Field Emission from Self-Assembled Arrays of Lanthanum Monosulfide Nanoprotrusions

The field emission properties of LaS nanoprotrusions called nanodomes, formed by pulsed laser deposition on porous anodic alumina films, have been analyzed with scanning anode field emission microscopy. The voltage necessary to produce a given field emission current is 3.5 times less for nanodomes than for thin films. Assuming the same work function for LaS thin films and nanoprotrusions, that is, 1 eV, a field enhancement factor of 5.8 is extracted for the nanodome emitters from Fowler-Nordheim plots of the field emission data. This correlates well with the aspect ratio of the tallest nanodomes observed in atomic force micrograph measurements

Rare-earth monosulfides as durable and efficient cold cathodes

In their rocksalt structure, rare-earth monosulfides offer a more stable alternative to alkali metals to attain low or negative electron affinity when deposited on various III-V and II-VI semiconductor surfaces. In this article, we first describe the successful deposition of Lanthanum Monosulfide via pulsed laser deposition on Si and MgO substrates and alumina templates. These thin films have been characterized by X-ray diffraction, atomic force microscopy, high resolution transmission electron microscopy, ellipsometry, Raman spectroscopy, ultraviolet photoelectron spectroscopy and Kelvin probe measurements. For both LaS/Si and LaS/MgO thin films, the effective work function of the submicron thick thin films was determined to be about 1 eV from field emission measurements using the Scanning Anode Field Emission Microscopy technique. The physical reasons for these highly desirable low work function properties were explained using a patchwork field emission model of the emitting surface. In this model, nanocrystals of low work function materials having a orientation perpendicular to the surface and outcropping it are surrounded by a matrix of amorphous materials with higher work function. To date, LaS thin films have been used successfully as cold cathode emitters with measured emitted current densities as high as 50 A/cm2. Finally, we describe the successful growth of LaS thin films on InP substrates and, more recently, the production of LaS nanoballs and nanoclusters using Pulsed Laser Ablation.Comment: 61 pages, 24 figure

Thermodynamic, kinetic, and structural parameterization of human carbonic anhydrase interactions toward enhanced inhibitor design

The aim of rational drug design is to develop small molecules using a quantitative approach to optimize affinity. This should enhance the development of chemical compounds that would specifically, selectively, reversibly, and with high affinity interact with a target protein. It is not yet possible to develop such compounds using computational (i.e., in silico) approach and instead the lead molecules are discovered in high-throughput screening searches of large compound libraries. The main reason why in silico methods are not capable to deliver is our poor understanding of the compound structure–thermodynamics and structure–kinetics correlations. There is a need for databases of intrinsic binding parameters (e.g., the change upon binding in standard Gibbs energy (ΔGint), enthalpy (ΔHint), entropy (ΔSint), volume (ΔVintr), heat capacity (ΔCp,int), association rate (ka,int), and dissociation rate (kd,int)) between a series of closely related proteins and a chemically diverse, but pharmacophoric group-guided library of compounds together with the co-crystal structures that could help explain the structure–energetics correlations and rationally design novel compounds. Assembly of these data will facilitate attempts to provide correlations and train data for modeling of compound binding. Here, we report large datasets of the intrinsic thermodynamic and kinetic data including over 400 primary sulfonamide compound binding to a family of 12 catalytically active human carbonic anhydrases (CA). Thermodynamic parameters have been determined by the fluorescent thermal shift assay, isothermal titration calorimetry, and by the stopped-flow assay of the inhibition of enzymatic activity. Kinetic measurements were performed using surface plasmon resonance. Intrinsic thermodynamic and kinetic parameters of binding were determined by dissecting the binding-linked protonation reactions of the protein and sulfonamide. The compound structure–thermodynamics and kinetics correlations reported here helped to discover compounds that exhibited picomolar affinities, hour-long residence times, and million-fold selectivities over non-target CA isoforms. Drug-lead compounds are suggested for anticancer target CA IX and CA XII, antiglaucoma CA IV, antiobesity CA VA and CA VB, and other isoforms. Together with 85 X-ray crystallographic structures of 60 compounds bound to six CA isoforms, the database should be of help to continue developing the principles of rational target-based drug design

Field Emission from Self-Assembled Arrays of Lanthanum Monosulfide Nanoprotrusions

