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101.
Zachary S. Kean Dr. Sergey Akbulatov Dr. Yancong Tian Prof. Ross A. Widenhoefer Dr. Roman Boulatov Prof. Stephen L. Craig 《Angewandte Chemie (International ed. in English)》2014,53(52):14508-14511
A catalyst that couples a photoswitch to the biaryl backbone of a chiral bis(phosphine) ligand, thus allowing photochemical manipulation of ligand geometry without perturbing the electronic structure is reported. The changes in catalyst activity and selectivity upon switching can be attributed to intramolecular mechanical forces, thus laying the foundation for a new class of catalysts whose selectivity can be varied smoothly and in situ over a useful range by controlling molecular stress experienced by the catalyst during turnover. Forces on the order of 100 pN are generated, thus leading to measurable changes in the enantioselectivities of asymmetric Heck arylations and Trost allylic alkylations. The differential coupling between applied force and competing stereochemical pathways is quantified and found to be more efficient for the Heck arylations. 相似文献
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Stacey M. Frumm Zi Peng Fan Kenneth N. Ross Jeremy R. Duvall Supriya Gupta Lynn VerPlank Byung-Chul Suh Edward Holson Florence F. Wagner William B. Smith Ronald M. Paranal Christopher F. Bassil Jun Qi Giovanni Roti Andrew L. Kung James E. Bradner Nicola Tolliday Kimberly Stegmaier 《Chemistry & biology》2013,20(5):713-725
104.
Ross F. Koby Alicia M. Doerr Nicholas R. Rightmire Nathan D. Schley Dr. William W. Brennessel Prof. Brian K. Long Prof. Timothy P. Hanusa 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(31):8195-8202
Without solvents present, the often far-from-equilibrium environment in a mechanochemically driven synthesis can generate high-energy, non-stoichiometric products not observed from the same ratio of reagents used in solution. Ball milling 2 equiv. K[A’] (A’=[1,3-(SiMe3)2C3H3]−) with CaI2 yields a non-stoichiometric calciate, K[CaA’3], which initially forms a structure ( 1 ) likely containing a mixture of pi- and sigma-bound allyl ligands. Dissolved in arenes, the compound rearranges over the course of several days to a structure ( 2 ) with only η3-bound allyl ligands, and that can be crystallized as a coordination polymer. If dissolved in alkanes, however, the rearrangement of 1 to 2 occurs within minutes. The structures of 1 and 2 have been modeled with DFT calculations, and 2 initiates the anionic polymerization of methyl methacrylate and isoprene; for the latter, under the mildest conditions yet reported for a heavy Group 2 species (one-atm pressure and room temperature). 相似文献
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M.J. Grosskopf R.P. Drake C.C. Kuranz E.M. Rutter J.S. Ross N.L. Kugland C. Plechaty B.A. Remington A. Spitkovsky L. Gargate G. Gregori A. Bell C.D. Murphy J. Meinecke B. Reville Y. Sakawa Y. Kuramitsu H. Takabe H.-S. Park 《High Energy Density Physics》2013,9(1):192-197
Experiments investigating the physics of interpenetrating, collisionless, ablated plasma flows have become an important area of research in the high-energy-density field. In order to evaluate the feasibility of designing experiments that will generate a collisionless shock mediated by the Weibel instability on the National Ignition Facility (NIF) laser, computer simulations using the Center for Radiative Shock Hydrodynamics (CRASH) radiation-hydrodynamics model have been carried out. This paper reports assessment of whether the experiment can reach the required scale size while maintaining the low interflow collisionality necessary for the collisionless shock to form. Comparison of simulation results with data from Omega experiments shows the ability of the CRASH code to model these ablated systems. The combined results indicate that experiments on the NIF are capable of reaching the regimes necessary for the formation of a collisionless shock in a laboratory experiment. 相似文献
110.
Ionizable amino acids in protein‐based hydrogels can confer pH‐responsive behavior. Because elastin‐like polypeptides (ELPs) have an established sequence and can crosslink to form hydrogels, they are an ideal system for creating pH‐sensitive materials. This study examines different parameters that might affect pH‐sensitive behavior and characterizes the mechanical and physical properties between pH 3 and 11 of three ELP‐based crosslinked hydrogels. The first finding is that varying the amount of crosslinker affects the overall stiffness and resilience of the hydrogels but does not strongly affect water content, swelling ratio, or pH sensitivity. Second, the choice of two popular tag sequences, which vary in histidine and aspartic acid content, does not have a strong effect on pH‐sensitive properties. Last, selectively blocking lysine and tyrosine residues through acetylation significantly decreases the pH‐sensitive zeta potential. Acetylated hydrogels also demonstrate different behavior at low pH values with reduced swelling, reduced water content, and higher stiffness. Overall, this work demonstrates that ELP hydrogels with ionizable groups are promising materials for environmentally‐responsive applications such as drug delivery, tissue engineering, and microfluidics. 相似文献