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Silver nanoclusters to be fractioned strongly absorb UV light at 365 nm due to the metal-based electronic transitions, so the irradiated light cannot pass through the lanes (bands) of silver nanoclusters in the plate gel. On the other hand, the residual light can pass through the gel and excite a fluorescent screen. Then, the lanes containing silver nanoclusters make shadows on the screen.
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Silver nanoclusters to be fractioned strongly absorb UV light at 365 nm due to the metal-based electronic transitions, so the irradiated light cannot pass through the lanes (bands) of silver nanoclusters in the plate gel. On the other hand, the residual light can pass through the gel and excite a fluorescent screen. Then, the lanes containing silver nanoclusters make "shadows" on the screen.
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15844386157
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Taking the silver core as a sphere with the bulk density covered with an outermost layer of close-packed silver atoms (13.92 atoms/nm2; this value can be estimated from the radius of a silver atom 0.144 nm, the cores of 1 and 2 contain ∼36 and ∼68 Ag atoms, of which ∼25 and ∼45 atoms lie on the nanocluster surface, respectively. Note that, for the estimation of the number of surface atoms, the skin is taken as the center of the outermost silver atoms Terrill, R. H, Postlethwaite, T. A, Chen, C.-h, Poon, C.-D, Terzis, A, Chen, A, Hutchison, J. E, Clark, M. R, Wignall, G, Londono, J. D, Superfine, R, Falvo, M, Johnson, C. S, Jr, Samulski, E. T, Murray, R. W. J. Am Chem. Soc, 1995, 117, 12537
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2; this value can be estimated from the radius of a silver atom 0.144 nm), the cores of 1 and 2 contain ∼36 and ∼68 Ag atoms, of which ∼25 and ∼45 atoms lie on the nanocluster surface, respectively. Note that, for the estimation of the number of surface atoms, the skin is taken as the center of the outermost silver atoms (Terrill, R. H.; Postlethwaite, T. A.; Chen, C.-h.; Poon, C.-D.; Terzis, A.; Chen, A.; Hutchison, J. E.; Clark, M. R.; Wignall, G.; Londono, J. D.; Superfine, R.; Falvo, M.; Johnson, C. S., Jr.; Samulski, E. T.; Murray, R. W. J. Am Chem. Soc., 1995, 117, 12537).
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2) (Mohtat, N.; Byloos, M.; Soucy, M.; Morin, S.; Morin, M. J. Electroanal. Chem. 2000, 484, 120; this packing density was calculated for the Ag(111) surface), 1 and 2 would have 9-10 and 16-17 thiol molecules on their surface, respectively.
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2) (Mohtat, N.; Byloos, M.; Soucy, M.; Morin, S.; Morin, M. J. Electroanal. Chem. 2000, 484, 120; this packing density was calculated for the Ag(111) surface), 1 and 2 would have 9-10 and 16-17 thiol molecules on their surface, respectively.
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42149147104
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To further demonstrate the spectral differences, absorption spectra of the nanocluster compounds (ID/IL/WIDSO/ILSO) were normalized at around 255 nm and compared with each other. See the Supporting Information for more detail.
-
To further demonstrate the spectral differences, absorption spectra of the nanocluster compounds (ID/IL/WIDSO/ILSO) were normalized at around 255 nm and compared with each other. See the Supporting Information for more detail.
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42149125297
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Actually, the fractioned bands 1eD/1eL and 2eD/2eL were somewhat diffusive, indicating that the qualities of these compounds were relatively poor as compared to those of the corresponding normally prepared samples. Hence, we carefully cut the lanes of 1eD/1eL and 2eD/2eL as sharp and similar as possible to the other cases, b In addition, we conducted field-emission scanning transmission electron microscopy (FE-STEM) for the D-Pen-exchanged compounds 1eD and 2eD. Unfortunately, clear images could not be obtained probably due to the very small size and high reactivity of the clusters under the electron-beam irradiation, but we confirmed that there was no size growth in these compounds
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eD. Unfortunately, clear images could not be obtained probably due to the very small size and high reactivity of the clusters under the electron-beam irradiation, but we confirmed that there was no size growth in these compounds.
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In ref 21a, it was reported that cysteine-capped silver nanoparticles were decomposed to form gray precipitates under highly acidic conditions pH < 3
-
(b) In ref 21a, it was reported that cysteine-capped silver nanoparticles were decomposed to form gray precipitates under highly acidic conditions (pH < 3).
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41
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33749599105
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Although this detail of the decomposition mechanism is not clear at present, it is probably due to a high chemical reactivity of small silver nanoclusters in the reaction with hydrochloric acid, which might produce silver chloride Li, L, Zhu, Y.-J. J. Colloid Interface Sci. 2006, 303, 415
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(c) Although this detail of the decomposition mechanism is not clear at present, it is probably due to a high chemical reactivity of small silver nanoclusters in the reaction with hydrochloric acid, which might produce silver chloride (Li, L.; Zhu, Y.-J. J. Colloid Interface Sci. 2006, 303, 415.)
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42149189206
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When the absorption of the supernatant solution was used for the calibration, we failed to obtain the relationship probably because the solution still contained the running buffer components and thus interfered with the appropriate estimation
-
When the absorption of the supernatant solution was used for the calibration, we failed to obtain the relationship probably because the solution still contained the running buffer components and thus interfered with the appropriate estimation.
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42149165254
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Calibration curve (relationship between ee and CD/Abs values) was carefully examined for 2 2D/2L/2D50/2 L50, Although a linear relationship could be obtained, the slopes of the regression line were different between 2D/2D50 and 2L/2L50 series. See the Supporting Information for details. However, by using the respective calibration curve for the D- or L-Pen-exchanged samples, we estimated the reasonable enantiomeric excess of 2eD or 2eL to be ∼48 or ∼59% ee, respectively
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eL to be ∼48 or ∼59% ee, respectively.
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