The field emission properties of LaS nanoprotrusions called nanodomes, formed by pulsed laser deposition on porous anodic alumina films, have been analyzed with scanning anode field emission microscopy. The voltage necessary to produce a given field emission current is ∼3.5 times less for nanodomes than for thin films. Assuming the same work function for LaS thin films and nanoprotrusions, that is, ∼1 eV, a field enhancement factor of ∼5.8 is extracted for the nanodome emitters from Fowler-Nordheim plots of the field emission data. This correlates well with the aspect ratio of the tallest nanodomes observed in atomic force micrograph measurements

Field Emission from Self-Assembled Arrays of Lanthanum Monosulfide Nanoprotrusions

The field emission properties of LaS nanoprotrusions called nanodomes, formed by pulsed laser deposition on porous anodic alumina films, have been analyzed with scanning anode field emission microscopy. The voltage necessary to produce a given field emission current is ∼3.5 times less for nanodomes than for thin films. Assuming the same work function for LaS thin films and nanoprotrusions, that is, ∼1 eV, a field enhancement factor of ∼5.8 is extracted for the nanodome emitters from FowlerNordheim plots of the field emission data. This correlates well with the aspect ratio of the tallest nanodomes observed in atomic force micrograph measurements. The promise of producing extremely high current densities in near-vacuum with no external source (such as heater, primary electron-beam, or intense light source) has generated significant interest in robust, reproducible, and fieldemission-based cold cathodes Recently, we reported the first successful deposition of lanthanum monosulfide (LaS) thin films on Si substrates using pulsed laser deposition (PLD) The nanodomes are cone-shaped LaS structures with base diameter 2r ranging from 50 to 100 nm and height h ranging from 100 to 150 nm. They were found to grow on the boundaries separating regions of the anodic alumina film that have near perfect pore ordering. Their density is ∼10 9 /cm 2 , as extracted from the field emission-scanning electron micrographs (FE-SEM) and atomic force micrographs (AFM) such as those shown in The SAFEM technique was used to measure the FE current-voltage (I-V) characteristics at different surface locations. As the nanowires are buried inside the pores, they contribute very little, if any at all, to the net FE current. Moreover, FE measurements from the arrays of nanodomes and nanodots were possible because the regions joining adjacent nanodomes and nanodots are covered with a thin percolating network of LaS over the entire array. Its presence was confirmed by measuring a low resistance value of about 2 Ohms between two electrical contacts about 1 cm apart. For each location, a full set of I-V characteristics (total measured current versus applied voltage) for different values of d, the distance between the cathode surface and the probe ball, was measured. This set of measurements was then analyzed in order to extract the apparent current density αJ versus actual applied local field γF, where γ is the local geometrical field enhancement at the surface of the cathode In order to assess the FE properties from LaS nanoprotrusions, we have compared the FE from nanodome cathodes with that from planar thin film LaS cathodes. This comparative methodology was chosen because a precise quantitative estimation of γ from topographic measurements is still subject to controversy, except for a flat surface. These experimental measurements were performed for both LaS thin films of 100 nm thickness on Si wafers and LaS nanodomes on anodic alumina films. The analysis consisted of the following steps. (1) In order to restrict the analysis of the differences in the I-V data to the surface morphology of the cathodes, both SAFEM measurements were performed with the same probe ball-to-cathode distance d = 3.65 μm. Typical I-V characteristics are shown in (2) The total FE current versus applied voltage (I-V) characteristics were measured for different values of the probe-ball-to-cathode-surface distance d. From these data, the apparent current densities (α t f J and α nd J) as a a function of the applied local field were extracted ACKNOWLEDGMEN

The Arabidopsis B3 domain protein VERNALIZATION1 is involved in processes essential for development with structural and mutational studies revealing its DNA binding surface

The B3 DNA-binding domain is a plant-specific domain found throughout the plant kingdom from the alga Chlamydomonas to grasses and flowering plants. Over 100 B3 domain-containing proteins are found in the model plant Arabidopsis thaliana, and one of these is critical for accelerating flowering in response to prolonged cold treatment, an epigenetic process called vernalization. Despite the specific phenotype of genetic vrn1 mutants, the VERNALIZATION1 (VRN1) protein localizes throughout the nucleus and shows sequence-nonspecific binding in vitro. In this work, we used a dominant repressor tag that overcomes genetic redundancy to show that VRN1 is involved in processes beyond vernalization that are essential for Arabidopsis development. To understand its sequence-nonspecific binding, we crystallized VRN1(208-341) and solved its crystal structure to 1.6 angstrom resolution using selenium/single-wavelength anomalous diffraction methods. The crystallized construct comprises the second VRN1 B3 domain and a preceding region conserved among VRN1 orthologs but absent in other B3 domains. We established the DNA-binding face using NMR and then mutated positively charged residues on this surface with a series of 16 Ala and Glu substitutions, ensuring that the protein fold was not disturbed using heteronuclear single quantum correlation NMR spectra. The triple mutant R249E/R289E/R296E was almost completely incapable of DNA binding in vitro. Thus, we have revealed that although VRN1 is sequence-nonspecific in DNA binding, it has a defined DNA-binding surface

