Acetylene adsorption on silicon (100)-(4 × 2) revisited

The aim of this work is to revisit the problem of acetylene adsorption on silicon (100). Extending previous theoretical work and including van der Waals forces explicitly in the simulations we remove existing ambiguities about the adsorption sites. The simulated adsorption energies and scanning tunneling microscopy contours are in good agreement with experimental data, they support the interpretation of a two-dimer feature at the surface as resulting from the adsorption of two individual molecules. It is also found that the simulated apparent heights agree with experimental values, if the actual bandgap of silicon is taken into account.     

M−O Bonding Beyond the Oxo Wall: Spectroscopy and Reactivity of Cobalt(III)‐Oxyl and Cobalt(III)‐Oxo Complexes

Terminal oxo complexes of late transition metals are frequently proposed reactive intermediates. However, they are scarcely known beyond Group 8. Using mass spectrometry, we prepared and characterized two such complexes: [(N4Py)Co^III(O)]⁺ ( 1 ) and [(N4Py)Co^IV(O)]²⁺ ( 2 ). Infrared photodissociation spectroscopy revealed that the Co?O bond in 1 is rather strong, in accordance with its lack of chemical reactivity. On the contrary, 2 has a very weak Co?O bond characterized by a stretching frequency of ≤659 cm^?1. Accordingly, 2 can abstract hydrogen atoms from non‐activated secondary alkanes. Previously, this reactivity has only been observed in the gas phase for small, coordinatively unsaturated metal complexes. Multireference ab‐initio calculations suggest that 2 , formally a cobalt(IV)‐oxo complex, is best described as cobalt(III)‐oxyl. Our results provide important data on changes to metal‐oxo bonding behind the oxo wall and show that cobalt‐oxo complexes are promising targets for developing highly active C?H oxidation catalysts.     

Photocatalytic Nanoheterostructures and Chemically Bonded Junctions Made by Solution-Based Approaches

While single compound semiconductors were initially used for photocatalysis, combining two compounds to form a heterojunction significantly increases the photocatalysis performance. This review will outline how heterojunctions are superior, explain the different heterostructure architectures assembled from nanoparticles, and discuss the importance of achieving a large and quality contact in the junction, the heterojunction. Reference is made to methods for increasing the charge carrier performance and reducing recombination. Solution-based synthesis approaches, have been selected as the preferred route of manufacture, for the low cost scalability, and ability to combine a larger number of compounds. The main objective of this review article is to provide insight to the range of chemical solution-based methods for forming chemically bonded junction in nanoheterostructures for photocatalysis. Methods include chemical precipitation, impregnation, chemical bath deposition, hot injection, solvothermal, photo-deposition, electrochemical deposition, cation exchange and linker assisted assembly. The synthesis of different photocatalysts is addressed for each synthesis method. Solution synthesis is offered for coupling oxide semiconductors (i.e. TiO₂, ZnO, WO₃, Fe₂O₃, BiVO₄) with other oxides or metal chalcogenide quantum dots or metallic plasmonic nanoparticles.     

Ring expansion reactions of 4-amino-1,1-dioxo-[1,2,3,5]-thiatriazoles

An unusual ring-expansion reaction of 4-amino-1,1-dioxo-[1,2,3,5]-thiatriazoles has been identified that produces the relatively rare 5-amino-1,1-dioxo-[1,2,4,6]-thiatriazines and. Initial alkylation of the thiatriazole with alpha-halo-esters at N-3 produces alpha-substituted esters which, under basic reaction conditions, undergo opening of the thiatriazole ring and re-closure to a thiatriazine ring. Similar alkylations of with diethyl chloromalonate and ethyl dichloroacetate lead to the loss of SO2 and the production of triazine and triazole, apparently by an initial alkylation at N-5. The reaction of with phenacyl bromides or a phenacyl dibromide forms fully unsaturated 5-amino-1,1-dioxo-[1,2,4,6]-thiatriazines.     

Methacrylic maleic bifunctional stabilizer in emulsion polymerization

A new type of reactive surfactant, containing both a methacrylic and a maleic group, was prepared and engaged in batch and seeded emulsion polymerization of styrene and styrene-butyl acrylate. The stability of core-shell latexes versus electrolytes has been studied.     

A note on the design of hp-version interior penalty discontinuous Galerkin finite element methods for degenerate problems

^** Email: emmanuil.georgoulis{at}mcs.le.ac.uk^*** Email: al{at}maths.strath.ac.uk We consider a variant of the hp-version interior penalty discontinuousGalerkin finite element method (IP-DGFEM) for second-order problemsof degenerate type. We do not assume uniform ellipticity ofthe diffusion tensor. Moreover, diffusion tensors of arbitraryform are covered in the theory presented. A new, refined recipefor the choice of the discontinuity-penalization parameter (thatis present in the formulation of the IP-DGFEM) is given. Makinguse of the recently introduced augmented Sobolev space framework,we prove an hp-optimal error bound in the energy norm and anh-optimal and slightly p-suboptimal (by only half an order ofp) bound in the L² norm (the latter, for the symmetric versionof the IP-DGFEM), provided that the solution belongs to an augmentedSobolev space.     

Formation mechanism of solvent induced artifact arising from chromatographic purity testing of γ-irradiated chloramphenicol

Summary Different γ-irradiated chloramphenicol (CAP) samples were screened for impurities by recording melting point, solubility, pH and occurrence of additional spots on thin-layer plates according to the European Pharmacopoeia. Significant decomposition was detected as an intense spot in the TLC-test. The spot (r _f 0.7) which had an intensity >5% of the educt spot, depending on the irradiation dose, was eluted and concentrated from preparative TLC plates. The structure was confirmed by IR and¹H or¹³C-NMR and determined as the cyclic ketale condensation product of acetone and chloramphenicol. Formation of this by-product, which is acid-catalyzed, was determined as an artifact arising from purity testing. Not the τ-irradiation procedure itself but traces of acid in combination with acetone as the TLC solvent led to this condensation product which is especially detectable for small levels of protons (ca. 10⁻⁴ mol L⁻¹) stemming from hydrolysis of CAP or decomposition of residual solvents (CHCl₃) at low irradiation doses (8 kGy). Substitution of acetone by methanol solvent avoids this and misleading artifact from chromatographic purity investigations.     

Threshold behavior of e-H ionizing collisions

We present accurate ab initio numerical solutions of the full Schr?dinger equation for the electron-impact ionization of hydrogen near threshold using the propagating exterior complex scaling method. They provide strong support for the Wannier threshold law [Phys. Rev. 90, 817 (1953)], giving sigma proportional to E(1.122+/-0.015), and also give the energy dependence of the electrons' angular distribution as (pi-theta12) FWHM approximately 3.0E(1/4), in general agreement with classical and semiclassical predictions.     

Structure Effect of Imidazolium-Based Dicationic Ionic Liquids on Claisen Rearrangement

A large group of imidazolium-based dicationic ionic liquids (DILs) has been prepared in good yields. Thermal stability of all DILs has been determined. The effects of the reaction time, cation, imidazolium C₂–H acidity, and anion on the Claisen rearrangement of allyl phenyl ether have been investigated. Type of anion and the presence of the acidic C₂–H bond in the imidazolium moieties have proven to be essential for this reaction. The simple procedure and the possibility of avoiding the use catalysts and volatile organic solvents make this synthetic method environmentally benign and adaptable for large-scale applications.