Direct observation of structural defects in laser-deposited superconducting y-ba-cu-o thin films

The defect structure of in situ pulsed, laser-deposited, thin films of the high-transition temperature superconductor Y-Ba-Cu-O has been observed directly by atomic resolution electron microscopy. In a thin film with the nominal composition YBa(2)Cu(3)O(7) (123), stacking defects corresponding to the cationic stoichiometry of the 248, 247, and 224 compounds have been observed. Other defects observed include edge dislocations and antiphase boundaries. These defects, which are related to the nonequilibrium processing conditions, are likely to be responsible for the higher critical currents observed in these films as compared to single crystals.     

Direct observation of chaperone-induced changes in a protein folding pathway

How chaperone interactions affect protein folding pathways is a central problem in biology. With the use of optical tweezers and all-atom molecular dynamics simulations, we studied the effect of chaperone SecB on the folding and unfolding pathways of maltose binding protein (MBP) at the single-molecule level. In the absence of SecB, we find that the MBP polypeptide first collapses into a molten globulelike compacted state and then folds into a stable core structure onto which several alpha helices are finally wrapped. Interactions with SecB completely prevent stable tertiary contacts in the core structure but have no detectable effect on the folding of the external alpha helices. It appears that SecB only binds to the extended or molten globulelike structure and retains MBP in this latter state. Thus during MBP translocation, no energy is required to disrupt stable tertiary interactions.     

Direct observation of dissociated dislocations in garnet

Dislocation core structures in garnet [grossularite (Ca(2.9)Fe(II)(0.1))(Al(1.9)Fe(III)(0.1)Si(3.0)O(12)] have been examined with near atomic resolution transmission electron microscopy. Dissociated dislocations have been observed as parallel a/4<111> partial dislocations that are separated by stacking faults. The partial dislocations have narrow cores ( approximately 3 burgers vectors), and the stacking fault zone between the narrow partial dislocations is apparently a low-energy configuration that results from the occupancy of previously unfilled dodecahedral and tetrahedral sites. Previous studies of garnet dislocations suggested that dissociation involves departures from garnet stoichiometry (that is, trace amounts of impurities), but evidence of detectable amounts of impurities has not been found even in the highest resolution images. These results have implications for mantle mineral rheology and transformations as well as for ceramics of material science interest.     

Direct experimental observation of cells in phenomic lag

By employing cells mutating at a very high spontaneous rate and a grid plate containing a medium totally selective against mutant cells, direct microscopic observation was made of mutant cells of recent origin passing through a limited number of phenomic lag divisions.     

Direct observation of the three-state folding of a single protein molecule

We used force-measuring optical tweezers to induce complete mechanical unfolding and refolding of individual Escherichia coli ribonuclease H (RNase H) molecules. The protein unfolds in a two-state manner and refolds through an intermediate that correlates with the transient molten globule-like intermediate observed in bulk studies. This intermediate displays unusual mechanical compliance and unfolds at substantially lower forces than the native state. In a narrow range of forces, the molecule hops between the unfolded and intermediate states in real time. Occasionally, hopping was observed to stop as the molecule crossed the folding barrier directly from the intermediate, demonstrating that the intermediate is on-pathway. These studies allow us to map the energy landscape of RNase H.     

Epitaxial BiFeO3 multiferroic thin film heterostructures

Enhancement of polarization and related properties in heteroepitaxially constrained thin films of the ferroelectromagnet, BiFeO3, is reported. Structure analysis indicates that the crystal structure of film is monoclinic in contrast to bulk, which is rhombohedral. The films display a room-temperature spontaneous polarization (50 to 60 microcoulombs per square centimeter) almost an order of magnitude higher than that of the bulk (6.1 microcoulombs per square centimeter). The observed enhancement is corroborated by first-principles calculations and found to originate from a high sensitivity of the polarization to small changes in lattice parameters. The films also exhibit enhanced thickness-dependent magnetism compared with the bulk. These enhanced and combined functional responses in thin film form present an opportunity to create and implement thin film devices that actively couple the magnetic and ferroelectric order parameters.     

