Cooperative formation of inorganic-organic interfaces in the synthesis of silicate mesostructures

A model is presented to explain the formation and morphologies of surfactant-silicate mesostructures. Three processes are identified: multidentate binding of silicate oligomers to the cationic surfactant, preferential silicate polymerization in the interface region, and charge density matching between the surfactant and the silicate. The model explains present experimental data, including the transformation between lamellar and hexagonal mesophases, and provides a guide for predicting conditions that favor the formation of lamellar, hexagonal, or cubic mesostructures. Model Q(230) proposed by Mariani and his co-workers satisfactorily fits the x-ray data collected on the cubic mesostructure material. This model suggests that the silicate polymer forms a unique infinite silicate sheet sitting on the gyroid minimal surface and separating the surfactant molecules into two disconnected volumes.     

Explosive molecular ionic crystals

In ionic crystals of the form M(+)X(-), certain covalently bonded anion groups X(-) are particularly associated with instability. The heavier metal cations M(+) enhance this. Very sensitive explosives occur within the extended azide family, where X(-) = CNO(-), N(3)(-), NCO(-), or NCS(-) (an isoelectronic set of unsaturated linear triatomic anions). Another such family are the globular oxyanions X(-) = ClO(2)(-), ClO(3)(-), ClO(4)(-), NO(3)(-), and MnO(4)(-). Mishandling of NH(4)NO(3) or NH(4)ClO(4) has caused major disasters. An irreversible cyclic mechanism is proposed for such decomposition, involving mechanoelectronic band-gap excitation and coalescence of X with X(-). From an intracrystalline ion-molecule collision complex, the singly charged dianion X(2)(-), exothermic reactions proceed with high yield.     

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.     

Ultrafast vibrational dynamics at water interfaces

Time-resolved sum-frequency vibrational spectroscopy permits the study of hitherto neglected ultrafast vibrational dynamics of neat water interfaces. Measurements on interfacial bonded OH stretch modes revealed relaxation behavior on sub-picosecond time scales in close resemblance to that of bulk water. Vibrational excitation is followed by spectral diffusion, vibrational relaxation, and thermalization in the hydrogen-bonding network. Dephasing of the excitation occurs in 相似文献   

陕西关中不同时期小麦品种高分子量麦谷蛋白亚基变异分析

用 SDS聚丙稀酰胺凝胶电泳分析了陕西关中地区不同历史时期主要推广小麦品种的高分子量麦谷蛋白亚基组成 ,并计算了其品质得分。结果表明 ,陕西关中地区主要推广小麦品种的高分子量麦谷蛋白亚基构成欠佳 ,亚基类型贫乏。主要原因在于 5 +10亚基很少 ,2 +12亚基多 ;1亚基较多 ,2 *亚基没有 ,N类型多等。陕西关中 80年代至今推广的小偃 6号及用其作亲本选育的个别品种含有 14 +15亚基 ,这些品种的品质都很好。最后讨论了冬小麦品质育种的策略和方法。     

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.     

Femtosecond dynamics of electron localization at interfaces

The dynamics of two-dimensional small-polaron formation at ultrathin alkane layers on a silver(111) surface have been studied with femtosecond time- and angle-resolved two-photon photoemission spectroscopy. Optical excitation creates interfacial electrons in quasi-free states for motion parallel to the interface. These initially delocalized electrons self-trap as small polarons in a localized state within a few hundred femtoseconds. The localized electrons then decay back to the metal within picoseconds by tunneling through the adlayer potential barrier. The energy dependence of the self-trapping rate has been measured and modeled with a theory analogous to electron transfer theory. This analysis determines the inter- and intramolecular vibrational modes of the overlayer responsible for self-trapping as well as the relaxation energy of the overlayer molecular lattice. These results for a model interface contribute to the fundamental picture of electron behavior in weakly bonded solids and can lead to better understanding of carrier dynamics in many different systems, including organic light-emitting diodes.     

Linked reactivity at mineral-water interfaces through bulk crystal conduction

The semiconducting properties of a wide range of minerals are often ignored in the study of their interfacial geochemical behavior. We show that surface-specific charge density accumulation reactions combined with bulk charge carrier diffusivity create conditions under which interfacial electron transfer reactions at one surface couple with those at another via current flow through the crystal bulk. Specifically, we observed that a chemically induced surface potential gradient across hematite (alpha-Fe2O3) crystals is sufficiently high and the bulk electrical resistivity sufficiently low that dissolution of edge surfaces is linked to simultaneous growth of the crystallographically distinct (001) basal plane. The apparent importance of bulk crystal conduction is likely to be generalizable to a host of naturally abundant semiconducting minerals playing varied key roles in soils, sediments, and the atmosphere.     

Neutron scattering of solution-grown polymer crystals: molecular dimensions are insensitive to molecular weight

Neutron scattering gives information on molecular conformations in solid solutions of polymers of one isotope in another. Results on crystals of polyethylene grown from solution show a molecular dimension (in the form of a radius of gyration) that is almost invariant with the length of the chain. It is proposed that certain lengths of folded chains fold back onto themselves to form stacks of chain-folded ribbons ("superfolding").     

