Phonons localized at step edges: a route to understanding forces at extended surface defects

Inelastic helium atom scattering has been used to measure the phonons on a stepped metallic crystalline surface, Ni(977). When the scattering plane is oriented parallel to the step edges and perpendicular to the terraces, two branches of step-induced phonons are observed. These branches are identified as transversely polarized, step-localized modes that propagate along the step edge. Analysis reveals significant anisotropy in the force field near the step edge, with all forces near the step edge being substantially smaller than in the bulk. Such measurements provide valuable information on metallic bonding and interface stability near extended surface defects.     

Molecular recognition at crystal interfaces

Nucleation, growth, and dissolution of crystals have been studied by stereochemical approach involving molecular recognition at interfaces. A methodology is described for using ;;tailor-made' additives designed to interact stereospecifically with crystal surfaces during growth and dissolution. This procedure was instrumental in controlling crystal morphology and in revising the concept of the structure and symmetry of solid solutions. Consequently, it was applied to the transformation of centrosymmetric single crystals into solid solutions with polar arrangement displaying second-harmonic generation and to the performance of asymmetric synthesis of guest molecules inside centrosymmetric host crystals. The method has led to a discovery of a new ;;relay' mechanism explaining the effect of solvent on crystal growth. Finally, it allowed for the design of auxiliary molecules that act as promoters or inhibitors of crystal nucleation that can be used to resolve enantiomers and crystallize desired polymorphs.     

Nanoparticle assembly and transport at liquid-liquid interfaces

The self-assembly of particles at fluid interfaces, driven by the reduction in interfacial energy, is well established. However, for nanoscopic particles, thermal fluctuations compete with interfacial energy and give rise to a particle-size-dependent self-assembly. Ligand-stabilized nanoparticles assembled into three-dimensional constructs at fluid-fluid interfaces, where the properties unique to the nanoparticles were preserved. The small size of the nanoparticles led to a weak confinement of the nanoparticles at the fluid interface that opens avenues to size-selective particle assembly, two-dimensional phase behavior, and functionalization. Fluid interfaces afford a rapid approach to equilibrium and easy access to nanoparticles for subsequent modification. A photoinduced transformation is described in which nanoparticles, initially soluble only in toluene, were transported across an interface into water and were dispersed in the water phase. The characteristic fluorescence emission of the nanoparticles provided a direct probe of their spatial distribution.     

Photo-tautomerization of acetaldehyde to vinyl alcohol: a potential route to tropospheric acids

Current atmospheric models underestimate the production of organic acids in the troposphere. We report a detailed kinetic model of the photochemistry of acetaldehyde (ethanal) under tropospheric conditions. The rate constants are benchmarked to collision-free experiments, where extensive photo-isomerization is observed upon irradiation with actinic ultraviolet radiation (310 to 330 nanometers). The model quantitatively reproduces the experiments and shows unequivocally that keto-enol photo-tautomerization, forming vinyl alcohol (ethenol), is the crucial first step. When collisions at atmospheric pressure are included, the model quantitatively reproduces previously reported quantum yields for photodissociation at all pressures and wavelengths. The model also predicts that 21 ± 4% of the initially excited acetaldehyde forms stable vinyl alcohol, a known precursor to organic acid formation, which may help to account for the production of organic acids in the troposphere.     

Reactions at interfaces as a source of sulfate formation in sea-salt particles

Understanding the formation of sulfate particles in the troposphere is critical because of their health effects and their direct and indirect effects on radiative forcing, and hence on climate. Laboratory studies of the chemical and physical changes in sodium chloride, the major component of sea-salt particles, show that sodium hydroxide is generated upon reaction of deliquesced sodium chloride particles with gas-phase hydroxide. The increase in alkalinity will lead to an increase in the uptake and oxidation of sulfur dioxide to sulfate in sea-salt particles. This chemistry is missing from current models but is consistent with a number of previously unexplained field study observations.     

Collagen gels: design for a vitreous replace- ment

Clear, stable gels have been prepared from purified tropocollagen from calf skin; the collagen was solubilized with a proteolytic enzyme (Proctase) and stabilized by ultraviolet irradiation under nitrogen. These gels are clear, possess altered immunologic reactivity, and have properties of an ideal vitreous replacement. Implantations in rabbit and monkey eyes appear to be well tolerated, remain clear, and gradually disappear in about 2 months.     

Vertical aluminophosphate molecular sieve crystals grown at inorganic-organic interfaces

Tubular aluminophosphate molecular sieve crystals were grown at an organic interface with their channels (7 angstroms in cross section) vertical to the substrate. To induce surface nucleation and oriented growth of AIPO(4)-5 crystals, organophosphonate layers cross-linked with Zr(IV) were assembled on a gold substrate and the modified substrate was immersed in a hydrothermal bath containing reagents for the synthesis of the molecular sieve. Reflection-absorption infrared studies demonstrated the stability of the phosphonate layers under these conditions. Drastic changes in the morphology of the surface-grown crystals from spherical agglomerates to vertical needles to thin tilted needles could be achieved by adjusting the water content of the synthesis bath. Nitrogen sorption in these structures on a piezoelectric device confirmed the presence of zeolitic microporosity.     

Threonine deaminase: a novel activity stain on polyacrylamide gels

With phenazine methosulfate and nitro blue tetrazolium, an activity stain for threonine deaminase has been developed. Because the deamination reaction does not involve any overall oxidation or reduction, it is proposed that one of the intermediates of the reaction, alpha-aminocrotonate or alpha-iminobutyrate, is the reducing agent. Studies with ferricyanide as the artificial electron acceptor indicate that a decarboxylation of the intermediate occurs during the dye reduction.     

A chiral route to negative refraction

Negative refraction is currently achieved by driving the magnetic permeability and electrical permittivity simultaneously negative, thus requiring two separate resonances in the refracting material. The introduction of a single chiral resonance leads to negative refraction of one polarization, resulting in improved and simplified designs of negatively refracting materials and opening previously unknown avenues of investigation in this fast-growing subject.     

Galactose conversion to D-xylulose: an alternate route of galactose metabolism

Galactose dehydrogenase, a soluble enzyme of the mammalian liver, catalyzes the conversion of galactose to galactonic acid. This reaction, together with the subsequent formation of 3-ketogalactonic acid which can be decarboxylated to yield d-xylulose, is a newly discovered pathway for the metabolism of galactosee. This pathway may account for the oxidation of galactose observed in pathients with galactosemia.     

Colloidal solution of water in organic solvents: a microheterogeneous medium for enzymatic reactions

To simulate in vitro the conditions under which enzymes act in vivo, enzyme molecules have been entrapped in hydrated reverse micelles of a surfactant in organic solvents. In this system the catalytic activity of one of the enzymes studied (peroxidase) became much higher than in water, and the specificity of the other enzyme (alcohol dehydrogenase) was dramatically altered.     

在不同温度下土壤胶体分散系稳定性分析

本文采用土壤胶体Zeta电位测定仪测定了砒砂岩、沙、5种比例砒砂岩与沙复配土、4个年份盐碱土共11种材料在不同温度下的Zeta电位值,分析了不同材料在相同温度范围内的Zeta电位特性和趋势,评价不同材料的胶体分散系稳定性。