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The reaction was performed in an NMR tube using deuterated DMF solvent such that reaction conversion could be determined simply by comparing the integration of the signals due to the appearing 1,2,3-triazole product with those due to disappearing 3 in the 1H NMR spectrum
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1H NMR spectrum.
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The mixed monolayer surfaces were reported to contain 45% azide moieties when deposited from a 1:1 molar ratio solution of azidoundecanethiol and octanethiol. See Ref. [14b].
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The mixed monolayer surfaces were reported to contain 45% azide moieties when deposited from a 1:1 molar ratio solution of azidoundecanethiol and octanethiol. See Ref. [14b].
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57549119320
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While the azide function is the limiting reagent for surface-based reactions, it begins the reaction in vast excess at the surface in comparison to the added alkyne and catalyst. Throughout the reaction, the azide moieties are depleted while excess of the alkyne molecules diffuse freely, presumably maintaining a constant concentration. While these concentration effects are difficult to mimic in traditional homogeneous reaction strategies, the decreased reagent degrees of freedom affecting the potential energy landscape for the surface reactions in comparison to solution reactions introduces additional significant differences. However, the flooding conditions in alkyne were adapted as a reasonably close representation of the concentration conditions at the surface
-
While the azide function is the limiting reagent for surface-based reactions, it begins the reaction in vast excess at the surface in comparison to the added alkyne and catalyst. Throughout the reaction, the azide moieties are depleted while excess of the alkyne molecules diffuse freely, presumably maintaining a constant concentration. While these concentration effects are difficult to mimic in traditional homogeneous reaction strategies, the decreased reagent degrees of freedom affecting the potential energy landscape for the surface reactions in comparison to solution reactions introduces additional significant differences. However, the flooding conditions in alkyne were adapted as a reasonably close representation of the concentration conditions at the surface.
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A kinetic plot similar to Figure 4b showing the full reaction time for the Solution-Surface reaction is included in the Supporting Information.
-
A kinetic plot similar to Figure 4b showing the full reaction time for the Solution-Surface reaction is included in the Supporting Information.
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62
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A freely diffusing particle will move about 1 micrometer in 1 millisecond
-
A freely diffusing particle will move about 1 micrometer in 1 millisecond.
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65
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57549113897
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The resolution achieved using the Reagent-Stamping protocol was similar to that of traditional microcontact printing for spatially selective reactions see refs, 8-10
-
The resolution achieved using the Reagent-Stamping protocol was similar to that of traditional microcontact printing for spatially selective reactions (see refs. [8-10]).
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