Characterization and crystal structure of the type IIG restriction endonuclease RM.BpuSI

A type IIG restriction endonuclease, RM.BpuSI from Bacillus pumilus, has been characterized and its X-ray crystal structure determined at 2.35Å resolution. The enzyme is comprised of an array of 5-folded domains that couple the enzyme's N-terminal endonuclease domain to its C-terminal target recognition and methylation activities. The REase domain contains a PD-x15-ExK motif, is closely superimposable against the FokI endonuclease domain, and coordinates a single metal ion. A helical bundle domain connects the endonuclease and methyltransferase (MTase) domains. The MTase domain is similar to the N6-adenine MTase M.TaqI, while the target recognition domain (TRD or specificity domain) resembles a truncated S subunit of Type I R–M system. A final structural domain, that may form additional DNA contacts, interrupts the TRD. DNA binding and cleavage must involve large movements of the endonuclease and TRD domains, that are probably tightly coordinated and coupled to target site methylation status

DNA synapsis through transient tetramerization triggers cleavage by Ecl18kI restriction enzyme

To cut DNA at their target sites, restriction enzymes assemble into different oligomeric structures. The Ecl18kI endonuclease in the crystal is arranged as a tetramer made of two dimers each bound to a DNA copy. However, free in solution Ecl18kI is a dimer. To find out whether the Ecl18kI dimer or tetramer represents the functionally important assembly, we generated mutants aimed at disrupting the putative dimer–dimer interface and analysed the functional properties of Ecl18kI and mutant variants. We show by atomic force microscopy that on two-site DNA, Ecl18kI loops out an intervening DNA fragment and forms a tetramer. Using the tethered particle motion technique, we demonstrate that in solution DNA looping is highly dynamic and involves a transient interaction between the two DNA-bound dimers. Furthermore, we show that Ecl18kI cleaves DNA in the synaptic complex much faster than when acting on a single recognition site. Contrary to Ecl18kI, the tetramerization interface mutant R174A binds DNA as a dimer, shows no DNA looping and is virtually inactive. We conclude that Ecl18kI follows the association model for the synaptic complex assembly in which it binds to the target site as a dimer and then associates into a transient tetrameric form to accomplish the cleavage reaction

Mineralogical and geochemical analysis of Fe-phases in drill-cores from the Triassic Stuttgart Formation at Ketzin CO₂ storage site before CO₂ arrival

Reactive iron (Fe) oxides and sheet silicate-bound Fe in reservoir rocks may affect the subsurface storage of CO2 through several processes by changing the capacity to buffer the acidification by CO2 and the permeability of the reservoir rock: (1) the reduction of three-valent Fe in anoxic environments can lead to an increase in pH, (2) under sulphidic conditions, Fe may drive sulphur cycling and lead to the formation of pyrite, and (3) the leaching of Fe from sheet silicates may affect silicate diagenesis. In order to evaluate the importance of Fe-reduction on the CO2 reservoir, we analysed the Fe geochemistry in drill-cores from the Triassic Stuttgart Formation (Schilfsandstein) recovered from the monitoring well at the CO2 test injection site near Ketzin, Germany. The reservoir rock is a porous, poorly to moderately cohesive fluvial sandstone containing up to 2–4 wt% reactive Fe. Based on a sequential extraction, most Fe falls into the dithionite-extractable Fe-fraction and Fe bound to sheet silicates, whereby some Fe in the dithionite-extractable Fe-fraction may have been leached from illite and smectite. Illite and smectite were detected in core samples by X-ray diffraction and confirmed as the main Fe-containing mineral phases by X-ray absorption spectroscopy. Chlorite is also present, but likely does not contribute much to the high amount of Fe in the silicate-bound fraction. The organic carbon content of the reservoir rock is extremely low (<0.3 wt%), thus likely limiting microbial Fe-reduction or sulphate reduction despite relatively high concentrations of reactive Fe-mineral phases in the reservoir rock and sulphate in the reservoir fluid. Both processes could, however, be fuelled by organic matter that is mobilized by the flow of supercritical CO2 or introduced with the drilling fluid. Over long time periods, a potential way of liberating additional reactive Fe could occur through weathering of silicates due to acidification by CO2