\u8017\u901f\u7387\u6216\u4ea7\u7269\u751f\u6210\u901f\u7387\u53ef\u6839\u636e\u5438\u5149\u5ea6\u968f\u65f6\u95f4\u7684\u6539\u53d8\u800c\u83b7\u53d6\uff08\u5e94\u7528Beer\u5b9a\u5f8b\uff09\uff0c\u56e0\u6b64\uff0c\u539f\u4f4d\u7d2b\u5916-\u53ef\u89c1\u5149\u8c31\u540c\u6837\u5c5e\u4e8e\u79ef\u5206\u76d1\u6d4b\u6280\u672f\u3002\u6839\u636e\u6240\u9009\u62e9\u7684\u5149\u8c31\u5438\u6536\u533a\u57df\uff0c\u539f\u4f4d\u7d2b\u5916-\u53ef\u89c1\u5149\u8c31\u6280\u672f\u5728\u65e0\u673a\u6216\u91d1\u5c5e\u6709\u673a\u53cd\u5e94\u4f53\u7cfb\u4e2d\u7684\u5e94\u7528\u8981\u6bd4\u5728\u7eaf\u6709\u673a\u53cd\u5e94\u4e2d\u7684\u66f4\u4e3a\u5e7f\u6cdb\uff0c\u5178\u578b\u5b9e\u4f8b\u4e3b\u8981\u6d89\u53ca\u9490\u8bd5\u5242\u4fc3\u8fdb\u7684\u00a0Barbier \u53cd\u5e946<\/sup>\u3002\uff08\u56fe3\uff09<\/p>\n

\"\"<\/a><\/p>\n

\u56fe3 \u539f\u4f4d\u7d2b\u5916-\u53ef\u89c1\u5149\u8c31<\/p>\n

4.\u53cd\u5e94\u91cf\u70ed\u6cd5<\/b><\/strong><\/p>\n

\u53cd\u5e94\u91cf\u70ed\u6cd5\uff08Calorimetry<\/a>\uff09\u540c\u6837\u53ef\u4ee5\u7528\u4e8e\u76d1\u6d4b\u53cd\u5e94\u8fc7\u7a0b\uff0c\u56e0\u4e3a\u8be5\u4eea\u5668\u68c0\u6d4b\u51fa\u7684\u53cd\u5e94\u77ac\u65f6\u70ed\u901a\u91cf\uff08instantaneous\u00a0heat flux<\/a>\uff09\u4e0e\u53cd\u5e94\u8fc7\u7a0b\u7684\u7113\u53d8\u5316\u76f4\u63a5\u76f8\u5173\u3002\u7531\u4e8e\u6240\u6536\u96c6\u7684\u539f\u59cb\u6570\u636e\u4e0e\u901f\u7387\u4e0e\u65f6\u95f4\u6210\u6b63\u6bd4\uff0c\u56e0\u6b64\uff0c\u53cd\u5e94\u91cf\u70ed\u6cd5\u5c5e\u4e8e\u5fae\u5206\u76d1\u6d4b\u6280\u672f7,8<\/sup>\u3002\u6839\u636e\u6240\u6536\u96c6\u7684\u539f\u59cb\u6570\u636e\uff0c\u53ef\u4ee5\u5bf9\u5b9e\u9a8c\u66f2\u7ebf\u7684\u591a\u9879\u5f0f\u79ef\u5206\u8fdb\u884c\u62df\u5408\uff0c\u8fdb\u800c\u83b7\u5f97\u8d77\u59cb\u539f\u6599\u6216\u4ea7\u7269\u6d53\u5ea6\u968f\u65f6\u95f4\u53d8\u5316\u7684\u4fe1\u606f9<\/sup>\u3002\u867d\u7136\u53cd\u5e94\u91cf\u70ed\u6cd5\u76f8\u6bd4\u5176\u4ed6\u65b9\u6cd5\u5e94\u7528\u8f83\u5c11\uff0c\u7136\u800c\uff0c\u8be5\u65b9\u6cd5\u5374\u662f\u50ac\u5316\u5242\u7b5b\u9009\u7684\u6709\u6548\u5de5\u5177\u4e4b\u4e0010<\/sup>\u3002\u6b64\u5916\uff0c\u53cd\u5e94\u91cf\u70ed\u6cd5\u540c\u6837\u80fd\u591f\u5e94\u7528\u4e8e\u5355\u4e2a\u53cd\u5e94\u7684\u673a\u7406\u7814\u7a76\uff0c\u5178\u578b\u5b9e\u4f8b\u6d89\u53ca\u812f\u6c28\u9178\u50ac\u5316\u7684\u919b\u7c7b\u5316\u5408\u7269\u7684\u03b1-\u80fa\u5316\u4ee5\u53ca\u94af\u50ac\u5316\u7684Buchwald-Hartwig\u80fa\u5316\u53cd\u5e943,11<\/sup>\u3002\uff08\u56fe4 \uff09<\/p>\n