Direct visual observation of thermal capillary waves

We studied the free fluid-fluid interface in a phase-separated colloid-polymer dispersion with laser scanning confocal microscopy and directly observed thermally induced capillary waves at the interface in real space. Experimental results for static and dynamic correlation functions validate the capillary wave model down to almost the particle level. The ultralow interfacial tension, the capillary length, and the capillary time are found to be in agreement with independent measurements. Furthermore, we show that capillary waves induce the spontaneous breakup of thin liquid films and thus are of key importance in the process of droplet coalescence.     

Direct observation of dynamical heterogeneities in colloidal hard-sphere suspensions

The real-space dynamics in a model system of colloidal hard spheres was studied by means of time-resolved fluorescence confocal scanning microscopy. Direct experimental evidence for the presence of dynamical heterogeneities in a dense liquid was obtained from an analysis of particle trajectories in two-dimensional slices of the bulk sample. These heterogeneities manifest themselves as a non-Gaussian probability distribution of particle displacements and also affect the onset of long-time diffusive behavior.     

Direct observation of molecular preorganization for chirality transfer on a catalyst surface

The chemisorption of specific optically active compounds on metal surfaces can create catalytically active chirality transfer sites. However, the mechanism through which these sites bias the stereoselectivity of reactions (typically hydrogenations) is generally assumed to be so complex that continued progress in the area is uncertain. We show that the investigation of heterogeneous asymmetric induction with single-site resolution sufficient to distinguish stereochemical conformations at the submolecular level is finally accessible. A combination of scanning tunneling microscopy and density functional theory calculations reveals the stereodirecting forces governing preorganization into precise chiral modifier-substrate bimolecular surface complexes. The study shows that the chiral modifier induces prochiral switching on the surface and that different prochiral ratios prevail at different submolecular binding sites on the modifier at the reaction temperature.     

Direct observation of the femtosecond excited-state cis-trans isomerization in bacteriorhodopsin

Femtosecond optical measurement techniques have been used to study the primary photoprocesses in the light-driven transmembrane proton pump bacteriorhodopsin. Light-adapted bacteriorhodopsin was excited with a 60-femtosecond pump pulse at 618 nanometers, and the transient absorption spectra from 560 to 710 nanometers were recorded from -50 to 1000 femtoseconds by means of 6-femtosecond probe pulses. By 60 femtoseconds, a broad transient hole appeared in the absorption spectrum whose amplitude remained constant for about 200 femtoseconds. Stimulated emission in the 660- to 710-nanometer region and excited-state absorption in the 560- to 580-nanometer region appeared promptly and then shifted and decayed from 0 to approximately 150 femtoseconds. These spectral features provide a direct observation of the 13-trans to 13-cis torsional isomerization of the retinal chromophore on the excited-state potential surface. Absorption due to the primary ground-state photoproduct J appears with a time constant of approximately 500 femtoseconds.     

Direct observation of chemical bond dynamics on surfaces

The dynamics of chemisorbed species as they swing to-and-fro on their adsorption sites may be directly observed with electron-stimulated desorption. The observation of the thermal disorder in adsorbate chemical bond directions, through studies of the thermal excitation of librational modes, allows one to visualize the potential energy surfaces controlling the structure and dynamics of adsorbates on single crystal metal and semiconductor surfaces. This information may be useful in understanding surface diffusion as well as the spatial aspects of surface chemical reactions.     

Direct observation of nodes and twofold symmetry in FeSe superconductor

We investigated the electron-pairing mechanism in an iron-based superconductor, iron selenide (FeSe), using scanning tunneling microscopy and spectroscopy. Tunneling conductance spectra of stoichiometric FeSe crystalline films in their superconducting state revealed evidence for a gap function with nodal lines. Electron pairing with twofold symmetry was demonstrated by direct imaging of quasiparticle excitations in the vicinity of magnetic vortex cores, Fe adatoms, and Se vacancies. The twofold pairing symmetry was further supported by the observation of striped electronic nanostructures in the slightly Se-doped samples. The anisotropy can be explained in terms of the orbital-dependent reconstruction of electronic structure in FeSe.     

Direct electrochemical measurements inside a 2000 angstrom thick polymer film by scanning electrochemical microscopy

An extremely small, conically shaped Pt microelectrode tip (with a radius of 30 nanometers) and the precise positioning capabilities of the scanning electrochemical microscope were used to penetrate a thin (200 nanometers) polymer film and obtain directly the standard potential and kinetic parameters of an electrode reaction within the film. The thickness of the film was determined while it was immersed in and swollen by an electrolyte solution. The film studied was the perfluorosulfonate Nafion containing Os(bpy)(3)(2+) (bpy, 2,2'-bipyridine) cast on an indium tin oxide surface. The steady-state response at the ultramicroelectrode allowed direct determination of the rate constant for heterogeneous electron transfer K(o) and the diffusion coefficient D without complications caused by transport in the liquid phase, charge exchange at the liquid-polymer interface, and resistive drop.     

