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1.
Influence theory is a foundational theory of physics that is not based on traditional empirically defined concepts, such as positions in space and time, mass, energy, or momentum. Instead, the aim is to derive these concepts, and their empirically determined relationships, from a more primitive model. It is postulated that there exist things, which are call particles, that influence one another in a discrete and directed fashion resulting in a partially ordered set of influence events. The problem of consistent quantification of the influence events is considered. Observers are modeled as particle chains (observer chains) as if an observer were able to track a particle and quantify the influence events that the particle experiences. From these quantified influence events, consistent quantification of the universe of events based on the observer chains is studied. Herein, the kinematics and dynamics of particles from the perspective of influence theory are both reviewed and further developed. 相似文献
2.
Haixing Guan Qianwen Zhang Prof. Dr. Patrick J. Walsh Prof. Dr. Jianyou Mao 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(13):5210-5215
A unique nickel/organic photoredox co-catalyzed asymmetric reductive cross-coupling between α-chloro esters and aryl iodides is developed. This cross-electrophile coupling reaction employs an organic reductant (Hantzsch ester), whereas most reductive cross-coupling reactions use stoichiometric metals. A diverse array of valuable α-aryl esters is formed under these conditions with high enantioselectivities (up to 94 %) and good yields (up to 88 %). α-Aryl esters represent an important family of nonsteroidal anti-inflammatory drugs. This novel synergistic strategy expands the scope of Ni-catalyzed reductive asymmetric cross-coupling reactions. 相似文献
3.
4.
Wenjun Yang Bo Ling Bowen Hu Haolin Yin Prof. Dr. Jianyou Mao Prof. Dr. Patrick J. Walsh 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(1):167-172
An umpolung 1,4-addition of aryl iodides to enals promoted by cooperative (terpy)Pd/NHC catalysis was developed that generates various bioactive β,β-diaryl propanoate derivatives. This system is not only the first reported palladium-catalyzed arylation of NHC-bound homoenolates but also expands the scope of NHC-induced umpolung transformations. A diverse array of functional groups such as esters, nitriles, alcohols, and heterocycles are tolerated under the mild conditions. This method also circumvents the use of moisture-sensitive organometallic reagents. 相似文献
5.
Louise B. Wright J. Pablo Palafox-Hernandez P. Mark Rodger Stefano Corni Tiffany R. Walsh 《Chemical science》2015,6(9):5204-5214
Peptide sequences that can discriminate between gold facets under aqueous conditions offer a promising route to control the growth and organisation of biomimetically-synthesised gold nanoparticles. Knowledge of the interplay between sequence, conformations and interfacial properties is essential for predictable manipulation of these biointerfaces, but the structural connections between a given peptide sequence and its binding affinity remain unclear, impeding practical advances in the field. These structural insights, at atomic-scale resolution, are not easily accessed with experimental approaches, but can be delivered via molecular simulation. A current unmet challenge lies in forging links between predicted adsorption free energies derived from enhanced sampling simulations with the conformational ensemble of the peptide and the water structure at the surface. To meet this challenge, here we use an in situ combination of Replica Exchange with Solute Tempering with Metadynamics simulations to predict the adsorption free energy of a gold-binding peptide sequence, AuBP1, at the aqueous Au(111), Au(100)(1 × 1) and Au(100)(5 × 1) interfaces. We find adsorption to the Au(111) surface is stronger than to Au(100), irrespective of the reconstruction status of the latter. Our predicted free energies agree with experiment, and correlate with trends in interfacial water structuring. For gold, surface hydration is predicted as a chief determining factor in peptide–surface recognition. Our findings can be used to suggest how shaped seed-nanocrystals of Au, in partnership with AuBP1, could be used to control AuNP nanoparticle morphology. 相似文献
6.
When poly(ethylene terephthalate) was quenched from above Tg and then heated, it exhibited a step increase in thickness in the glass transition region at every rate tested. When the polymer was cooled more slowly than it was heated, a higher Tg and a slightly larger step increase in thickness were observed as the cooling rate was reduced. These experimental results appear to be adequately interpreted on the basis of the normal structural changes that occur in a glass as its thermal history is varied. Two observations, however, were not easily included in this view. First, the polymer, on cooling from above Tg, exhibited an abnormally high expansion coefficient over much of the range of temperature in which it exists as a fluid. Second, the polymer exhibited a step increase in thickness when it was heated at the same rate at which it had previously been cooled. 相似文献
7.
Polyethersulfone has been shown to be miscible with phenoxy resin. Cast films were found to be clear and show a single, composition-dependent glass transition-Blends were found to phase separate on heating with a lower critical solution temperature around 185°C. The heat of mixing of low molecular weight analogs was small and negative, suggesting a favorable interaction between the polymers. Phase diagrams were simulated using the equation-of-state theory of Flory and co-workers and were found to agree closely with the observed behavior. The water vapor sorption of the blends was investigated, and this also suggested a weak favorable interaction between the polymers. 相似文献
8.
Control of chemoselectivity is one of the most challenging problems facing chemists and is particularly important in the synthesis of bioactive compounds and medications. Herein, the first highly chemoselective tandem C(sp3)–H arylation/[1,2]-Wittig rearrangement of pyridylmethyl ethers is presented. The efficient and operationally simple protocols enable generation of either arylation products or tandem arylation/[1,2]-Wittig rearrangement products with remarkable selectivity and good to excellent yields (60–99%). Choice of base, solvent, and reaction temperature play a pivotal role in tuning the reactivity of intermediates and controlling the relative rates of competing processes. The novel arylation step is catalyzed by a Pd(OAc)2/NIXANTPHOS-based system via a deprotonative cross-coupling process. The method provides rapid access to skeletally diverse aryl(pyridyl)methanol core structures, which are central components of several medications. 相似文献
9.
A procedure for the selective deprotection of p-methoxybenzyl ethers using catalytic amounts of DDQ and of sodium nitrite, with oxygen as the terminal oxidant, is reported. 相似文献
10.
The syntheses of boronates derived from the reaction of dioxaborolanes and dioxaborinanes with either organolithium or organomagnesium reagents are investigated along with their subsequent use in the palladium cross coupling reaction. The intrinsic stability of these cyclic esters contributes to their facile reaction with both lithium and magnesium nucleophiles at mild and safe conditions. We have found that many of the reactions proceed at room temperature which is a significant improvement over the traditional routes which require cryogenic temperatures. The scope of these reactions and their practical application to large scale process synthesis is described. 相似文献