Catalytic phenol hydroxylation with dioxygen: extension of the tyrosinase mechanism beyond the protein matrix.
Catalytic phenol hydroxylation with dioxygen: extension of the tyrosinase mechanism beyond the protein matrix.
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DOI：
10.1002/anie.201301249
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发表时间：
2013-05-10
影响因子：
16.6
通讯作者：
Herres-Pawlis, Sonja
中科院分区：
文献类型：
--
作者：
Hoffmann, Alexander;Citek, Cooper;Binder, Stephan;Goos, Arne;Ruebhausen, Michael;Troeppner, Oliver;Ivanovic-Burmazovic, Ivana;Wasinger, Erik C.;Stack, T. Daniel P.;Herres-Pawlis, Sonja
生物无机化学的顶峰是能够利用从金属酶中收集到的见解来设计能够在自然系统之外影响催化反应性的小型类似物。[1，2]活性位点的结构模拟是将合成催化剂插入酶机制的尝试。这种机制的演变选择压力的效率和遍历充满活力的路径，障碍和威尔斯既不太高，也不太深的能量催化周转的一个关键因素。[3]金属酶优于小金属络合物的一个优点是在蛋白质基质中金属中心的位点隔离以及随之而来的减弱破坏性衰变过程-反应槽的能力。这种保护提供了进入允许穿过屏障和威尔斯的热状态的途径。合成配合物也必须避免任何有害的反应，通常需要故意加入保护性的上层结构。[4，5]这些限制使得在具有天然底物的合成复合物中再现酶催化反应性成为一个重大挑战，正如缺乏良好的实例所证明的那样，将催化机制从活性位点转化为合成系统的智力投资是合理的，通过比较自然界与分子氧的灵活性来执行催化单加氧酶型化学[6-9]。以及合成化学家对外来试剂的依赖，
A pinnacle of bio-inorganic chemistry is the ability to leverage insights gleaned from metalloenzymes toward the design of small analogues capable of effecting catalytic reactivity outside the context of the natural system.[1, 2] Structural mimicry of active sites is an attempt to insert a synthetic catalyst into an enzymatic mechanism. Such a mechanism evolves by selection pressures for efficiency and traverses an energetic path, with barriers and wells neither too high nor too deep in energy—a critical factor of catalytic turnover.[3] An advantage of metalloenzymes over small metal complexes is the site-isolation of the metal center in the protein matrix and the attendant ability to attenuate destructive decay processes—reaction sinks. This protection provides access to thermal regimes that allow barriers and wells to be traversed. Synthetic complexes too must avoid any deleterious reactions, often necessitating the deliberate incorporation of protective superstructures.[4, 5] Such limitations make reproducing enzymatic catalytic reactivity in a synthetic complex with native substrates a significant challenge, as evidenced by the dearth of good examples, despite decades of effort.The intellectual investment of translating a catalytic mechanism from an active site to a synthetic system is justified by a comparison of Nature s dexterity with dioxygen to perform catalytic monooxygenase-type chemistry [6–9] and the dependence of synthetic chemists on exotic reagents for
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影响因子：
15
作者：
Herres-Pawlis, Sonia;Verma, Pratilk;Stack, T. Daniel P.
通讯作者：
Stack, T. Daniel P.
DOI：
10.1039/c39910001611
发表时间：
1991-11-15
影响因子：
--
作者：
CASELLA, L;GULLOTTI, M;DIGENNARO, P
通讯作者：
DIGENNARO, P
影响因子：
15
作者：
Kodera, M;Katayama, K;Suzuki, M
通讯作者：
Suzuki, M
影响因子：
15
作者：
Mirica, LM;Vance, M;Stack, TDP
通讯作者：
Stack, TDP
影响因子：
15
作者：
Palavicini, S;Granata, A;Casella, L
通讯作者：
Casella, L