Direct observation of internal spin structure of magnetic vortex cores

Thin film nanoscale elements with a curling magnetic structure (vortex) are a promising candidate for future nonvolatile data storage devices. Their properties are strongly influenced by the spin structure in the vortex core. We have used spin-polarized scanning tunneling microscopy on nanoscale iron islands to probe for the first time the internal spin structure of magnetic vortex cores. Using tips coated with a layer of antiferromagnetic chromium, we obtained images of the curling in-plane magnetization around and of the out-of-plane magnetization inside the core region. The experimental data are compared with micromagnetic simulations. The results confirm theoretical predictions that the size and the shape of the vortex core as well as its magnetic field dependence are governed by only two material parameters, the exchange stiffness and the saturation magnetization that determines the stray field energy.     

PbSe nanocrystal solids for n- and p-channel thin film field-effect transistors

Initially poorly conducting PbSe nanocrystal solids (quantum dot arrays or superlattices) can be chemically "activated" to fabricate n- and p-channel field effect transistors with electron and hole mobilities of 0.9 and 0.2 square centimeters per volt-second, respectively; with current modulations of about 10(3) to 10(4); and with current density approaching 3 x 10(4) amperes per square centimeter. Chemical treatments engineer the interparticle spacing, electronic coupling, and doping while passivating electronic traps. These nanocrystal field-effect transistors allow reversible switching between n- and p-transport, providing options for complementary metal oxide semiconductor circuits and enabling a range of low-cost, large-area electronic, optoelectronic, thermoelectric, and sensing applications.     

基于梯度扩散薄膜技术评估稻田土壤中镉的生物有效性

为了给重金属污染农田土壤的安全性评估提供方法学指导,以稻田土壤-水稻体系为对象,通过比较化学提取法(土壤溶液法和0.01 mol·L~(-1)Ca Cl2提取法)和梯度扩散薄膜技术(DGT)所提取的有效态镉(Cd)含量与水稻谷粒中Cd含量(0.06~2.16 mg·kg~(-1))的相关关系,阐述DGT是否能更准确评估Cd的生物有效性及其作用机理。结果表明,土壤Cd全量与谷粒中Cd含量、几种有效态Cd提取量均未显示出显著相关性,不能真实反映Cd的生物有效性。DGT提取的Cd含量与谷粒Cd含量的相关性系数(R_(线性)~2=0.89和R_(曲线)~2=0.94)高于土壤溶液法(R_(线性)~2=0.87和R_(曲线)~2=0.92)和0.01 mol·L~(-1)Ca Cl2提取法(R_(线性)~2=0.80和R_(曲线)~2=0.83),R值分析表明DGT技术模拟了根部吸收土壤Cd过程中土壤固-液释放补给动态过程。因此,与传统化学提取法相比,DGT技术能更好地预测Cd污染土壤(0.31~10.64 mg·kg~(-1))中Cd的生物有效性。     

Direct observation of native DNA structures with the scanning tunneling microscope

Uncoated double-stranded DNA dissolved in a salt solution was deposited on graphite and imaged in air with the scanning tunneling microscope (STM). The resolution was such that the major and minor grooves could be distinguished. The pitch of the helix varied between 27 and 63 angstroms in the images obtained. Thus the STM can be useful for structural studies of a variety of uncoated and isolated biomolecules.     

Direct observation of global protein motion in hemoglobin and myoglobin on picosecond time scales

Picosecond phase-grating spectroscopy is highly sensitive to density changes and provides a new holographic approach to the study of protein dynamics. Photodissociation of carbon monoxide from heme proteins induces a well-defined transition from a ligated to a deoxy structure that is important to hemoglobin and myoglobin functionality. Grating spectroscopy was used to observe protein-driven density waves on a picosecond time scale after carbon monoxide dissociation. This result demonstrates that global tertiary structure changes of proteins occur on an extremely fast time scale and provides new insight into the biomechanics of deterministic protein motion.