molecular diffusivity
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Author(s):  
Nasrollah Rezaei-Ghaleh ◽  
Jaime Agudo-Canalejo ◽  
Christian Griesinger ◽  
Ramin Golestanian

2021 ◽  
Vol 104 (3) ◽  
Author(s):  
Lakshminarayana M. H. Reddy ◽  
S. Kokou Dadzie

ACS Nano ◽  
2021 ◽  
Vol 15 (9) ◽  
pp. 14947-14953
Author(s):  
Tian Huang ◽  
Bo Li ◽  
Huan Wang ◽  
Steve Granick

2021 ◽  
Author(s):  
Tian Huang ◽  
Bo Li ◽  
Huan Wang ◽  
Steve Granick

Bipolar reactions have been provoked by reports of boosted diffusion during chemical and enzymatic reactions. To some, it is intuitively reasonable that relaxation to truly Brownian motion after passing an activation barrier can be slow, but to others the notion is so intuitively unphysical that they suspect the supporting experiments to be artifact. Here we study a chemical reaction according to whose mechanism some intermediate species should speed up while others slow down in predictable ways, if the boosted diffusion interpretation holds. Experimental artifacts would do not know organic chemistry mechanism, however. Accordingly, we scrutinize the absolute diffusion coefficient (D) during intermediate stages of the CuAAC reaction (coppercatalyzed azide-alkyne cycloaddition click reaction), using proton pulsed field-gradient nuclear magnetic resonance (PFG-NMR) to discriminate between the diffusion of various reaction intermediates. For the azide reactant, its D increases during reaction, peaks at the same time as peak reaction rate, then returns to its initial value. For the alkyne reagent, its D decreases consistent with presence of the intermediate large complexes formed from copper catalyst and its ligand, except for the 2Cu-alk complex whose more rapid D may signify that this species is the real reactive complex. For the product of this reaction, its D increases slowly as it detaches from the triazolide catalyst complex. These examples of enhanced diffusion for some molecular species and depressed diffusion for others causes us to conclude that diffusion coefficients during these elementary reactions are influenced by two components: hydrodynamic radius increase from complex formation, which slows diffusion, and energy release rate during the chemical reaction, which speeds it up. We discuss possible mechanisms and highlight that too little is yet understood about slow solvent reorganization during chemical reactions.<br>


2021 ◽  
Author(s):  
Tian Huang ◽  
Bo Li ◽  
Huan Wang ◽  
Steve Granick

Bipolar reactions have been provoked by reports of boosted diffusion during chemical and enzymatic reactions. To some, it is intuitively reasonable that relaxation to truly Brownian motion after passing an activation barrier can be slow, but to others the notion is so intuitively unphysical that they suspect the supporting experiments to be artifact. Here we study a chemical reaction according to whose mechanism some intermediate species should speed up while others slow down in predictable ways, if the boosted diffusion interpretation holds. Experimental artifacts would do not know organic chemistry mechanism, however. Accordingly, we scrutinize the absolute diffusion coefficient (D) during intermediate stages of the CuAAC reaction (coppercatalyzed azide-alkyne cycloaddition click reaction), using proton pulsed field-gradient nuclear magnetic resonance (PFG-NMR) to discriminate between the diffusion of various reaction intermediates. For the azide reactant, its D increases during reaction, peaks at the same time as peak reaction rate, then returns to its initial value. For the alkyne reagent, its D decreases consistent with presence of the intermediate large complexes formed from copper catalyst and its ligand, except for the 2Cu-alk complex whose more rapid D may signify that this species is the real reactive complex. For the product of this reaction, its D increases slowly as it detaches from the triazolide catalyst complex. These examples of enhanced diffusion for some molecular species and depressed diffusion for others causes us to conclude that diffusion coefficients during these elementary reactions are influenced by two components: hydrodynamic radius increase from complex formation, which slows diffusion, and energy release rate during the chemical reaction, which speeds it up. We discuss possible mechanisms and highlight that too little is yet understood about slow solvent reorganization during chemical reactions.<br>


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