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This article presents reaction rate data for the simple hydrolysis of acetic anhydride in the acetonitrile/water and acetone/water cosolvent systems and regression analyses using recently developed thermodynamic rate equations that contain electrostatic and solvent-solute terms. The isomole fraction plots for these reaction systems are linear, and previous theoretical work has shown that the electrostatic term is negligible for such systems. On the other hand, the reaction rates are dependent upon the cosolvent mole fraction, indicating that the solvent-solute term, which is modeled empirically, is significant. The results of the analyses provide the foundation for a paradigm shift away from the emphasis on electrostatic effects to more tenable explanations of kinetic behavior in solvent systems. 相似文献
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H. M. Wiseman 《Foundations of Physics》1998,28(11):1619-1631
Heisenberg's position-measurement-momentum-disturbance relation is derivable from the uncertainty relation (q)(p) h/2 only for the case when the particle is initially in a momentum eigenstate. Here I derive a new measurement-disturbance relation which applies when the particle is prepared in a twin-slit superposition and the measurement can determine at which slit the particle is present. The relation is d × p 2h/, where d is the slit separation and p = DM(Pf, Pi) is the Monge distance between the initial Pi(p) and final Pf(p) momentum distributions. 相似文献
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The orientation of a monoclonal, anti-streptavidin human IgG1 antibody on a model hydrophobic, CH(3)-terminated surface (1-dodecanethiol self-assembled monolayer on gold) was studied by monitoring the mechanical coupling between the adsorbed layer and the surface as well as the binding of molecular probes to the antibodies. In this study, the streptavidin antigen was used as a probe for the Fab portions of the antibody, while bacteria-derived Protein G' was used as a probe for the Fc region. Bovine serum albumin (BSA) acted as a blocking protein. Monolayer coverage occurred around 468 ng/cm(2). Below 100 ng/cm(2), antibodies were found to adsorb flat-on, tightly coupled to the surface and unable to capture their antigen, whereas the Fc region was able to bind Protein G'. At half-monolayer coverage, there was a transition in the mechanism of adsorption to allow for vertically oriented antibodies, as evidenced by the binding of both Protein G' and streptavidin as well as looser mechanical coupling with the surface. Monolayer coverage was characterized by a reduced level in probe binding per antibody and an even less rigid coupling to the surface. 相似文献
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The 1964 theorem of John Bell shows that no model that reproduces the predictions of quantum mechanics can simultaneously satisfy the assumptions of locality and determinism. On the other hand, the assumptions of signal locality plus predictability are also sufficient to derive Bell inequalities. This simple theorem, previously noted but published only relatively recently by Masanes, Acin and Gisin, has fundamental implications not entirely appreciated. Firstly, nothing can be concluded about the ontological assumptions of locality or determinism independently of each other—it is possible to reproduce quantum mechanics with deterministic models that violate locality as well as indeterministic models that satisfy locality. On the other hand, the operational assumption of signal locality is an empirically testable (and well-tested) consequence of relativity. Thus Bell inequality violations imply that we can trust that some events are fundamentally unpredictable, even if we cannot trust that they are indeterministic. This result grounds the quantum-mechanical prohibition of arbitrarily accurate predictions on the assumption of no superluminal signalling, regardless of any postulates of quantum mechanics. It also sheds a new light on an early stage of the historical debate between Einstein and Bohr. 相似文献
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