Elucidating the performance of UV-based photochemical processes for the removal of trace organic contaminants: Degradation and toxicity evaluation.

In this study, the performance of standalone ultraviolet (UV) photolysis and UV-based advanced oxidation processes (AOPs), namely, UV/hydrogen peroxide, UV/chlorine, UV/persulphate, and UV/permonosulphate, were investigated for the degradation of 31 trace organic contaminants (TrOCs). Under the tested conditions, standalone UV photolysis did not achieve effective removal of TrOCs. To improve the degradation efficiency of UV photolysis, four different oxidants were added individually to the test solution. The effect of these oxidants in the absence of UV irradiation was also explored and only chlorine showed promising degradation of some contaminants. During the chlorination of 31 investigated TrOCs, only six demonstrated greater than 50% degradation. The combined UV-based AOPs demonstrated much improved degradation (ranging from 65 to 100%) depending on TrOC-structure and oxidant concentration. The UV/hydrogen peroxide process showed similar degradation of TrOCs, irrespective of the functional groups (i.e., electron withdrawing groups, EWGs and electron donating groups, EDGs) present in their structures. Conversely, the UV/sulphate and UV/chlorine based processes achieved better degradation of the TrOCs with EDGs in their structures. TrOCs degradation improved up to 40% when oxidants concentrations were increased from 0.1 to 1 mM, and further increasing the concentration to 2 mM did not improve degradation. Toxicity evaluation using bioluminescence test (BLT assay) demonstrated that except for UV/hydrogen peroxide, all UV-based AOPs increased the toxicity of the treated effluent, indicating generation of toxic by-products. This study elucidates the performance of four different UV-based AOPs for the removal of commonly detected diverse TrOCs for the first time.

A new method to quantify the human visual threshold from melanopsin sensitive ganglion cells.

Traditional photoreceptors utilize the chromophore retinal to absorb light coupled with a unique opsin protein to specify receptor spectral sensitivity. Light absorption triggers a cascade of events transducing light energy to neural signals beginning with graded potentials in receptors (rods and cones) and bipolar cells in outer and middle retina eventuating in action potentials at the inner retinal amacrine and ganglion cell levels. Unlike traditional photoreceptors, ganglion cells in the inner retina (intrinsically photosensitive retinal ganglion cells, ipRGCs) absorb short wavelength, blue light utilizing their photopigment melanopsin. Assessment across multiple species show that the ipRGCs mediate myriad visual and non-visual functions including photo-entrainment and circadian rhythms, the pupillary light reflex, sleep, alertness, cognition, mood, and even conscious visual perception. Some ipRGC functions can persist despite blindness in animal models and humans exemplifying their multidisciplinary control of visual and non-visual functions. In previous research we used selective chromatic adaptation (blue stimulus on a bright amber field) to suppress input from rods, red and green sensitive cones to identify retinal and cortical responses from ipRGCs. Herein we used a similar approach, coupled with a filter to block input from blue sensitive cones, to develop a clinically expedient method to measure the full-field, putative visual threshold from human ipRGCs. This metric may expand our ability to detect, diagnose and monitor ocular and neurologic disease and provide a global retinal metric of ipRGCs as a potential outcome measure for studies using gene therapy to arrest and/or improve vision in hereditary retinal diseases.

Evaluating the Stability of Cellulose Nanofiber Pickering Emulsions Using MRI and Relaxometry.

