ライフサイエンスコーパス: outer sphere

1 ositive charges of the magnesium ion and its outer sphere.

2 nificantly greater than those calculated for outer sphere activation barriers, with deviations betwee

3 Outer-sphere adsorption is found to dominate over inner-

4 hematite surfaces and additionally revealed outer-sphere adsorption modes not seen in the EXAFS.

5 species is shown to display both inner- and outer-sphere adsorption to the flat {1014} and the stepp

6 mary amine catalyst with a methyl-terminated outer-sphere also produces alcohol, albeit at a rate tha

7 The outer-sphere analysis indicates an Fe-Zn separation of a

8 Both outer-sphere and inner-sphere pathways for the reduction

9 ow comparable electrochemical activities for outer-sphere and inner-sphere redox reactions.

10 Electron transfer is outer-sphere and uncoupled from proton transfer.

11 i-acidity of the ligand central ring and the outer-sphere anion.

12 tic reactions: inner-sphere syn-addition and outer-sphere anti-addition (Friedel-Crafts-type mechanis

13 s involved in the formation of the precursor outer-sphere associate appear to be important overall ra

14 in which the stereodetermining step involves outer-sphere bromine abstraction from a [(bisphosphine)R

15 Rather, the lipid phosphate groups provided outer-sphere calcium coordination through intervening wa

16 yer; we propose counterions to be inner- and outer-sphere calcium ions, with a population of inner-sp

17 luminate general principles of non-selective outer-sphere cation binding in RNA structure and functio

18 Probe molecules were used to assess outer-sphere charge transfer (Fe(CN)6(4-)) and organic c

19 An outer-sphere complex and a monodentate inner-sphere comp

20 ed through transition-state stabilization by outer-sphere complex formation with substrate.

21 At both I = 0.02 and 0.1 M, the outer-sphere complex loading reaches maximum at pH appro

22 dicated that Cr(VI) was loosely sorbed as an outer-sphere complex on Mn(IV)O(2), while Cr(III) was ti

23 t-energy structure calculated to be an As-up outer-sphere complex.

24 s in the first coordination shell similar to outer-sphere complexation and a second coordination with

25 tion, and the competition between inner- and outer-sphere complexation.

26 (SCM), we have shown that sulfate forms both outer-sphere complexes and bidentate-binuclear inner-sph

27 xes, whereas Cr(VI) likely adsorbs mainly as outer-sphere complexes and Cd(II) as a mixture of inner-

28 In contrast, the formation of outer-sphere complexes and subsequent conformation chang

29 significant increase in relative fraction of outer-sphere complexes for all three oxyanions with incr

30 te on schwertmannite, whereas selenate forms outer-sphere complexes in the aluminum octahedral interl

31 n behavior of anions forming both inner- and outer-sphere complexes on mineral surfaces.

32 e(II) was associated with more weakly bound, outer-sphere complexes on silica-ferrihydrite compared t

33 Air-drying drastically converts the outer-sphere complexes to the inner-sphere complexes.

34 (RH) on the concentrations of Li+ inner- and outer-sphere complexes was then explored, the concentrat

35 Results suggest also that metal involved in outer-sphere complexes would display isotopic exchange b

36 plexes and Cd(II) as a mixture of inner- and outer-sphere complexes.

37 An outer-sphere concerted hydrogen transfer was found to be

38 In contrast, in outer sphere contact ion-pairs 7, 8, 9, and 10, the anio

39 ns, consistent with its ability to make only outer sphere contacts.

40 ozyme is a unique model to study the role of outer-sphere coordinated cations in folding of a catalyt

41 Simulations reveal that outer-sphere coordinated Mg(2+) ions fluctuate on the sa

42 inuum of diffuse ions, we observe a layer of outer-sphere coordinated Mg(2+) that is transiently boun

43 of 41 types of inner-sphere and 95 types of outer-sphere coordinating patterns.

44 ore important to consider the possibility of outer-sphere coordination of catalytic metal ions in rib

45 the cleavage activity of RNase P, suggesting outer-sphere coordination of O6 on G379 to a metal ion.

46 ermic changes, consistent with predominantly outer-sphere coordination.

