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PF can also accept an H-bond in H-bonding solvents. According to our quantum chemical calculations, such a bond may slightly reduce the Stokes shift and the reorganization energy (Supporting Information, Section 1.7S). Such a bond should be sterically less favorable in N-methyl formamide, explaining its proximity to the non-H-bonding solvents in Figure 2.
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116 Similar to free PF in water, cosolvents rapidly destroy the anomaly for the bound dye. This effect does not seem to be related to cosolvent adsorption (no cosolvent adsorption to the surface of this protein was observed, Topolev, V. V.; Krishtalik, L. I. Biofizika 1999, 44, 992-995) or to a change in the protein conformation, Khurgin, I. I.; Azizov, I. M.; Abaturov, L. V.; Kogan, G. A.; Rosliakov, V. I. Biofizika 1972, 17, 390-395. A detailed account of the cosolvent effect will be published elsewhere.
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Krishtalik, L.I.2
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110
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0015345488
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116 Similar to free PF in water, cosolvents rapidly destroy the anomaly for the bound dye. This effect does not seem to be related to cosolvent adsorption (no cosolvent adsorption to the surface of this protein was observed, Topolev, V. V.; Krishtalik, L. I. Biofizika 1999, 44, 992-995) or to a change in the protein conformation, Khurgin, I. I.; Azizov, I. M.; Abaturov, L. V.; Kogan, G. A.; Rosliakov, V. I. Biofizika 1972, 17, 390-395. A detailed account of the cosolvent effect will be published elsewhere.
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Khurgin, I.I.1
Azizov, I.M.2
Abaturov, L.V.3
Kogan, G.A.4
Rosliakov, V.I.5
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112
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12344323344
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note
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2 ≈ 12, on the basis of the gas-phase TD/MPW1PW1/6-31G(d,p) calculation and the similarity of the sizes of these probes.
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113
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0001761172
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Ma, J.; Bout, D. V.; Berg, M. J. Chem. Phys. 1995, 103, 9146.
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Ma, J.1
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114
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12344270774
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note
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st) only, 2-4 charges corresponding to the largest atomic charges in a polarizable oblate spheroid cavity can be used for C153 and PF instead.
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115
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0032525651
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Newton, M. D.; Basilevsky, M. V.; Rostov, I. V. Chem. Phys. 1998, 232, 201.
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117
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12344268676
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note
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c ≈ 2.5). This is the case for acetonitrile analyzed in ref 9.
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-
118
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12344287820
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note
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It follows from the response theory that equilibrium density changes in response to static electric field are identically zero for the linear response of a solvent whose electrically neutral molecules have antisymmetric charge density and symmetric nonelectrostatic potential with respect to the molecule center (e.g., a dipole inside a sphere), because the density change in such a solvent may not depend on inversion of the electric field direction. For asymmetric solvent molecules, linear density changes are not forbidden.
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119
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37049078565
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See a compilation of solvent acidity scales: Catalan, J.; Gomez, J.; Saiz, J. L.; Couto, A.; Ferraris, M.; Laynez, J. J. Chem. Soc., Faraday Trans. 2 1995, 12, 2301.
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Ferraris, M.5
Laynez, J.6
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121
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12344294356
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note
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s for AO in water is also accompanied by an anomalous solvent isotope effect. This effect is not observed in methanol.
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123
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12344336218
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note
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30 We also found similar sensitivity for the specular reflection model. Thus, all these heuristic models are in qualitative disagreement with the data.
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124
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12344249483
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note
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30 It is unclear whether such energies containing significant nondielectric contributions from ion-solvent electron donor-acceptor interactions and from the solvent pre-existing potential can be described in terms of the solvent dielectric properties. Furthermore, the fitting function directly couples changes in solute cavity size to solute charge. We are not aware of any indication that such direct interaction between solute electric field and mass (solvent density near solute) is important. In contrast, such coupling, if it exists, seems to be insignificant for our probe, because the measured reorganization energies are almost insensitive to pressure; Sections 4.1 and 5.
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127
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84947373046
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134
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12344312946
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note
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108 The absence of an anomalous response for C153 may be explained (e.g., assuming that anomalous polarization fluctuations occur at 1-2.5 Å length scales, which is within the range of charge redistribution of PF and outside the range of C153).
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135
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12344284617
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note
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1.
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136
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12344323343
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note
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2Co). We verified that the inclusion of these generated data into the analysis presented in Table 1 would produce similar results.
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