Magnetic resonance imaging (MRI) relaxometry and diffusion methods were used to highlight the instability mechanisms of oil-in-water Pickering emulsions stabilized by cellulose nanofibers (CNFs). Four different Pickering emulsions using different oils (n-dodecane and olive oil) and concentrations of CNFs (0.5 and 1.0 wt %) were systematically investigated over a period of one month after emulsification. The separation into a free oil, emulsion layer, and serum layer and the distribution of flocculated/coalesced oil droplets in several hundred micrometers were captured in MR images using fast low-angle shot (FLASH) and rapid acquisition with relaxation enhancement (RARE) sequences. The components of the Pickering emulsions (e.g., free oil, emulsion layer, oil droplets, and serum layer) were observable by different voxelwise relaxation times and apparent diffusion coefficients (ADCs) and reconstructing in the apparent T1, T2, and ADC maps. The mean T1, T2, and ADC of the free oil and serum layer corresponded well with MRI results for pure oils and water, respectively. Comparing the relaxation properties and translational diffusion coefficients of pure dodecane and olive oil obtained from NMR and MRI resulted in similar T1 and ADC but significantly different T2 depending on the sequence used. The diffusion coefficients of olive oil measured by NMR were much slower than dodecane. The ADC of the emulsion layer for dodecane emulsions did not correlate with the viscosity of the emulsions as the CNF concentration increased, suggesting the effects of restricted diffusion of oil/water molecules due to droplet packing.

Evaluation of growth, meat quality, and sensory characteristics of wool, hair, and composite lambs.

The objectives of this study were to evaluate the growth rates, carcass quality, shelf-life, tenderness, sensory characteristics, volatile compounds, and fatty acid composition of wool, hair, and composite (wool × hair) lambs. Twenty-one wether lambs [wool (Suffolk × Polypay/Targhee; n = 7), hair (Dorper × Dorper; n = 7), and composite (Dorper × Polypay/Targhee; n = 7)] were fed from weaning to finishing at the University of Idaho Sheep Center and subsequently harvested under United States Department of Agriculture inspection at the University of Idaho Meat Lab. At 48 h postmortem, carcass measurements were taken to determine the percent boneless closely trimmed retail cuts, yield grade, and quality grade. Loins were fabricated from each carcass and wet-aged at 0°C until 10-d postmortem. Following aging, 2.54-cm bone-in loin chops were cut and randomly assigned to 4 d of retail display, Warner-Bratzler Shear Force (WBSF), or sensory analyses. Thiobarbituric acid reactive substances were analyzed on days 0 and 4 of retail display while subjective and objective color measurements were observed once daily. Samples (24 g) were also collected for volatile compound and fatty acid analysis. A mixed model analysis of variance was used to assess breed differences. Discernable effects were considered at P < 0.05. Wool lambs had heavier hot carcass weights (P < 0.001), larger rib-eye area (P = 0.015), and higher dressing percent (P < 0.001) than the other breeds. There was an interaction observed between breed and days of retail display for browning (P = 0.006). On day 1 chops from the composite breed had more browning than chops from the wool breed. No differences were observed between groups for lean muscle L* values (P = 0.432), a* values (P = 0.757), and b* values (P = 0.615). Differences were not observed in lipid oxidation (P = 0.159), WBSF (P = 0.540), or consumer acceptability (P = 0.295). There were differences found for 7 of the 45 fatty acids detected and in 3 of the 67 volatile compounds detected. In conclusion, wool lambs were heavier and had a greater carcass yield than the hair lamb carcasses. Regardless of breed, consumers did not detect sensory traits that would impact their eating experience.

The U.S. lamb industry has been steadily losing production operations since the 1990s due to a decline in lamb consumption, caused by consumer flavor preferences, an increase in synthetic fabrics, and importation from Australia and New Zealand. This has limited the overall need for U.S. producers. The focus of this research was to evaluate the differences among wool, hair, and composite groups of lamb for growth traits, carcass characteristics, shelf-life stability, consumer flavor, volatile compounds, and fatty acid profiling. The study found the wool group maintained a higher overall weight, as well as a taller shoulder height, and heart girth circumference over the hair group. The wool group also had a superior final carcass size; however, the quality grade did not differ between the composite and wool groups. There was no difference between groups for consumer sensory levels or cook loss. Minimal variation was shown throughout the retail shelf-life; however, general discoloration increased as expected during retail display. Tenderness levels between groups were also similar. Volatile compounds showed differences for three compounds with variation between groups. Fatty acid analysis also determined seven compounds of interest; however, common fatty acids known to be flavor factors were not different between groups.

Stuck in the past? Rumination-related memory integration.