47 in an acyl-transferase ribozyme acts through outer-sphere coordination.

48 mode, type of ancillary ligand, solvent, and outer-sphere counteranions.

49 yano-terminated catalyst, demonstrating that outer-sphere dielectric constant affects catalyst activi

50 ive theoretical treatment of the kinetics of outer sphere electrochemical reactions.

51 faradaic current for either inner-sphere or outer-sphere electrochemical reactions.

52 ster to the SAM, which otherwise has a large outer sphere electron transfer barrier.

53 ld facilitate O O bond cleavage of H2O2, but outer sphere electron transfer from a second H2O2 in ano

54 de to Cu(II) in one portion of the cycle and outer sphere electron transfer from Cu(I) to superoxide

55 and quantum-chemical calculations suggest an outer sphere electron transfer from the COF to the co-ca

56 n 4-fluoroiodobenzene and benzene through an outer sphere electron transfer pathway, which expands th

57 As a radical clock experiment ruled out outer sphere electron transfer, an inner sphere electron

58 are consistent with the previously proposed outer sphere electron-transfer mechanism for N-methylqui

59 agents do not facilitate defect formation by outer-sphere electron and/or proton transfers, and thus

60 The self-exchange rate constant for outer-sphere electron transfer between [Co(H(2)bim)(3)](

61 pends on pH; (3) a significant inhibition to outer-sphere electron transfer for the Ru(IV)=O2+/Ru(III

62 ascorbate monoanion, which does not react by outer-sphere electron transfer in solution, and complex

63 none mechanism operates, then an alternative outer-sphere electron transfer must also exist to accoun

64 ow Mg2+ concentrations that is attributed to outer-sphere electron transfer on the basis of the known

65 rations argue against oxidative addition and outer-sphere electron transfer pathways for perfluoroare

66 The second electron transfer, also an outer-sphere electron transfer process, occurs along a t

67 particles do not become deactivated for the outer-sphere electron transfer reaction after attachment

68 ffusional encounter of O(2) with protein, an outer-sphere electron transfer to O(2), and proton trans

69 For strong reducing agents the initial outer-sphere electron transfer, alone or possibly couple

70 n various pieces of evidence against initial outer-sphere electron transfer, proton transfer, or subs

71 t with simple rate limitation by an initial, outer-sphere electron transfer, suggesting that the line

72 In terms of the Marcus theory of outer-sphere electron transfer, we show here that D283,

73 te, making the red site unfavorable for fast outer-sphere electron transfer, while providing an excha

74 tionship (FER) based on the Marcus theory of outer-sphere electron transfer.

75 ctron oxidant capable of effectively driving outer-sphere electron-transfer reactions with reagents h

76 librium acid association to 1 is followed by outer-sphere electron-transfer reduction of 2 by decamet

77 ion sphere of ruthenium via an unprecedented outer-sphere electrophilic fluorination mechanism.

78 imary amine catalysts, consisting of a polar outer-sphere environment derived from cyano-terminated c

79 inocatalysis are critically dependent on the outer-sphere environment.

80 ized state pK of Mn(3+)SOD corresponds to an outer-sphere event whereas that of Fe(3+)SOD corresponds

81 Outer-sphere EXAFS analysis indicates an Fe-Zn separatio

82 experimental evidence for the importance of outer-sphere H-bonding interactions for the exceptional

83 We studied extremely fast kinetics of an outer-sphere heterogeneous electron transfer (ET) reacti

84 For an outer-sphere heterogeneous electron transfer, Ox + e = R

85 ylate ligand, which in turn is influenced by outer-sphere hydrogen bonding.

86 echanistic criterion is proposed for various outer-sphere/inner-sphere ET processes based on the rela

87 roposed to be first activated by CuO through outer-sphere interaction, the rate-limiting step, follow

88 erize ligation to nucleotide base nitrogens, outer-sphere interactions with phosphate groups, distanc

89 These results highlight the role played by outer-sphere interactions, and the structural constraint

90 These outer sphere ion-pairs begin to exhibit significant evid

91 Outer-sphere ion clusters are inferred in many important

92 ectrostatic interactions may assemble stable outer-sphere ion clusters in organic solutions, elucidat

93 At higher temperatures, no outer-sphere ion pairs are formed, and the larger cluste

94 tructural inner-sphere ion and one catalytic outer-sphere ion.

