Diffusiophoresis in suspensions of highly charged soft particles

Diffusiophoresis phenomenon of aoft particles suspended in binary electrolyte solutions is explored theoretically in this study based on the spherical cell model, focusing on the chemiphoresis component in absence of diffusion potential. Both the electrostatic and hydrodynamic aspects of the boundary confinement, or steric effect, due to the presence of neighboring particles are examined extensively under various electrokinetic conditions. Significant local extrema are found in mobility profiles expressed as functions of the Debye length in general, synchronized with the strength of the motion-inducing double layer polarization. Moreover, a seemingly peculiar phenomenon is observed that the soft particles may move faster in more concentrated suspensions. The competition between the simultaneous enhancement of the motion-inducing electric driving force and the motion-retarding hydrodynamic drag force from the boundary confinement effect of the neighboring particles is found to be responsible for it. The above findings are also demonstrated experimentally in a very recent study on the diffusiophoretic motion of soft particles through porous collagen hydrogels. The results presented here are useful in various practical applications of soft particles like drug delivery.     

Nondiffusive spin dynamics in a two-dimensional electron gas

We describe measurements of spin dynamics in the two-dimensional electron gas in GaAs/GaAlAs quantum wells. Optical techniques, including transient spin-grating spectroscopy, are used to probe the relaxation rates of spin polarization waves in the wave vector range from zero to 6x10(4) cm-1. We find that the spin polarization lifetime is maximal at a nonzero wave vector, in contrast with expectations based on ordinary spin diffusion, but in quantitative agreement with recent theories that treat diffusion in the presence of spin-orbit coupling.     

Spatial updating, spatial transients, and regularities of a complex automaton with nonperiodic architecture

We study the dynamics of patterns exhibited by rule 52, a totalistic cellular automaton displaying intricate behaviors and wide regions of active/inactive synchronization patches. Systematic computer simulations involving 2(30) initial configurations reveal that all complexity in this automaton originates from random juxtaposition of a very small number of interfaces delimiting active/inactive patches. Such interfaces are studied with a sidewise spatial updating algorithm. This novel tool allows us to prove that the interfaces found empirically are the only interfaces possible for these periods, independently of the size of the automata. The spatial updating algorithm provides an alternative way to determine the dynamics of automata of arbitrary size, a way of taking into account the complexity of the connections in the lattice.     

Spectral editing in solid-state MAS NMR of quadrupolar nuclei using selective satellite inversion

A sensitivity enhancement method based on selective adiabatic inversion of a satellite transition has been employed in a (pi/2)CT-(pi)ST1-(pi/2)CT spectral editing sequence to both enhance and resolve multisite NMR spectra of quadrupolar nuclei. In addition to a total enhancement of 2.5 times for spin 3/2 nuclei, enhancements up to 2.0 times is reported for the edited sites in a mixture of rubidium salts.     

Three‐Phase Barker Arrays

A 3‐phase Barker array is a matrix of third roots of unity for which all out‐of‐phase aperiodic autocorrelations have magnitude 0 or 1. The only known truly two‐dimensional 3‐phase Barker arrays have size 2 × 2 or 3 × 3. We use a mixture of combinatorial arguments and algebraic number theory to establish severe restrictions on the size of a 3‐phase Barker array when at least one of its dimensions is divisible by 3. In particular, there exists a double‐exponentially growing arithmetic function T such that no 3‐phase Barker array of size with exists for all . For example, , , and . When both dimensions are divisible by 3, the existence problem is settled completely: if a 3‐phase Barker array of size exists, then .     

Perturbation of Spin Crossover Behavior by Covalent Post‐Synthetic Modification of a Porous Metal–Organic Framework

Covalent post‐synthetic modification is a versatile method for gaining high‐level synthetic control over functionality within porous metal–organic frameworks and for generating new materials not accessible through one‐step framework syntheses. Here we apply this topotactic synthetic approach to a porous spin crossover framework and show through detailed comparison of the structures and properties of the as‐synthesised and covalently modified phases that the modification reaction proceeds quantitatively by a thermally activated single‐crystal‐to‐single‐crystal transformation to yield a material with lowered spin‐switching temperature, decreased lattice cooperativity, and altered color. Structure–function relationships to emerge from this comparison show that the approach provides a new route for tuning spin crossover through control over both outer‐sphere and steric interactions.     

A Plausible Simultaneous Synthesis of Amino Acids and Simple Peptides on the Primordial Earth

Following his seminal work in 1953, Stanley Miller conducted an experiment in 1958 to study the polymerization of amino acids under simulated early Earth conditions. In the experiment, Miller sparked a gas mixture of CH₄, NH₃, and H₂O, while intermittently adding the plausible prebiotic condensing reagent cyanamide. For unknown reasons, an analysis of the samples was not reported. We analyzed the archived samples for amino acids, dipeptides, and diketopiperazines by liquid chromatography, ion mobility spectrometry, and mass spectrometry. A dozen amino acids, 10 glycine‐containing dipeptides, and 3 glycine‐containing diketopiperazines were detected. Miller’s experiment was repeated and similar polymerization products were observed. Aqueous heating experiments indicate that Strecker synthesis intermediates play a key role in facilitating polymerization. These results highlight the potential importance of condensing reagents in generating diversity within the prebiotic chemical inventory.