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Reactions on post-transition-state bifurcation (PTSB) energy surfaces are an important class of reaction in which classical rate theories, such as the transition state theory, fail to account for the selectivity. Quasiclassical trajectory molecular dynamic (QCT-MD) simulation is an important computational approach to understanding reactions mechanisms, especially for reactions that cannot be predicted from conventional rate theories. However, the applicability of direct dynamic simulations is hampered by huge computational costs for collecting a statistically meaningful set of trajectories, making it difficult to compare simulation results with theoretical or physical insights-based predictions (non-MD predictions). In this work, we examine the PTSB of Schmidt-Aubé reactions studied by Tantillo and co-workers. With machine-learning using kernel-ridge regression (KRR) to predict atomic forces, statistical reliability was enhanced by significantly increasing the number of trajectories. With KRR, the bottleneck of simulating dynamics (atomic forces in QCT-MD with density functional theory) was accelerated more than 100-fold. We found that this KRR-aided QCT-MD approach is successful in predicting branching ratios with a much larger number of trajectories. With our approach, statistical errors are greatly reduced, and hypothetical non-MD models for predicting selectivity are tested with much higher confidence. By comparison with non-MD models, dynamical properties that affect branching ratios become more clearly described.

The recently developed Quasiparticle Energy (QE) scheme, based on a DFT calculation with one more (or less) electron, offers a good description of excitation energies, even with charge transfer characters. In this work, QE is further extended to calculate electron transfer (ET) couplings involving two excited states. We tested it with a donor-acceptor complex, consisting of a furan and a 1,1-dicyanoethylene (DCNE), in which two low lying charge transfer and local excitation states are involved. With generalized Mülliken-Hush and fragment charge-difference schemes, couplings from the QE approach generally agree well with those obtained from TDDFT, except that QE couplings exhibit better exponential distance dependence. Couplings from half-energy gaps with an external field are also calculated and reported. Our results show that the QE scheme is robust in calculating ET couplings with greatly reduced computational time.

Stimuli-responsive materials are increasingly needed for the development of smart electronic, mechanical, and biological devices and systems relying on switchable, tunable, and adaptable properties. Herein, we report a novel pH- and temperature-responsive binary supramolecular assembly involving a long-chain hydroxyamino amide (HAA) and an inorganic hydrotrope, boric acid, with highly tunable viscous and viscoelastic properties. The system under investigation demonstrates a high degree of control over its viscosity, with the capacity to achieve over four orders of magnitude of control through the concomitant manipulation of pH and temperature. In addition, the transformation from non-Maxwellian to Maxwellian fluid behavior could also be induced by changing the pH and temperature. Switchable rheological properties were ascribed to the morphological transformation between spherical vesicles, aggregated/fused spherical vesicles, and bicontinuous gyroid structures revealed by cryo-TEM studies. The observed transitions are attributed to the modulation of the head group spacing between HAA molecules under different pH conditions. Specifically, acidic conditions induce electrostatic repulsion between the protonated amino head groups, leading to an increased spacing. Conversely, under basic conditions, the HAA head group spacing is reduced due to the intercalation of tetrahydroxyborate, facilitated by hydrogen bonding.

Luteolin (LUT), a plant-derived flavone, exhibits various bioactivities; however, the poor aqueous solubility hampers its applications. Here, we revealed bioconversion of LUT by Bacillus subtilis BCRC 80517, yielding three water-soluble phosphate conjugates. These derivatives were identified as luteolin 4'- O -phosphate ( L4'P ), luteolin 3'- O -phosphate ( L3'P ), and luteolin 7- O -phosphate ( L7P ) by LC-ESI-MS/MS and NMR. Besides, we found that Bacillus subtilis BCRC 80517 was able to convert different levels of LUT but showed a limited conversion rate. By observing bacterial morphology with transmission electron microscopy and confocal fluorescence microscopy, we found that LUT disrupted the bacterial membrane integrity, which explained the incomplete conversion. Additionally, we revealed a spontaneous intramolecular transesterification of L4'P to L3'P , the thermodynamically more stable form, under acidic conditions and proposed the possible mechanism involving a cyclic phosphate as the intermediate. This study provides insight into development of a potent structural modification strategy to enhance the solubility of LUT through biophosphorylation.

