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.     

Straightforward Approach for Preparing Durable Antibacterial ZnO Nanoparticle Coatings on Flexible Substrates

Flexible antibacterial materials have gained utmost importance in protection from the distribution of bacteria and viruses due to the exceptional variety of applications. Herein, we demonstrate a readily scalable and rapid single-step approach for producing durable ZnO nanoparticle antibacterial coating on flexible polymer substrates at room temperature. Substrates used are polystyrene, poly(ethylene-co-vinyl acetate) copolymer, poly(methyl methacrylate), polypropylene, high density polyethylene and a commercial acrylate type adhesive tape. The deposition was achieved by a spin-coating process using a slurry of ZnO nanoparticles in toluene. A stable modification layer was obtained when toluene was a solvent for the polymer substrates, namely polystyrene and poly(ethylene-co-vinyl acetate). These coatings show high antibacterial efficiency causing >5 log decrease in the viable counts of Gram-negative bacteria Escherichia. coli and Gram-positive bacteria Staphylococcus aureus in 120 min. Even after tapping these coated surfaces 500 times, the antibacterial properties remained unchanged, showing that the coating obtained by the presented method is very robust. In contrast to the above findings, the coatings are unstable when toluene is not a solvent for the substrate.     

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.     

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.     

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.     

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.     

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.     

Effect of light polarization on holographic recording in glassy azocompounds and chalcogenides

Light polarization effects on a holographic grating recording in a glassy chalcogenide a-As₄₀S₁₅Se₄₅ film has been experimentally studied and compared with previously studied glassy molecular azobenzene film 8a at 633, using s − s,p − p, CE-1 and CE-2 circular-elliptic recording-beam polarizations (differing by light electric field rotation directions). The azocompound exhibited much higher self-diffraction efficiency (SDE) and diffraction efficiency whereas chalcogenide was more sensitive. Their recording efficiency polarization dependences also were different. SDE up to 45% was achieved in 8a with p − p and up to 2.6% in a-As₄₀S₁₅Se₄₅ with CE-2 polarized recording beams. The polarization changes in the diffraction process were studied as well in these and other materials (11, 16, 19 and a-As₂S₃ film, LiTaO₃:Fe crystal). It was found that light polarization changes in the process of diffraction from gratings recorded vectorially by s−p polarizations depended on chemical composition, wavelength, and exposure time. Vector gratings with SDE up to 25% were recorded in 8a, rotating a linear polarization by 90°. No light polarization changes were found in azobenzene 19 and chalcogenide films and in LiTaO₃:Fe crystal, thus showing a vector recording of scalar holograms. The recording mechanisms in azocompounds and chalcogenides are discussed and compared.     

Random Tensor Theory: Extending Random Matrix Theory to Mixtures of Random Product States

We consider a problem in random matrix theory that is inspired by quantum information theory: determining the largest eigenvalue of a sum of p random product states in \({(\mathbb {C}^d)^{\otimes k}}\), where k and p/d ^k are fixed while d → ∞. When k = 1, the Mar?enko-Pastur law determines (up to small corrections) not only the largest eigenvalue (\({(1+\sqrt{p/d^k})^2}\)) but the smallest eigenvalue \({(\min(0,1-\sqrt{p/d^k})^2)}\) and the spectral density in between. We use the method of moments to show that for k > 1 the largest eigenvalue is still approximately \({(1+\sqrt{p/d^k})^2}\) and the spectral density approaches that of the Mar?enko-Pastur law, generalizing the random matrix theory result to the random tensor case. Our bound on the largest eigenvalue has implications both for sampling from a particular heavy-tailed distribution and for a recently proposed quantum data-hiding and correlation-locking scheme due to Leung and Winter.Since the matrices we consider have neither independent entries nor unitary invariance, we need to develop new techniques for their analysis. The main contribution of this paper is to give three different methods for analyzing mixtures of random product states: a diagrammatic approach based on Gaussian integrals, a combinatorial method that looks at the cycle decompositions of permutations and a recursive method that uses a variant of the Schwinger-Dyson equations.