Memories connected to ruminative concerns repetitively capture attention, even in situations designed to alter them. However, recent research on memory updating suggests that memory for benign substitutes (e.g., reinterpretations) might be facilitated by integration with the ruminative memories. As a first approach, two experiments (Ns = 72) mimicked rumination-related memories with rumination-themed stimuli and an imagery task. College undergraduates screened for ruminative status first studied and imaged ruminative cue-target word pairs, and then in a second phase they studied the same cues re-paired with benign targets (along with new and repeated pairs). On the test of cued recall of benign targets, they judged whether each recalled word had been repeated or changed across the two phases (or was new in the second phase). When target changes were not remembered, recall of benign targets revealed proactive interference that was insensitive to ruminative status. However, when participants remembered change and the ruminative targets, their recall of benign targets was facilitated, particularly if they identified as ruminators (Experiment 1). When the test simply asked for recall of either or both targets (Experiment 2), ruminators recalled both targets more frequently than did others. These outcomes suggest that ruminative memories might provide bridges to remembering associated benign memories, such as reinterpretations, under conditions consistent with everyday ruminative retrieval.

Diffusion Measurements To Understand Dynamics and Structuring in Solutions Involving a Homologous Series of Ionic Liquids.

The self-diffusion coefficients of each of the components in mixtures containing pyridine and each of the homologous series 1-alkyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imides in acetonitrile were determined using NMR diffusometry (i. e., Pulsed Gradient Spin Echo). The nature of solvation was found to change significantly with the proportion of salt in the mixtures. Increased diffusion coefficients (when corrected for viscosity) for the molecular components were observed with increasing proportion of ionic liquid and with increasing alkyl chain length on the cation. Comparison of the molecular solvents suggests increased interactions in solution of the pyridine with other components of the mixture, consistent with the proposed interactions shown previously to drive changes in reaction kinetics. Discontinuities were seen in the diffusion data for each species in solution across different ionic liquids between the hexyl and octyl derivatives, suggesting a change in the structuring in solution as the alkyl chain on the cation changes and demonstrating the importance of such when considering homologous series.

Characterisation of internal oxygen concentration of strawberry (Fragaria × ananassa) and blueberry (Vaccinium corymbosum).

Gas exchange mechanisms play crucial roles in maintaining fruit post-harvest quality in perishable fruit such as strawberry (Fragaria×ananassa Duch.) and blueberry (Vaccinium corymbosum L.). The internal oxygen concentration ([O2 ]) of strawberry and blueberry were measured using Clark-type oxygen sensing electrodes. The volume of intercellular voids in strawberry was obtained by micro-computed tomography (micro-CT). In both berries, internal [O2 ] was consistent and relatively high across measured tissues. The overall [O2 ] was well above the Michaelis constant (K m ) for cytochrome c oxidase in both fruit and different from previously examined grape (Vitis vinifera L.) berry mesocarp with near zero minimum [O2 ]. In strawberry and blueberry, cell vitality was also maintained at full maturity in the mesocarp. Higher storage temperature (i.e. 20 vs 4°C) reduced internal [O2 ] of strawberry. Pedicel detachment in blueberry was associated with greater fruit dehydration and lower internal [O2 ] after short-term storage of 12h. The results suggest that the intercellular voids of the fruit's mesocarp provide an efficient gas exchange route for maintaining high fruit internal [O2 ] post-harvest.

Estimates of fine fuel litter biomass in the northern Great Basin reveal increases during short fire-free intervals associated with invasive annual grasses.