\"\"<\/a><\/p>\n

\u56fe4 \u91cf\u70ed\u6280\u672f<\/p>\n

5.\u5176\u4ed6\u6280\u672f<\/b><\/strong><\/p>\n

\u867d\u7136GC\u3001HPLC\u4ee5\u53caMS\u6cd5\u90fd\u662f\u5206\u8fa8\u4e00\u7cfb\u5217\u4e0d\u540c\u5316\u5408\u7269\u5f62\u6210\u7684\u6df7\u5408\u7269\uff08\u6709\u65f6\u751a\u81f3\u662f\u5bf9\u6620\u4f53\u6df7\u5408\u7269\uff09\u7684\u4f18\u826f\u6280\u672f\uff0c\u7136\u800c\uff0c\u8fd9\u7c7b\u6d4b\u91cf\u7684\u65f6\u95f4\u5206\u8fa8\u7387\u4e0d\u5982\u4e0a\u8ff0\u76d1\u6d4b\u6280\u672f\u66f4\u52a0\u7cbe\u786e\u3002\u5c3d\u7ba1\u5982\u6b64\uff0c\u8fd9\u7c7b\u76d1\u6d4b\u6280\u672f\u4ecd\u7136\u53ef\u4ee5\u7528\u4e8e\u53cd\u5e94\u76d1\u63a7\uff0c\u4f8b\u5982\u5728Heck\u53cd\u5e94\u7684\u7814\u7a76\u4e2d12<\/sup>\uff0c\u53cd\u5e94\u7684\u975e\u5747\u76f8\u7279\u6027\u59a8\u788d\u4e86\u4e0a\u8ff0\u76d1\u6d4b\u6280\u672f\u7684\u5e94\u7528\uff0c\u6b64\u5916\uff0c\u53cd\u5e94\u91cf\u70ed\u6cd5\u540c\u6837\u80fd\u591f\u5e94\u7528\u4e8e\u6709\u673a\u50ac\u5316\u5242\u7684SOMO\u6d3b\u5316\u7684\u7814\u7a7613<\/sup>\u3002\u5c3d\u7ba1\u5b58\u5728\u4e00\u4e9b\u4e0d\u8db3\u4e4b\u5904\uff0c\u7136\u800c\uff0c\u53cd\u5e94\u91cf\u70ed\u6280\u672f\u4ecd\u7136\u80fd\u591f\u7528\u4f5c\u4e4b\u524d\u76d1\u63a7\u65b9\u6cd5\u4e00\u79cd\u6709\u529b\u7684\u6821\u51c6\u65b9\u6cd5\u3002<\/p>\n

\u7efc\u4e0a\uff0cChem-Station\u5c0f\u7f16\u4ecb\u7ecd\u4e86\u4e00\u7cfb\u5217\u65b0\u7684\u53cd\u5e94\u76d1\u63a7\u6280\u672f\u5728\u53cd\u5e94\u8fc7\u7a0b\u52a8\u529b\u5b66\u5206\u6790\u65b9\u9762\u7684\u5e94\u7528\uff0c\u4e0a\u8ff0\u76d1\u63a7\u6280\u672f\u4e3aRPKA\u5206\u6790\u63d0\u4f9b\u4e86\u5f3a\u5927\u6570\u636e\u652f\u6491\uff0c\u901a\u8fc7\u5bf9\u6240\u5f97\u6570\u636e\u7684\u5206\u6790\uff0c\u6709\u52a9\u4e8e\u5bf9\u524d\u671f\u53cd\u5e94\u7684\u4f18\u5316\u4ee5\u53ca\u5bf9\u53cd\u5e94\u673a\u7406\u7684\u7814\u7a76\u3002\u4e0b\u671f\uff0cChem-Station\u5c0f\u7f16\u5c06\u5bf9\u53cd\u5e94\u8fc7\u7a0b\u52a8\u529b\u5b66\u5206\u6790\u7684\u76f8\u5173\u539f\u7406\u8fdb\u884c\u8be6\u7ec6\u63cf\u8ff0\u3002<\/p>\n

