Response to Comment on "Following Molecular Mobility during Chemical Reactions: No Evidence for Active Propulsion" and "Molecular Diffusivity of Click Reaction Components: The Diffusion Enhancement Question".

In their Comment (DOI: 10.1021/jacs.2c02965) on two related publications by our groups (J. Am. Chem. Soc. 2021, 143, 20884-20890; DOI: 10.1021/jacs.1c09455) and another (J. Am. Chem. Soc. 2022, 144, 1380-1388; DOI: 10.1021/jacs.1c11754), Huang and Granick discuss the diffusion NMR measurements of molecules during a copper-catalyzed azide-alkyne cycloaddition (CuAAC) "click" reaction. Here we respond to these comments and maintain that no diffusion enhancement was observed for any species during the reaction. We show that the relaxation agent does not interfere with the CuAAC reaction kinetics nor the diffusion of the molecules involved. Similarly, the gradient pulse length and diffusion time do not affect the diffusion coefficients. Peak overlap was completely removed in our study with the use of hydrazine as the reducing agent. The steady-state assumption does not hold for these diffusion measurements that take several minutes, which is the reason monotonic gradient orders are not suitable. Finally, we discuss the other reactions where similar changes in diffusion have been claimed. Our conclusions are fully supported by the results represented in our original JACS Article and the corresponding Supporting Information.

Following Molecular Mobility during Chemical Reactions: No Evidence for Active Propulsion.

The reported changes in self-diffusion of small molecules during reactions have been attributed to "boosted mobility". We demonstrate the critical role of changing concentrations of paramagnetic ions on nuclear magnetic resonance (NMR) signal intensities, which led to erroneous measurements of diffusion coefficients. We present simple methods to overcome this problem. The use of shuffled gradient amplitudes allows accurate diffusion NMR measurements, even with time-dependent relaxation rates caused by changing concentrations of paramagnetic ions. The addition of a paramagnetic relaxation agent allows accurate determination of both diffusion coefficients and reaction kinetics during a single experiment. We analyze a copper-catalyzed azide-alkyne cycloaddition "click" reaction, for which boosted mobility has been claimed. With our methods, we accurately measure the diffusive behavior of the solvent, starting materials, and product and find no global increase in diffusion coefficients during the reaction. We overcome NMR signal overlap using an alternative reducing agent to improve the accuracy of the diffusion measurements. The alkyne reactant diffuses slower as the reaction proceeds due to binding to the copper catalyst during the catalytic cycle. The formation of this intermediate was confirmed by complementary NMR techniques and density functional theory calculations. Our work calls into question recent claims that molecules actively propel or swim during reactions and establishes that time-resolved diffusion NMR measurements can provide valuable insight into reaction mechanisms.

Robust spatial analysis of sequestered metals in a Southern California Bioswale.

Bioswales are a type of permeable green infrastructure designed to slow stormwater and clean runoff by sequestering pollutants such as heavy metals. Measurements of dissolved pollutants before and after the bioswale often justify their ability to clean this runoff, but research addressing the physical and chemical sequestration of these pollutants is scarce. Soil samples were taken from an arid bioswale and analyzed for concentrations of aluminum, cobalt, chromium, copper, iron, magnesium, manganese, nickel, lead, vanadium and zinc. Heat maps of the concentration of these metals in soil were generated via Empirical Bayesian Kriging (EBK) and demonstrate that location-specific sequestration differs between metals within the same swale. Sequential extraction with a modified Tessier et al. (1979) protocol coupled with profiles of metal concentration versus distance along the main flow axis in the bioswale illustrate that the carbonate soil fraction contains elevated concentrations of zinc, lead, cobalt, and manganese, metals sequestered by the bioswale with statistical significance.

Dye-sensitized solar cells: sensitizer-dependent injection into ZnO nanotube electrodes.

Two porphyrin-based dyes with carboxylic acid tethers of differing acidity in both protonated and deprotonated forms were examined on ZnO nanotube electrodes. All of the dyes have similar surface coverage, but only the more acidic dye in the acid form injects electrons well; this dye is the only one that corrodes the ZnO. In control experiments on TiO(2) nanoparticle electrodes, both dyes load and inject in protonated and deprotonated forms. These results are consistent with a requirement that the dye must partially corrode the ZnO surface in order for efficient injection to occur. Alternatively, it may possibly point to a coupling of electron injection to proton uptake.