Exotic annual grasses invasion across northern Great Basin rangelands has promoted a grass-fire cycle that threatens the sagebrush (Artemisia spp.) steppe ecosystem. In this sense, high accumulation rates and persistence of litter from annual species largely increase the amount and continuity of fine fuels. Here, we highlight the potential use and transferability of remote sensing-derived products to estimate litter biomass on sagebrush rangelands in southeastern Oregon, and link fire regime attributes (fire-free period) with litter biomass spatial patterns at the landscape scale. Every June, from 2018 to 2021, we measured litter biomass in 24 field plots (60 m × 60 m). Two remote sensing-derived datasets were used to predict litter biomass measured in the field plots. The first dataset used was the 30-m annual net primary production (NPP) product partitioned into plant functional traits (annual grass, perennial grass, shrub, and tree) from the Rangeland Analysis Platform (RAP). The second dataset included topographic variables (heat load index -HLI- and site exposure index -SEI-) computed from the USGS 30-m National Elevation Dataset. Through a frequentist model averaging approach (FMA), we determined that the NPP of annual and perennial grasses, as well as HLI and SEI, were important predictors of field-measured litter biomass in 2018, with the model featuring a high overall fit (R2 = 0.61). Model transferability based on extrapolating the FMA predictive relationships from 2018 to the following years provided similar overall fits (R2 ≈ 0.5). The fire-free period had a significant effect on the litter biomass accumulation on rangelands within the study site, with greater litter biomass in areas where the fire-free period was <10 years. Our findings suggest that the proposed remote sensing-derived products could be a key instrument to equip rangeland managers with additional information towards fuel management, fire management, and restoration efforts.

Sodium and Potassium Concentrations and Somatic Cell Count of Human Milk Produced in the First Six Weeks Postpartum and Their Suitability as Biomarkers of Clinical and Subclinical Mastitis.

The sodium (Na) concentration and the ratio of Na to potassium (K; Na/K) in human milk are used commonly as biomarkers of subclinical mastitis, but limited data exist on their relationship to and ability to predict clinical mastitis. Here, we assessed concentrations of Na, K, Na/K, and somatic cell count (SCC), a mammary health biomarker used in the dairy industry, in milk prospectively collected from both breasts of 41 women over the first 6 weeks postpartum. Although values differed over time postpartum, there were no differences in mean values between breasts. Nearly one-quarter (24%) of participants experienced clinical mastitis. Somatic cell counts >4.76 × 105 cells/mL were most strongly related to development of clinical mastitis in the following week (odds ratio, 7.81; 95% CI, 2.15−28.30; p = 0.002), although relationships were also observed for SCC > 4.00 × 105 cells/mL and Na concentration >12 mmol/L. Estimates of the prevalence of subclinical mastitis in women who never progressed to clinical mastitis differed by biomarker but ranged from 20 to 75%. Despite these findings, positive predictive values (PPV) of the biomarkers for identifying clinical mastitis were low (≤0.34), indicating additional research is needed to identify single biomarkers or composite measures that are highly specific, sensitive, and predictive of clinical mastitis in women.

A volumetric and intra-diffusion study of solutions of AlCl3 in two ionic liquids - [C2TMEDA][Tf2N] and [C4mpyr][Tf2N].

Intra-diffusion coefficients (DSi) have been measured for the ionic liquid constituent ions and aluminium-containing species in aluminium chloride (AlCl3) solutions in the ionic liquids 1-(2-dimethyl-aminoethyl)-dimethylethylammonium bis(trifluoromethylsulfonyl)amide ([C2TMEDA][Tf2N]) and N-butyl-N-methylpyrrolidinium bis(trifluoromethylsulfonyl)amide ([C4mpyr][Tf2N]), to investigate whether spectroscopically detected interactions between the ions and AlCl3 affect these properties. Such electrolyte solutions are of interest for the electrowinning of aluminium. The temperature, composition and molar volume dependences are investigated. Apparent (Vϕ,1) and partial molar (V1) volumes for AlCl3 have been calculated from solution densities. For [C2TMEDA][Tf2N] solutions, Vϕ,1 increases with increasing solute concentration; for [C4mpyr][Tf2N] solutions, it decreases. In pure [C2TMEDA][Tf2N], the cation diffuses more quickly than the anion, but this changes as the AlCl3 concentration increases. In the [C4mpyr][Tf2N] solutions, the intra-diffusion coefficient ratio remains equal to that for the pure ionic liquid and the aluminium species diffuses at approximately the same rate as the anion at each composition. The intra-diffusion coefficients can be fitted to the Ertl-Dullien free volume power law by superposing the iso-concentration curves with concentration dependent, but temperature independent, molar volume offsets. This suggests that they are primarily dependent on the molar volume and secondarily on a colligative thermodynamic factor due to dilution by AlCl3. AlCl3 complexation by [Tf2N]- and [C2TMEDA]+, confirmed by 27Al, 15N and 19F NMR spectroscopy, seems to play a minor role. Our results indicate that the application of free volume theories might be fruitful in the study of the transport properties of ionic liquid solutions and mixtures.