95 occurred, but less CA was retained than via outer-sphere kaolinite-CA complexation.

96 Here, we characterize trefoil-shaped outer-sphere lanthanide chloride and nitrate ion cluster

97 carboxylate abandons the role it plays as an outer sphere ligand in wild-type rat beta, rotating away

98 net that Co(NH(3))(6)(3+) ions displace only outer sphere magnesium ions.

99 stead, a hydride moiety is transferred in an outer-sphere manner to afford an ion-pair, and the corre

100 r is retained, consistent with the canonical outer sphere mechanism invoked for palladium-catalyzed a

101 imental and computational studies support an outer sphere mechanism where the N-H proton hydrogen bon

102 diate with O(2) and are inconsistent with an outer-sphere mechanism for the reaction of the reduced e

103 s disfavored relative to an unusual stepwise outer-sphere mechanism involving sequential proton and h

104 ness of the iridium complexes argued for the outer-sphere mechanism of the homogeneous oxidation reac

105 cals and proceeds by an unexpected binuclear outer-sphere mechanism to cleanly form trans-insertion p

106 Most of the reactions proceed through an outer-sphere mechanism, affording linear products when m

107 and attacks the protonated substrate via an outer-sphere mechanism.

108 ecarboxylation and the reaction occurs in an outer-sphere mechanism.

109 and reductive dechlorination proceeding via outer sphere mechanisms), in studies of in situ attenuat

110 ncer ligands, of noninnocent ligands, and of outer sphere mechanisms.

111 died to distinguish between inner sphere and outer sphere mechanisms.

112 without metal-ligand cooperation, inner- and outer-sphere mechanisms) leads us to conclude that the m

113 vent (aqueous ionic solution) is the primary outer-sphere medium for oxidation, contributing 0.60 eV

114 Distribution functions reveal that outer-sphere Mg(2+) are positioned by electronegative at

115 Outer-sphere Mg(2+) are separated from the RNA by a sing

116 Diffusion analysis suggests transient outer-sphere Mg(2+) dynamics are glassy.

117 Since outer-sphere Mg(2+) ions account for most of the Mg(2+)

118 Outer-sphere Mg(2+) ions responsible for these effects a

119 evealed the requirement of a fully hydrated (outer-sphere) Mg2+ ion for catalytic activity.

120 1 have been analyzed quantitatively using an outer-sphere model for bimolecular spin relaxation to ex

121 h inversion of configuration, followed by an outer sphere nucleophilic attack that leads to a second

122 ns of the NISE model whereby Na adsorbed via outer-sphere on zeolite Y, inner-sphere on ZSM-5, and a

123 electrode reactions have been investigated: outer-sphere (one-electron oxidation of ferrocenylmethyl

124 CN)6] as well as in contact with a series of outer-sphere, one-electron redox couples in nonaqueous e

125 interaction with the phosphate 5' to A7 but outer-sphere or structural effects that cause perturbati

126 With the outer-sphere oxidant ferrocenium, the data are consisten

127 oxidation and generally considered to be an outer-sphere oxidant.

128 Oxidations of these phenols by outer-sphere oxidants yield distonic radical cations (*)

129 field and are accessible to both inner- and outer-sphere oxidants: Cr(2+)- converts into Cr(3+)-subs

130 odium sequestering reagent, (5) inner versus outer sphere oxidation and (6) stability with respect to

131 Outer-sphere oxidation of this intermediate by 2 equiv o

132 bonds is energetically favored, followed by outer-sphere oxidation to intermediate [1A(OH)2](0).

133 on the HOPG surface ensures that the simple outer-sphere pathway mediates ultrafast electron transfe

134 ner-sphere pathways are lower in energy than outer-sphere pathways.

135 uction of Ru(NH3)6(3+), a model one electron outer sphere process, and applied to the derivation of t

136 Our work suggests that outer-sphere protein reorganization is the dominant acti

137 First, the energetics of outer-sphere proton and electron transfer as well as cou

138 ere Rb(+) slowly transforms to a less stable outer-sphere Rb(+).

