Secondary electron emission control in X-ray photoelectron spectroscopy

Secondary electron emission (SEE) is a major player in surface charging during X-ray photoelectron spectroscopy (XPS); its characteristics and applicability as a current source for electrical measurements are studied. We employ sample biasing and a top retarding grid to control the photoelectron current, and further compare their I–V characteristics with direct spectroscopy of the secondary electrons. Using silica-coated gold substrates, the effect of sample work function on the emitted secondary electrons is shown and fine control over the surface potential gradients, in the range of 10–100 meV, is achieved. XPS-based chemically resolved electrical measurements (CREM) can thus be extended to the positive current regime.     

Inhibitors of biotin biosynthesis as potential herbicides

Isosteric derivatives and analogues of the 7-keto-8-aminopelargonic acid (KAPA), 7,8-diaminopelargonic acid (DAPA) and desthiobiotin (DTB) vitamer intermediates involved in the biosynthetic pathway of biotin were prepared and evaluated as potential herbicides. The most active compound was desmethyl-KAPA which displayed a GR₅₀ (concentration of the active compound that causes a 50% growth inhibition) value of 8 ppm, where values <50 ppm are considered herbicidal. Other KAPA analogs where the terminal Me group was replaced by bulkier substituents such as Et, i-Pr and HOCH₂ showed moderate activity.     

Isothermal titration calorimetry as a new tool to investigate chiral interactions at crystal surfaces

In this communication we describe for the first time the use of isothermal titration calorimetry (ITC) to measure the energetics of adsorption of enantiomers from aqueous onto chiral crystal surfaces. Our results demonstrate that ITC can be used to measure chiral interactions at crystal surfaces.     

Energy level and band alignment for GaAs-alkylthiol monolayer-Hg junctions from electrical transport and photoemission experiments

A series of p- and n-GaAs-S-C(n)H(2n+1) || Hg junctions are prepared, and the electronic transport through them is measured. From current-voltage measurements, we find that, for n-GaAs, transport occurs by both thermionic emission and tunneling, with the former dominating at low forward bias and the latter dominating at higher forward bias. For p-GaAs, tunneling dominates at all bias voltages. By combining the analysis of the transport data with results from direct and inverse photoemission spectroscopy, we deduce an energy band diagram of the system, including the tunnel barrier and, with this barrier and within the Simmons tunneling model, extract an effective mass value of 1.5-1.6m(e) for the electronic carriers that cross the junctions. We find that transport is well-described by lowest unoccupied and highest occupied states at 1.3-1.4 eV above and 2.0-2.2 eV below the Fermi level. At the same time, the photoemission data indicate that there are continua of states from the conduction band minimum and the valence band maximum, the density of which varies with energy. On the basis of our results, it appears likely that, for both types of junctions, electrons are the main carrier type, although holes may contribute significantly to the transport in the p-GaAs system.     

Topological hochschild homology of extensions of ?/p? by polynomials, and of ?[x]/(xn) and ?[x]/(xn?1)

Topological Hochschild homology is calculated for the rings /p[x]/(f(x)) (where p is prime and f(x) /p[x] any polynomial), [x]/(x ⁿ) and [x]/(x ⁿ–1). A spectral sequence argument is used for calculating the homology of the topological Hochschild homology spectrum, from which its stable homotopy structure can be read off since the spectrum is known for a priori reasons to be a restricted product of Eilenberg-MacLane spectra.     

Molecular length, monolayer density, and charge transport: lessons from Al-AlOx/alkyl-phosphonate/Hg junctions

A combined electronic transport-structure characterization of self-assembled monolayers (MLs) of alkyl-phosphonate (AP) chains on Al-AlOx substrates indicates a strong molecular structural effect on charge transport. On the basis of X-ray reflectivity, XPS, and FTIR data, we conclude that "long" APs (C14 and C16) form much denser MLs than do "short" APs (C8, C10, C12). While current through all junctions showed a tunneling-like exponential length-attenuation, junctions with sparsely packed "short" AP MLs attenuate the current relatively more efficiently than those with densely packed, "long" ones. Furthermore, "long" AP ML junctions showed strong bias variation of the length decay coefficient, β, while for "short" AP ML junctions β is nearly independent of bias. Therefore, even for these simple molecular systems made up of what are considered to be inert molecules, the tunneling distance cannot be varied independently of other electrical properties, as is commonly assumed.     

Effects of acyl donor type, catalyst type, and reaction conditions on the activity and selectivity of Friedel-Crafts acylation

Acylation of anisole and 3-methylanisole was performed with several acylating reagents (acetylation by AcCl and Ac₂O and bromoacetylation by BrAcCl and (BrAc)₂O) over different solid acid catalysts. The reaction conditions were optimized with respect to the acylation reagent, overall yield, solid acid catalyst, and the products selectivities. While acylation of anisole with acetyl chloride or acetic anhydride resulted in its full conversion to para-substituted acetophenone, the use of bromoacetyl bromide or bromoacetic anhydride yielded also the ortho-substituted product. Acylation of 3-methylanisole also yielded both para- and ortho-substitutions, and the products distribution was affected by the reaction conditions and catalyst type. It was found that while more acidic catalysts (caesium salt of heteropolyacid and zeolites) were the most active towards anisole acylation, the most active catalysts for the acylation of 3-methylanisole were ion-exchange catalysts. Employing HY-740 zeolite resulted in the highest ortho-selectivity in the acylation of anisole with bromoacetyl bromide and bromoacetic anhydride and in the acylation of 3-methylanisole with acetic anhydride.     

Microwave-assisted synthesis of tin sulfide nanoflakes and their electrochemical performance as Li-inserting materials

A novel and quick method has been developed for the preparation of tin sulfide (SnS and SnS₂) nanoflakes in high yield (≈93%) by a microwave irradiation technique for 10–40 min. The sulfides were synthesized in a simple domestic microwave oven (DMO) using stannic chloride and stanous chloride as the precursors of tin and thiourea as the precursor of sulfur in ethylene glycol under argon atmosphere. Elemental sulfur and sodium thiosulfate were also tried as precursors of sulfur. The structures, morphologies, compositions, and physical properties of the products were characterized by powder X-ray diffraction (XRD), differential scanning calorimetry, energy dispersive X-ray analysis, transmission electron microscopy, selected area electron diffraction, Raman spectroscopy, and standard electrochemical techniques. The XRD patterns indicate that the as-synthesized product, obtained after microwave irradiation, is crystalline orthorhombic in the case of the SnS phase and amorphous in the case of SnS₂. Heat treatment of this SnS₂ produced a crystalline hexagonal phase. A possible mechanism for the formation of the tin sulfide nanoflakes is proposed herein. The electrochemical performance of these materials as Li-insertion materials was investigated in a number of electrolyte solutions and was found to be highly sensitive to the solution composition. A stable reversible capacity higher than 600 mAh/g could be obtained with SnS electrodes.