Viscosity modifying agents are one of the most critical components of hydraulic fracturing fluids, ensuring the efficient transport and deposition of proppant into fissures. To improve the productivity index of hydraulic fracturing processes, better viscosifiers with a higher proppant carrying capacity and a lower potential of formation damage are needed. In this work, we report the development of a novel viscoelastic system relying on the complexation of zwitterionic octadecylamidopropyl betaine (OAPB) and diethylenetriamine (DTA) in water. At a concentration of 2 wt%, the zwitterionic complex fluid had a static viscosity of 9 to 200 poise, which could be reversibly adjusted by changing the suspension pH. The degree of pH-responsiveness ranged from 10 to 27 depending on the shear rate. At a given concentration and optimum pH value, the zwitterionic viscosifiers showed a two-orders-of-magnitude reduction in settling velocity of proppant compared to polyacrylamide solution (slickwater). By adjusting the pH between 4 and 8, the networked structure of the gel could be fully assembled and disassembled. The lack of macromolecular residues at the dissembled state can be beneficial for hydraulic fracturing application in avoiding the permeation damage issues encountered in polymer and linear-gel-based fracturing fluids. The reusability and the unnecessary permanent breakers are other important characteristics of these zwitterionic viscosifiers., Competing Interests: The authors declare that there is no conflict of interest., (This journal is © The Royal Society of Chemistry.)

13 C kinetic isotope effects (KIEs) for the photoredox-promoted [2 + 2] cycloaddition of enones were determined in homocoupling and heterocoupling examples. The only significant KIEs were observed at the β carbon, indicating that C β -C β bond formation is irreversible. However, these KIEs were much lower than computational predictions, suggesting that product selectivity is determined in part by a step prior to C β -C β bond formation. The results are explained as arising from a competition between C-C bond formation and electron exchange between substrate alkenes. This idea is supported by a relatively small substituent effect on substrate selectivity. The possible rates for electron transfer and bond-forming steps are analyzed, and the competition appears plausible, particularly if the mechanism involves a complex between reduced and neutral enone molecules.

Multi-component reactions assemble complex molecules in a highly effective way, however, they often suffer from long reaction times. We demonstrate that acceleration of a five-component spiro-pyrrolidine construction can be achieved in microdroplets and thin films. The deposition method and mild heating are crucial factors for product formation. Three key intermediates were captured by mass spectrometry to elucidate the tandem reaction mechanism. We also found that hydrogen bonding can significantly flatten the energy barrier at the air-liquid interface.

Large intramolecular 13 C kinetic isotope effects (KIEs) for the di-π-methane rearrangement of benzobarrelene fit with statistical expectations from heavy-atom tunneling when a low-energy sensitizer is employed, but much lower KIEs are observed with higher-energy sensitizers. These results in combination with trajectory studies suggest that the excess vibrational energy available from triplet energy transfer leads to hot and nonstatistical dynamics in the rearrangement.

Studies extending across multiple life stages promote an understanding of factors influencing health across the life span. Existing work has largely focused on individual-level rather than area-level early life determinants of health. In this study, we linked multiple data sets to examine whether early life state-level characteristics were predictive of health and mortality decades later. The sample included 143,755 U.S. employees, for whom work life claims and administrative data were linked with early life state-of-residence and mortality. We first created a "state health risk score" (SHRS) and "state mortality risk score" (SMRS) by modeling state-level contextual characteristics with health status and mortality in a randomly selected 30% of the sample (the "training set"). We then examined the association of these scores with objective health status and mortality in later life in the remaining 70% of the sample (the "test set") using multivariate linear and Cox regressions, respectively. The association between the SHRS and adult health status was β=0.14 (95%CI: 0.084, 0.20), while the hazard ratio for the SMRS was 0.96 (95%CI: 0.93, 1.00). The association between the SHRS and health was not statistically significant in older age groups at a p-level of 0.05, and there was a statistically significantly different association for health status among movers compared to stayers. This study uses a life course perspective and supports the idea of "sensitive periods" in early life that have enduring impacts on health. It adds to the literature examining populations in the U.S. where large linked data sets are infrequently available.