139 en shown through intensive research to be an outer-sphere reaction.

140 analysis of the voltammetric response of an outer sphere redox couple can be used to track changes i

141 icarbollide) is used as a fast, one-electron outer sphere redox couple in dye-sensitized solar cells.

142 of demonstrating fast electron transfer) for outer sphere redox couples, the following factors must b

143 A series of nonadsorbing, one-electron, outer-sphere redox couples with formal reduction potenti

144 te constants for this series of one-electron outer-sphere redox couples.

145 selectivity that does not exist in classical outer-sphere redox mediators.

146 perometry and cyclic voltammetry of an ideal outer-sphere redox probe, reversible ferrocene methanol

147 The electrochemical response of several outer-sphere redox probes on such BTB/CD electrodes is c

148 reactions from nanoparticle TiO(2) films to outer-sphere redox shuttles were investigated.

149 ON, it supports rapid electron exchange with outer-sphere redox systems, but not with dopamine, which

150 ery strong hydrogen atom donor as well as an outer-sphere reductant.

151 ved from 14% to 80% simply by addition of an outer-sphere reductant.

152 e of both hydrogen peroxide and one-electron outer-sphere reductants increases by 3 orders of magnitu

153 are very strong nucleophiles, they are mild outer-sphere reductants.

154 Outer-sphere reductive single electron transfer (OS-SET)

155 endent molecular dynamics simulations and an outer-sphere relaxation model, to quantitatively charact

156 tion is advanced that is based on changes in outer-sphere reorganization as a function of pH.

157 on energies, allows for an estimation of the outer-sphere reorganization energies with values as low

158 ese differences are attributed to the large, outer-sphere reorganization energy for charge transfer a

159 It is found that the outer-sphere reorganization energy is extremely small.

160 ggested to be due to small reductions in the outer-sphere reorganization energy of both component pro

161 ated with density functional theory, and the outer-sphere reorganization energy of the protein is cal

162 Decomposing the outer-sphere reorganization free energy, we find that th

163 ntly because of the dominant contribution of outer-sphere reorganization to the activation barrier; w

164 ling combined with a strong increase of the (outer-sphere) reorganization energy with increasing dist

165 ates, the DAAA reaction proceeds through an "outer sphere" S(N)2 type of attack on the pi-allylpallad

166 e tautomer in primary amine catalysts having outer-sphere silanols partially replaced by aprotic func

167 Model reactants for outer-sphere single electron transfer generated large in

168 Ferrocenes, which are typically air-stable outer-sphere single-electron transfer reagents, were fou

169 oth steps proceed by a low activation energy outer-sphere single-electron-transfer (SET) mechanism.

170 molecules facilitate the PCET necessary for outer-sphere SOD activity.

171 be ascribed to putative translocation of an outer-sphere solvent molecule, which could destabilize t

172 ue mainly to the compensation of the smaller outer-sphere solvent reorganization energy for PCET by t

173 PCET depend on the inner-sphere (solute) and outer-sphere (solvent) reorganization energies and on th

174 suggest the operation of a pathway involving outer-sphere stereoinvertive transmetalation.

175 These results provide support for an outer sphere transfer of hydrogen to the imine to genera

176 This step is accompanied by a proton-coupled outer-sphere transfer of the first electron from a C-H s

177 In addition to a floppy outer-sphere transition state which leads directly to ET

178 I(2) (and SmI(2)[bond]HMPA complexes) and an outer-sphere-type ET for the reduction of alkyl iodides

179 dded in a web of hydrogen bonds involving an outer sphere tyrosine residue (Tyr42).

180 ide new insight into the contribution of the outer sphere tyrosine to the stability of the dimanganes

181 The formation of secondary bonds in the outer sphere using, for example, electrostatic or H-bond

182 mate the contribution to relaxivity from the outer-sphere water molecules surrounding MS-325.

183 for Mg2+, and a weak catalytic site that is outer sphere with little preference for a particular div

184 crucial process is the transformation of an outer-sphere Zn/S complex to an inner-sphere ion pair.