\u53c2\u8003\u6587\u732e<\/b><\/strong><\/h4>\n
    \n
  1. Blackmond, D. G., Angew. Chem. Int. Ed. <\/i><\/em>2005,<\/b><\/strong>44<\/i><\/em>(28), 4302-4320, doi:10.1002\/anie.200462544.<\/u><\/a><\/li>\n
  2. Blackmond, D. G.; Ropic, M.; Stefinovic, M., Org. Process Res. Dev. <\/i><\/em>2006,<\/b><\/strong>10<\/i><\/em>(3), 457-463, doi:10.1021\/op060033k.<\/u><\/a><\/li>\n
  3. Shekhar, S.; Ryberg, P.; Hartwig, J. F.; Mathew, J. S.; Blackmond, D. G.; Strieter, E. R.; Buchwald, S. L., J. Am. Chem. Soc. <\/i><\/em>2006,<\/b><\/strong>128<\/i><\/em>(11), 3584-3591, doi:10.1021\/ja045533c.<\/u><\/a><\/li>\n
  4. Zuend, S. J.; Jacobsen, E. N., J. Am. Chem. Soc. <\/i><\/em>2009,<\/b><\/strong>131<\/i><\/em>(42), 15358-15374, doi:10.1021\/ja9058958<\/u><\/a>.<\/li>\n
  5. Denmark, S. E.; Burk, M. T.,PNAS<\/i><\/em>.2010,<\/b><\/strong>107<\/i><\/em>(48), 20655-20660, doi:10.1073\/pnas.1005296107 <\/u><\/a><\/li>\n
  6. Choquette, K. A.; Sadasivam, D. V.; Flowers, R. A., J. Am. Chem. Soc. <\/i><\/em>2011,<\/b><\/strong>133<\/i><\/em>(27), 10655-10661, doi:10.1021\/ja204287n.<\/u><\/a><\/li>\n
  7. Mathew, J. S.; Klussmann, M.; Iwamura, H.; Valera, F.; Futran, A.; Emanuelsson, E. A. C.; Blackmond, D. G., J. Org. Chem. <\/i><\/em>2006,<\/b><\/strong>71<\/i><\/em>(13), 4711-4722, doi:10.1021\/jo052409i.<\/u><\/a><\/li>\n
  8. Steel, C.; Naqvi, K. R., J<\/i><\/em>.<\/i><\/em>Phys<\/i><\/em>.<\/i><\/em>Chem<\/i><\/em>.<\/i><\/em>\u00a0<\/i><\/em>1991,<\/b><\/strong>95<\/i><\/em>\u00a0(26), 10713-10718, doi:10.1021\/j100179a037.<\/u><\/a><\/li>\n
  9. Blackmond, D. G.; Rosner, T.; Pfaltz, A., Org. Process Res. Dev. <\/i><\/em>1999,<\/b><\/strong>3<\/i><\/em>(4), 275-280, doi:10.1021\/op990024u.<\/u><\/a><\/li>\n
  10. Hein, J. E.; Armstrong, A.; Blackmond, D. G., Org. Lett. <\/i><\/em>2011,<\/b><\/strong>13<\/i><\/em>(16), 4300-4303, doi:10.1021\/ol201639z.<\/u><\/a><\/li>\n
  11. Singh, U. K.; Strieter, E. R.; Blackmond, D. G.; Buchwald, S. L., J. Am. Chem. Soc. <\/i><\/em>2002,<\/b><\/strong>124<\/i><\/em>(47), 14104-14114, doi:10.1021\/ja026885r.<\/u><\/a><\/li>\n
  12. Herrmann, W. A.; Brossmer, C.; Reisinger, C.-P.; Riermeier, T. H.; \u00d6fele, K.; Beller, M., Chem. Eur. J. <\/i><\/em>1997,<\/b><\/strong>3<\/i><\/em>(8), 1357-1364, doi:10.1002\/chem.19970030823.<\/u><\/a><\/li>\n
