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In this study, a well-defined organic capsule assembled from two octa acid (OA) molecules acting as host and select arylazoisoxazoles (AAIO) acting as guests were employed to demonstrate that confined molecules have restricted freedom that translates into reaction selectivity in both ground and excited states. The behavior of these AAIO guests in confined capsules was found to be different from that found in both crystals, where there is very little freedom, and in isotropic solvents, where there is complete freedom. Through one-dimensional (1D) and two-dimensional (2D) 1H NMR spectroscopic experiments, we have established a relationship between structure, dynamics and reactivity of molecules confined in an OA capsule. Introduction of CF3 and CH3 substitution at the 4-position of the aryl group of AAIO reveals that in addition to space confinement, weak interactions between the guest and the OA capsule control the dynamics and reactivity of guest molecules. 1H NMR studies revealed that there is a temperature-dependence to guest molecules tumbling (180° rotation along the capsular short axis) within an OA capsule. While 1H NMR points to the occurrence of tumbling motion, MD simulations and simulation of the temperature-dependent NMR signals provide an insight into the mechanism of tumbling within OA capsules. Thermal and photochemical isomerization of AAIO were found to occur within an OA capsule just as in organic solvents. The observed selectivity noted during thermal and photo induced isomerization of OA encapsulated AAIOs can be qualitatively understood in terms of the well-known concepts due to Bell−Evans− Polanyi (BEP principle), Hammond and Zimmerman. 

Abstract In this work, we examine the effects of spatial dephasing of coherences on the transmission and reflection probabilities for electrons with energyEincident to a one-dimensional rectangular barrier of heightV₀. Statistical models are presented where the coherence between different scattering pathways or ‘Feynman paths’ undergo dephasing over a length scale,L_ϕ. For incident waves withE>V₀, three different dephasing models that attenuate the contributions of spatial coherence to the transmission and reflection probabilities while preserving unitarity (i.e., conserving charge) were investigated. In the tunneling regime (incident waves withE<V₀), however, preserving unitarity requiresL_ϕ→ ∞ , suggesting that elastic tunneling through a rectangular barrier is 100% spatially coherent for these dephasing models. However, wave absorption models are shown to preserve unitarity in the tunneling regime, which is not the case for scattering above the barrier. 

Spectra and images derived from the Fourier transformation of time-domain signals can often exhibit overshoots and/or “ringing” near sharp features. Such artifacts are due to the slow convergence of the Fourier series near such features, an effect referred to as the Gibbs phenomenon. While usually viewed as being purely mathematical in origin, the Gibbs phenomenon can often be found in a variety of physical situations, such as in imaging and spectroscopy. In this work, a physical description of the Gibbs phenomenon is presented where it is interpreted as an interference effect whereby slower destructive interference or “Fourier dephasing” occurs near sharp spectral features compared with the Fourier dephasing observed away from such features. Differences in Fourier dephasing can be exploited to localize magnetization near physical boundaries on timescales about an order of magnitude faster than can be achieved using conventional frequency or spatially selective pulses. This localization, which is reversible, also occurs on much faster timescales than can be attributed to irreversible sources, such as restricted diffusion or spatial variations of the intrinsic spin relaxation within the sample. 

In this work, the second-order kinetics of molecules exchanging between chemically distinct microenvironments, such as those found in nanoemulsions, is studied using nuclear magnetic resonance (NMR). A unique aspect of NMR exchange studies in nanoemulsions is that the difference in molecular resonance frequencies between the two phases, which determines whether the exchange is fast, intermediate, or slow on the NMR timescale, can depend upon the emulsion droplet composition, which is also determined by the kinetic exchange constants themselves. Within the fast-exchange regime, changes in resonance frequencies and line widths with dilution were used to extract the exchange rate constants from the NMR spectra in a manner analogous to determining the kinetic parameters in NMR ligand binding experiments. As a demonstration, the kinetic exchange parameters of isoflurane release from an emulsification of isoflurane and perflurotributylamine (FC43) were determined using NMR dilution and diffusion studies.