MRI Detection of Hepatic N-Acetylcysteine Uptake in Mice.

This proof-of-concept study looked at the feasibility of using a thiol-water proton exchange (i.e., CEST) MRI contrast to detect in vivo hepatic N-acetylcysteine (NAC) uptake. The feasibility of detecting NAC-induced glutathione (GSH) biosynthesis using CEST MRI was also investigated. The detectability of the GSH amide and NAC thiol CEST effect at B0 = 7 T was determined in phantom experiments and simulations. C57BL/6 mice were injected intravenously (IV) with 50 g L-1 NAC in PBS (pH 7) during MRI acquisition. The dynamic magnetisation transfer ratio (MTR) and partial Z-spectral data were generated from the acquisition of measurements of the upfield NAC thiol and downfield GSH amide CEST effects in the liver. The 1H-NMR spectroscopy on aqueous mouse liver extracts, post-NAC-injection, was performed to verify hepatic NAC uptake. The dynamic MTR and partial Z-spectral data revealed a significant attenuation of the mouse liver MR signal when a saturation pulse was applied at -2.7 ppm (i.e., NAC thiol proton resonance) after the IV injection of the NAC solution. The 1H-NMR data revealed the presence of hepatic NAC, which coincided strongly with the increased upfield MTR in the dynamic CEST data, providing strong evidence that hepatic NAC uptake was detected. However, this MTR enhancement was attributed to a combination of NAC thiol CEST and some other upfield MT-generating mechanism(s) to be identified in future studies. The detection of hepatic GSH via its amide CEST MRI contrast was inconclusive based on the current results.

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.

Rapid Online Analysis of Photopolymerization Kinetics and Molecular Weight Using Diffusion NMR.

Online, high-throughput molecular weight analysis of polymerizations is rare, with most studies relying on tedious sampling techniques and batchwise postanalysis. The ability to track both monomer conversion and molecular weight evolution in real time could underpin precision polymer development and facilitate study of rapid polymerization reactions. Here, we use a single time-resolved diffusion nuclear magnetic resonance (NMR) experiment to simultaneously study the kinetics and molecular weight evolution during a photopolymerization, with in situ irradiation inside the NMR instrument. As a model system, we used a photoinduced electron transfer reversible addition-fragmentation chain transfer (PET-RAFT) polymerization. The data allow diffusion coefficients and intensities to be calculated every 14 s from which the polymer size and monomer conversion can be extracted. Key to this approach is (1) the use of shuffled gradient amplitudes in the diffusion NMR experiment to access reactions of any rate, (2) the addition of a relaxation agent to increase achievable time resolution and, (3) a sliding correction that accounts for viscosity changes during polymerization. Diffusion NMR offers a uniquely simple, translatable handle for online monitoring of polymerization reactions.

Full adoption of the most effective strategies to mitigate methane emissions by ruminants can help meet the 1.5 °C target by 2030 but not 2050.

To meet the 1.5 °C target, methane (CH4) from ruminants must be reduced by 11 to 30% by 2030 and 24 to 47% by 2050 compared to 2010 levels. A meta-analysis identified strategies to decrease product-based (PB; CH4 per unit meat or milk) and absolute (ABS) enteric CH4 emissions while maintaining or increasing animal productivity (AP; weight gain or milk yield). Next, the potential of different adoption rates of one PB or one ABS strategy to contribute to the 1.5 °C target was estimated. The database included findings from 430 peer-reviewed studies, which reported 98 mitigation strategies that can be classified into three categories: animal and feed management, diet formulation, and rumen manipulation. A random-effects meta-analysis weighted by inverse variance was carried out. Three PB strategies­namely, increasing feeding level, decreasing grass maturity, and decreasing dietary forage-to-concentrate ratio­decreased CH4 per unit meat or milk by on average 12% and increased AP by a median of 17%. Five ABS strategies­namely CH4 inhibitors, tanniferous forages, electron sinks, oils and fats, and oilseeds­decreased daily methane by on average 21%. Globally, only 100% adoption of the most effective PB and ABS strategies can meet the 1.5 °C target by 2030 but not 2050, because mitigation effects are offset by projected increases in CH4 due to increasing milk and meat demand. Notably, by 2030 and 2050, low- and middle-income countries may not meet their contribution to the 1.5 °C target for this same reason, whereas high-income countries could meet their contributions due to only a minor projected increase in enteric CH4 emissions.