煤基NaA分子筛材料的合成及其对Cd2+的吸附

为实现废弃物资源化利用,采用煤矸石为原料制备分子筛环境修复材料。通过对煤矸石（CG）的硅铝比进行调节,利用煅烧-水热晶化法分别在500℃和750℃下成功合成了NaA-500和NaA-750两种煤基NaA分子筛材料。进一步采用X射线衍射（XRD）、扫描电镜（SEM）等表征方法探讨了分子筛的结构特征和表观形貌,并对吸附过程进行吸附动力学和等温吸附线的研究分析,以深入探究其对Cd²⁺的吸附特性。结果表明：相比煤矸石,NaA-750和NaA-500对Cd²⁺的最高吸附量分别为392.9 mg·g^-1和208.9 mg·g^-1,分别是煤矸石的4.5倍和2.4倍,且NaA-750和NaA-500对Cd²⁺的吸附过程遵循准二级动力学规律。吸附等温线结果显示,NaA-500和NaA-750对Cd²⁺的吸附符合Langmuir等温吸附模型。综上所述,以煤矸石为原料制备的NaA型分子筛对Cd²⁺的吸附能力明显提升且具有较高的吸附容量,对去除废水中Cd²⁺具有潜在应用价值。     

Premelting at defects within bulk colloidal crystals

Premelting is the localized loss of crystalline order at surfaces and defects at temperatures below the bulk melting transition. It can be thought of as the nucleation of the melting process. Premelting has been observed at the surfaces of crystals but not within. We report observations of premelting at grain boundaries and dislocations within bulk colloidal crystals using real-time video microscopy. The crystals are equilibrium close-packed, three-dimensional colloidal structures made from thermally responsive microgel spheres. Particle tracking reveals increased disorder in crystalline regions bordering defects, the amount of which depends on the type of defect, distance from the defect, and particle volume fraction. Our observations suggest that interfacial free energy is the crucial parameter for premelting in colloidal and atomic-scale crystals.     

Colloidal jamming at interfaces: a route to fluid-bicontinuous gels

Colloidal particles or nanoparticles, with equal affinity for two fluids, are known to adsorb irreversibly to the fluid-fluid interface. We present large-scale computer simulations of the demixing of a binary solvent containing such particles. The newly formed interface sequesters the colloidal particles; as the interface coarsens, the particles are forced into close contact by interfacial tension. Coarsening is markedly curtailed, and the jammed colloidal layer seemingly enters a glassy state, creating a multiply connected, solidlike film in three dimensions. The resulting gel contains percolating domains of both fluids, with possible uses as, for example, a microreaction medium.     

Biomolecular interactions at phospholipid-decorated surfaces of liquid crystals

The spontaneous assembly of phospholipids at planar interfaces between thermotropic liquid crystals and aqueous phases gives rise to patterned orientations of the liquid crystals that reflect the spatial and temporal organization of the phospholipids. Strong and weak specific-binding events involving proteins at these interfaces drive the reorganization of the phospholipids and trigger orientational transitions in the liquid crystals. Because these interfaces are fluid, processes involving the lateral organization of proteins (such as the formation of protein- and phospholipid-rich domains) are also readily imaged by the orientational response of the liquid crystal, as are stereospecific enzymatic events. These results provide principles for label-free monitoring of aqueous streams for molecular and biomolecular species without the need for complex instrumentation.     

Full three-dimensional photonic bandgap crystals at near-infrared wavelengths

An artificial crystal structure has been fabricated exhibiting a full three-dimensional photonic bandgap effect at optical communication wavelengths. The photonic crystal was constructed by stacking 0.7-micrometer period semiconductor stripes with the accuracy of 30 nanometers by advanced wafer-fusion technique. A bandgap effect of more than 40 decibels (which corresponds to 99.99% reflection) was successfully achieved. The result encourages us to create an ultra-small optical integrated circuit including a three-dimensional photonic crystal waveguide with a sharp bend.     

Atomic force microscopy of the electrochemical nucleation and growth of molecular crystals

In situ atomic force microscopy reveals the morphology, surface topography, and growth and dissolution characteristics of microscopic single crystals of the low-dimensional organic conductor (tetrathiafulvalene)Br(0.76)' which are grown by electrocrystallization on a highly oriented pyrolytic graphite electrode in an atomic force microscope liquid cell. The growth modes and the distribution and orientation of topographic features on specific crystal faces, whose identity was determined by "atomic force microscope goniometry," can be correlated with the strength and direction of anisotropic solid-state intermolecular bonding. Growth on the (011) face of (tetrathiafulvalene)Br(0.76) crystals involves the formation of oriented self-similar triangular islands ranging in size from 200 to 5000 angstroms along a side. These nuclei eventually transform into rectangular rafts at larger length scales, where bulk intermolecular bonding interactions and surface energies dominate over nuclei-substrate interactions.     

活性炭与分子筛吸附乙烯诱导 巴厘菠萝开花的研究

为了开发一种新的菠萝催花方法、以200 mg/L 乙烯利溶液为对照、研究了两种吸附乙烯饱和的吸附剂 （活性炭和沸石分子筛）对菠萝品种巴厘的综合催花效果。结果表明院（1）活性炭吸附乙烯的能力及释放乙烯的速度 极显著高于分子筛;（2）沸石分子筛与乙烯利均可诱导巴厘菠萝100%成花、活性炭处理抽蕾率为30%~60%、二者花 期要比乙烯利延迟1~2 d;（3）催花后的菠萝小果数及单果重与乙烯吸附剂的投入量有关、吸附剂投放多、会降低菠 萝果实的小果数及果重、0.1~0.2 g分子筛以及活性炭处理催花后所结的菠萝小果数均极显著高于对照乙烯利、单果 重无显著差异;（4）分子筛及活性炭催花与乙烯利催花所结的果实在可溶性固形物尧总酸和维生素悦含量上无显著 差异。沸石分子筛吸附乙烯可以成功诱导巴厘菠萝开花、是一种新型的菠萝催花方法。     

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.