  13. Devery Iii, J. J.; Conrad, J. C.; MacMillan, D. W. C.; Flowers Ii, R. A., Angew. Chem. Int. Ed. <\/i><\/em>2010,<\/b><\/strong>49<\/i><\/em>(35), 6106-6110, doi:10.1002\/anie.201001673<\/u><\/a>.<\/li>\n<\/ol>\n","protected":false},"excerpt":{"rendered":"\u672c\u6587\u4f5c\u8005:\u77f3\u6cb9\u919a \u5bfc\u8bfb \u5728\u5316\u5b66\u9886\u57df\u4e2d\uff0c\u53cd\u5e94\u8fc7\u7a0b\u52a8\u529b\u5b66\u5206\u6790\uff08RPKA\uff09\u662f\u4f17\u591a\u52a8\u529b\u5b66\u6280\u672f\u4e2d\u7684\u4e00\u4e2a\u5b50\u96c6\uff0c\u7528\u4e8e\u786e\u5b9a\u5316\u5b66\u53cd\u5e94\u7684\u901f\u7387\u89c4\u5f8b\u4e0e\u9610\u660e\u5316\u5b66\u53cd\u5e94\u7684\u673a\u7406\u3002\u867d\u7136\u6307\u5bfc\u53cd\u5e94\u8fc7\u7a0b\u52a8\u529b\u5b66\u5206\u6790\u7684\u76f8\u5173\u6982\u5ff5\u5e76\u4e0d\u65b0\u9c9c\uff0c\u7136\u800c\uff0c\u8fd9\u4e00\u52a8\u529b\u5b66\u5206\u6790\u6280\u672f\u76f4\u81f3\u572820\u4e16\u7eaa90\u5e74\u4ee3\u672b\u624d\u7531D.\u00a0G.\u00a0Blackmond\u6559\u6388\uff08\u76ee\u524d\u5728Scripps\u7814\u7a76\u6240\u5de5\u4f5c\uff09\u6b63\u5f0f\u63d0\u51fa\u3002\uff0c\u5e76\u5728\u6b64\u540e\u83b7\u5f97\u8d8a\u6765\u8d8a\u5e7f\u6cdb\u7684\u5e94\u75281\u3002\u4e0e\u66f4\u5e38\u89c1\u7684\u62df\u4e00\u7ea7\u52a8\u529b\u5b66\u5206\u6790\uff08Pseudo-first-order analysis\uff09\u4e0d\u540c\uff0c \u7531\u4e8e\u53cd\u5e94\u673a\u7406\u53ef\u80fd\u56e0\u6240\u6d89\u53ca\u7269\u79cd\u7684\u76f8\u5bf9\u4e0e\u7edd\u5bf9\u6d53\u5ea6\u800c\u53d1\u751f\u6539\u53d8\uff0c\u56e0\u6b64\uff0c\u8fd9\u79cd\u65b9\u6cd5\u83b7\u5f97\u7684\u7ed3\u679c\u6bd4\u4f20\u7edf\u65b9\u6cd5\u66f4\u80fd\u4ee3\u8868\u76f8\u5173\u53cd\u5e94\u7269\u5728\u901a\u5e38\u5b9e\u9a8c\u6761\u4ef6\u4e0b\u7684\u53cd\u5e94\u884c\u4e3a\u3002\u6b64\u5916\uff0c\u901a\u8fc7\u89c2\u5bdf\u53cd\u5e94\u968f\u65f6\u95f4\u7684\u53d8\u5316\u800c\u83b7\u5f97\u7684\u76f8\u5173\u4fe1\u606f\uff0c\u80fd\u591f\u8fdb\u4e00\u6b65\u53d1\u73b0\u53cd\u5e94\u8fc7\u7a0b\u4e2d\u4e2d\u5b58\u5728\u7684\u8bf1\u5bfc\u671f\uff08induction periods\uff09\u3001\u50ac\u5316\u5242\u5931\u6d3b(catalyst deactivation)\u6216\u673a\u7406\u7a81\u53d8 (changes in mechanism) \u7b49\u5f02\u5e38\u884c\u4e3a\u3002 \u7b80\u4ecb \u53cd\u5e94\u8fc7\u7a0b\u52a8\u529b\u5b66\u5206\u6790 (RPKA) \u53ef\u4ee5\u5728\u53cd\u5e94\u4f53\u7cfb\u4e2d\u5b58\u5728\u4e24\u79cd\u6216\u591a\u79cd\u53cd\u5e94\u7269\u7684\u6d53\u5ea6\u540c\u6b65\u6539\u53d8\u7684\u5408\u6210\u5b9e\u9a8c\u6761\u4ef6\u4e0b\uff0c\u901a\u8fc7\u51c6\u786e\u539f\u4f4d\u76d1\u6d4b\u6574\u4f53\u53cd\u5e94\u8fc7\u7a0b\uff0c\u4ece\u800c\u83b7\u5f97\u5927\u91cf\u6570\u636e\uff0c\u8fdb\u800c\u7b80\u5316\u52a8\u529b\u5b66\u7814\u7a76\uff0c\u4e8b\u5b9e\u4e0a\uff0c\u8fd9\u4e0e\u5b9e\u9645\u5408\u6210\u5b9e\u9a8c\u8fc7\u7a0b\u4e2d\uff0c\u53cd\u5e94\u53c2\u6570\u53d1\u751f\u6539\u53d8\u7684\u65b9\u5f0f\u4e00\u81f4\u3002RPKA \u65b9\u6cd5\u7684\u4e3b\u8981\u4f18\u52bf\u4fbf\u662f\u53ef\u4ee5\u5728\u65b0\u53cd\u5e94\u7684\u65e9\u671f\u7814\u7a76\u4e2d\uff0c\u5feb\u901f\u83b7\u53d6\u91cd\u8981\u7684\u52a8\u529b\u5b66\u4fe1\u606f\uff0c\u4ece\u800c\u6709\u5229\u4e8e\u6307\u5bfc\u540e\u7eed\u7684\u53cd\u5e94\u4f18\u5316\u4e0e\u628a\u63e1\u53cd\u5e94\u673a\u7406\u7814\u7a76\u7684\u65b9\u54111\u3002   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\u56fe2 \u539f\u4f4d\u7ea2\u5916\u5149\u8c31 3.\u539f\u4f4d\u7d2b\u5916-\u53ef\u89c1\u5149\u8c31 \u4e0e\u539f\u4f4d\u7ea2\u5916\u5b9e\u9a8c\u7c7b\u4f3c\uff0c\u53ea\u8981\u8bd5\u5242\u6216\u4ea7\u7269\u5728\u7d2b\u5916-\u53ef\u89c1\u533a\u57df\u663e\u793a\u51fa\u7279\u5f81\u7684\u5438\u6536\u5cf0\uff0c\u5c31\u80fd\u591f\u9009\u7528\u539f\u4f4d\u7d2b\u5916-\u53ef\u89c1\u5438\u6536\u5149\u8c31\u6cd5\uff08in situ\u00a0UV-visible\u00a0absorbance spectroscopy\u00a0\uff09\u76d1\u6d4b\u53cd\u5e94\u8fdb\u7a0b\u3002\u7531\u4e8e\u53cd\u5e94\u7269\u6d88\u8017\u901f\u7387\u6216\u4ea7\u7269\u751f\u6210\u901f\u7387\u53ef\u6839\u636e\u5438\u5149\u5ea6\u968f\u65f6\u95f4\u7684\u6539\u53d8\u800c\u83b7\u53d6\uff08\u5e94\u7528Beer\u5b9a\u5f8b\uff09\uff0c\u56e0\u6b64\uff0c\u539f\u4f4d\u7d2b\u5916-\u53ef\u89c1\u5149\u8c31\u540c\u6837\u5c5e\u4e8e\u79ef\u5206\u76d1\u6d4b\u6280\u672f\u3002\u6839\u636e\u6240\u9009\u62e9\u7684\u5149\u8c31\u5438\u6536\u533a\u57df\uff0c\u539f\u4f4d\u7d2b\u5916-\u53ef\u89c1\u5149\u8c31\u6280\u672f\u5728\u65e0\u673a\u6216\u91d1\u5c5e\u6709\u673a\u53cd\u5e94\u4f53\u7cfb\u4e2d\u7684\u5e94\u7528\u8981\u6bd4\u5728\u7eaf\u6709\u673a\u53cd\u5e94\u4e2d\u7684\u66f4\u4e3a\u5e7f\u6cdb\uff0c\u5178\u578b\u5b9e\u4f8b\u4e3b\u8981\u6d89\u53ca\u9490\u8bd5\u5242\u4fc3\u8fdb\u7684\u00a0Barbier \u53cd\u5e946\u3002\uff08\u56fe3\uff09 \u56fe3 \u539f\u4f4d\u7d2b\u5916-\u53ef\u89c1\u5149\u8c31 4.\u53cd\u5e94\u91cf\u70ed\u6cd5 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G., Angew. Chem. Int. Ed. 2005,44(28), 4302-4320, doi:10.1002\/anie.200462544. Blackmond, D. G.; Ropic, M.; Stefinovic, M., Org. Process Res. Dev. 2006,10(3), 457-463, doi:10.1021\/op060033k. Shekhar, S.; Ryberg, P.; Hartwig, J. F.; Mathew, J. S.; Blackmond, D. G.; Strieter, E. R.; Buchwald, S. L., J. Am. Chem. Soc. 2006,128(11), 3584-3591, doi:10.1021\/ja045533c. Zuend, S. J.; Jacobsen, E. N., J. Am. Chem. Soc. 2009,131(42), 15358-15374, doi:10.1021\/ja9058958. 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