Impact of molar absorbance on anthocyanin content of the foods.

Anthocyanins are present in bright colored fruit and vegetables with growing evidence for their health benefits. Several methods exist in the literature to measure the total monomeric anthocyanin content in foods. Although the simplest method uses UV-Vis spectrophotometry, it requires the use of anthocyanin molar absorption coefficients (Ɛ). While commonly reported for some compounds, these values vary substantially between studies. This study collated and compared existing Ɛ values for a range of anthocyanin-3-glucosides, measured new Ɛ values for these compounds and underwent an inter-laboratory validation of spectrometry methods. The Ɛ values used for the determination of anthocyanin content in Australian blueberries, were shown to greatly affect the estimated total anthocyanin. Significant differences in the Ɛ values were observed when measured at 520 nm, or their absorbance maximum and substantial difference in the estimated total anthocyanins were observed when expressed as equivalent of cya-3-glu or mal-3-glu.

Preferential freezing avoidance localised in anthers and embryo sacs in wintering Daphne kamtschatica var. jezoensis flower buds visualised by magnetic resonance imaging.

To explore diversity in cold hardiness mechanisms, high resolution magnetic resonance imaging (MRI) was used to visualise freezing behaviours in wintering Daphne kamtschatica var. jezoensis flower buds, which have naked florets and no bud scales. MRI images showed that anthers remained stably supercooled to the range from -14 to -21°C or lower while most other tissues froze by -7°C. Freezing of some anthers detected in MRI images between -14 and -21°C corresponded with numerous low temperature exotherms and also with the 'all-or-nothing' type of anther injuries. In ovules/pistils, only embryo sacs remained supercooled at -7°C or lower, but slowly dehydrated during further cooling. Cryomicroscopic observation revealed ice formation in the cavities of calyx tubes and pistils but detected no ice in embryo sacs or in anthers. The distribution of ice nucleation activity in floral tissues corroborated the tissue freezing behaviours. Filaments likely work as the ice blocking barrier that prevents ice intrusion from extracellularly frozen calyx tubes to connecting unfrozen anthers. Unique freezing behaviours were demonstrated in Daphne flower buds: preferential freezing avoidance in male and female gametophytes and their surrounding tissues (by stable supercooling in anthers and by supercooling with slow dehydration in embryo sacs) while the remaining tissues tolerate extracellular freezing.

Diet Quality and Nutrition Behavior of Federal Nutrition Education Program Participants before and during the COVID-19 Pandemic.

Despite challenges due to the COVID-19 pandemic, reports from regional and national meetings of the Expanded Food and Nutrition Education program (EFNEP) have provided anecdotal evidence that the program has persevered, pivoted, and continued to positively impact the lives of some of the nation's most vulnerable populations. However, there have been necessary changes to program delivery, inevitable changes in the lives of participants, and changes in the food environment that may have impacted program outcomes. This study compares national EFNEP data (demographics, behavior change data, and 24 h dietary recall data) of participants from two federal fiscal years, before the COVID-19 pandemic and during the pandemic. Linear mixed model analysis of variance and covariance were used to assess the effects of year on program outcomes. Results of this study provide quantitative evidence of the resiliency of EFNEP to facilitate positive behavior changes related to diet quality, physical activity, food safety, food resource management, and food security. Amidst changes in the food environment during the COVID-19 pandemic, these results emphasize the importance and value of federal nutrition education programs in any food environment.

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.