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366) Our findings on the diethyl disulfide model system can be transferred to examples from the Protein Data Base.

--- ABSTRACT ---

PMID:24256142 DOI:10.1080/07391102.2013.851034

2015 Journal of biomolecular structure & dynamics

* How the disulfide conformation determines the disulfide/thiol redox potential.

- Protein disulfides can adopt a wide variety of conformations, each having different energies. Limited experimental data suggest that disulfides adopting a high energy have an enhanced likelihood for reduction, but the exact nature of this relation is not clear. Using a computational approach, we give insight on the conformational dependence of the redox behavior of the disulfide bond, which relates structure to reactivity. The relative energy of different conformations of the diethyl disulfide model system correlates with the disulfide/thiol redox potential E°. Insight in the calculated redox potentials is obtained via quantitative molecular orbital theory, and via the decomposition of E° into a vertical electron affinity and a subsequent reorganization term. We have identified the determinants of the disulfide conformational energies and characterized the barrier to rotation around the disulfide bond. Our findings on the diethyl disulfide model system can be transferred to examples from the Protein Data Base. In conclusion, strained disulfide conformations with a high conformational energy have a large tendency to be reduced. Upon reduction, unfavorable interactions are released. This explains why reorganization effects and not a higher tendency to accept electrons account for the high reduction potential of high-energy disulfides.

--- ABSTRACT END ---

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(1)88 suggest	(15)10 revealed	(29)3 for	(43)2 during
(2)27 indicate	(16)9 may	(30)3 highlighted	(44)2 give
(3)24 of	(17)8 show	(31)3 imply	(45)2 hold
(4)23 null	(18)7 showed	(32)3 indicated	(46)2 implicate
(5)23 from	(19)7 underscore	(33)3 regarding	(47)2 into
(6)17 are	(20)6 to	(34)3 that	(48)2 is
(7)17 support	(21)5 suggested	(35)3 the	(49)2 lend
(8)14 provide	(22)4 also	(36)3 will	(50)2 or
(9)12 have	(23)4 included	(37)2 add	(51)2 point
(10)12 highlight	(24)4 on	(38)2 at	(52)2 provided
(11)12 in	(25)4 reveal	(39)2 by	(53)2 related
(12)12 were	(26)4 we	(40)2 call	(54)2 should
(13)11 and	(27)3 could	(41)2 confirm	(55)2 suggesting
(14)10 demonstrate	(28)3 demonstrated	(42)2 contribute	(56)2 suggestive

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--- WordNet output for findings --- =>研究(調査)結果 Overview of noun findings The noun findings has 1 sense (no senses from tagged texts) 1. findings -- (a collection of tools and other articles used by an artisan to make jewelry or clothing or shoes) Overview of noun finding The noun finding has 3 senses (first 3 from tagged texts) 1. (16) determination, finding -- (the act of determining the properties of something, usually by research or calculation; "the determination of molecular structures") 2. (3) finding -- (the decision of a court on issues of fact or law) 3. (1) finding -- (something that is found; "the findings in the gastrointestinal tract indicate that he died several hours after dinner"; "an area rich in archaeological findings") --- WordNet end ---