Strain‐Promoted Cycloaddition of Cyclopropenes with o‐Quinones: A Rapid Click Reaction

Novel click reactions are of continued interest in fields as diverse as bio‐conjugation, polymer science and surface chemistry. Qualification as a proper “click” reaction requires stringent criteria, including fast kinetics and high conversion, to be met. Herein, we report a novel strain‐promoted cycloaddition between cyclopropenes and o‐quinones in solution and on a surface. We demonstrate the “click character” of the reaction in solution and on surfaces for both monolayer and polymer brush functionalization.     

A Criterion for Relative Compactness of a Sequence of Measure-Valued Random Processes

A criterion for relative compactness of a sequence of measure-valued processes is proved and exemplified.     

Water molecules in a protein cavity detected by a statistical-mechanical theory

Four water molecules confined in a small cavity of hen egg-white lysozyme were detected by means of the three-dimensional (3D) RISM theory, a statistical-mechanical theory of molecular solutions. This is the first theoretical realization of confined molecules in a protein without making nonsense tricks, such as placing the molecules in the space a priori. Possible impacts which the result may have on biochemistry and biophysics, including the molecular recognition, enzymatic reactions, etc., are discussed.     

Surface segregation of dissolved salt ions

Surface segregation of iodide, but not of fluoride or cesium ions, is observed by a combination of metastable impact electron spectroscopy (MIES) and ultraviolet photoelectron spectroscopy (UPS(HeI)) of amorphous solid water exposed to CsI or CsF vapor. The same surface ionic behavior is also derived from molecular dynamics (MD) simulations of the corresponding aqueous salt solutions. The MIES results show the propensity of iodide, but not fluoride, for the surface of the amorphous solid water film, providing thus strong evidence for the suggested presence of heavier halides (iodide, bromide, and to a lesser extent chloride) at the topmost layer of aqueous surfaces. In contrast, no appreciable surface segregation of ions is observed in methanol, neither in the experiment nor in the simulation. Furthermore, the present results indicate that, as far as the thermodynamic aspects of solvation of alkali halides are concerned, amorphous solid water and methanol surfaces behave similarly as surfaces of the corresponding liquids.     

Band-limited refinable functions for wavelets and framelets

Extending band-limited constructions of orthonormal refinable functions, a special class of periodic functions is used to generate a family of band-limited refinable functions. Characterizations of Riesz bases and frames formed by integer shifts of these refinable functions are obtained. Such families of refinable functions are employed to construct band-limited biorthogonal wavelet bases and biframes with desirable time-frequency localization.     

On the tricritical point on the (p,T)-phase diagram of Sn2P2S6 crystals

Using studies of the temperature dependence of the acoustic wave velocity at high hydrostatic pressures, a tricritical point where second-order phase transitions change to first-order ones was experimentally revealed on the pressure–temperature phase diagram of Sn₂P₂S₆ crystals. The behavior of the acoustic wave velocity is explained in the framework of mean-field theory.