Preparation, crystal structure, and thermal stability of the cadmium sulfide nanoclusters Cd6S44+ and Cd2Na2S4+in the sodalite cavities of zeolite A (LTA)

The crystal structure and thermal stability of two cadmium sulfide nanoclusters prepared in zeolite A (LTA) have been studied by XPS, TGA, and single-crystal and powder XRD. The crystal structures of Cd2.4Na3.2(Cd6S4)0.4(Cd2Na2S)0.6(H2O)> or =5.8[Si12Al12O48]-LTA (a = 12.2919(7) A, crystal 1 (hydrated)) and /Cd4Na2(Cd2O)(Na2O)/[Si12Al12O48]-LTA (a = 12.2617(4) A, crystal 2 (dehydrated)) were determined by single-crystal methods in the cubic space group Pm3m at 294(1) K. Crystal 1 was prepared by ion exchange of Na12-LTA in an aqueous stream 0.05 M in Cd2+, followed by washing in a stream of water, followed by reaction in an aqueous stream 0.05 M in Na2S. Crystal 2 was made by dehydrating crystal 1 at 623 K and 1 x 10(-6) Torr for 3 days. In crystal 1, Cd6S4(4+) nanoclusters were found in and extending out of about 40% of the sodalite cavities. Central to each Cd6S4(4+) cluster is a Cd4S4 unit (interpenetrating Cd2+ and S2- tetrahedra with near Td symmetry, Cd-S = 2.997(24) A, Cd-S-Cd = 113.8(12) degrees, and S-Cd-S = 58.1(24) degrees). Each of the two remaining Cd2+ ions bonds radially through a 6-ring of the zeolite framework to a sulfide ion of this Cd4S4 unit (Cd-S = 2.90(8) A). In each of the remaining 60% of the sodalite cavities of crystal 1, a planar Cd2Na2S4+ cluster was found (Cd-S/Na-S = 2.35(5)/2.56(14) A and Cd-S-Cd/Na-S-Na = 122(5)/92(7) degrees). Cd6S4(4+) and Cd2Na2S4+ are stable within the zeolite up to about 700 K in air. Upon vacuum dehydration at 623 K, all sulfur was lost (crystal 2). Instead as anions, only two oxide ions remain per sodalite unit. One bridges between two Cd2+ ions (Cd2O2+, Cd-O = 2.28(3) A) and the other between two Na+ ions (Na2O, Na-O = 2.21(10) A).     

Modulation of Foreign Body Reaction against PDMS Implant by Grafting Topographically Different Poly(acrylic acid) Micropatterns

The surface of poly(dimethylsiloxane) (PDMS) is grafted with poly(acrylic acid) (PAA) layers via surface‐initiated photopolymerization to suppress the capsular contracture resulting from a foreign body reaction. Owing to the nature of photo‐induced polymerization, various PAA micropatterns can be fabricated using photolithography. Hole and stripe micropatterns ≈100‐µm wide and 3‐µm thick are grafted onto the PDMS surface without delamination. The incorporation of PAA micropatterns provides not only chemical cues by hydrophilic PAA microdomains but also topographical cues by hole or stripe micropatterns. In vitro studies reveal that a PAA‐grafted PDMS surface has a lower proliferation of both macrophages (Raw 264.7) and fibroblasts (NIH 3T3) regardless of the pattern presence. However, PDMS with PAA micropatterns, especially stripe micropatterns, minimizes the aggregation of fibroblasts and their subsequent differentiation into myofibroblasts. An in vivo study also shows that PDMS samples with stripe micropatterns polarized macrophages into anti‐inflammatory M2 macrophages and most effectively inhibits capsular contracture, which is demonstrated by investigation of inflammation score, transforming‐growth‐factor‐β expression, number of macrophages, and myofibroblasts as well as the collagen density and capsule thickness.     

Anomalous Hall effect in sputter-deposited CoxTi1−xO2–δ films

Hall effect measurements were performed on epitaxial Co_xTi_1−xO_2–δ thin films grown on (0 0 1) LaAlO₃ by reactive RF magnetron co-sputter deposition. Magnetization measurements reveal ferromagnetic behavior in M–H loop at room temperature for Co_xTi_1−xO_2–δ thin films for which x?0.02. An anomalous Hall effect was observed for Co_0.10Ti_0.90O_2−δ films grown with the partial pressure of water P(H₂O)=4×10⁻⁴ Torr or less. These films exhibit a positive ordinary Hall coefficient and a positive magnetoresistance. X-ray diffraction on films grown under these conditions shows evidence for Ti_nO_2n−1 phase due to the deficiency of oxygen. In contrast, Hall measurements taken for undoped and Co-doped TiO₂ thin films grown under more oxidizing conditions show only the ordinary Hall effect with a negative Hall coefficient consistent with n-type conduction. For these films, the magnetoresistance was positive and increased monotonically with increasing magnetic field. The results suggest that Co-doped Ti_nO_2n−1 may be a dilute magnetic semiconducting oxide for which the carriers couple to the spin polarization.     

Ammonia Oxidation Enhanced by Photopotential Generated by Plasmonic Excitation of a Bimetallic Electrocatalyst

We study how visible light influences the activity of an electrocatalyst composed of Au and Pt nanoparticles. The bimetallic composition imparts a dual functionality: the Pt component catalyzes the electrochemical oxidation of ammonia to liberate hydrogen and the Au component absorbs visible light by the excitation of localized surface plasmon resonances. Under visible-light excitation, this catalyst exhibits enhanced electrochemical ammonia oxidation kinetics, outperforming previously reported electrochemical schemes. We trace the enhancement to a photochemical potential resulting from electron–hole carriers generated in the electrocatalyst by plasmonic excitation. The photopotential responsible for enhanced kinetics scales linearly with the light intensity—a general design principle for eliciting superlative photoelectrochemical performance from catalysts comprised of plasmonic metals or hybrids. We also determine a photochemical conversion coefficient.     

Aggregation of reduced graphene oxide and its nanohybrids with magnetite and elemental silver under environmentally relevant conditions

Journal of Nanoparticle Research - Utilizing solar energy for hydrogen evolution is a great challenge for its insufficient visible-light power conversion. In this paper, we report a facile...     

Liquid crystal aligning capabilities on surface-reformed indium-doped zinc oxide films via ion-beam exposure

We investigated the characteristics of a solution-processed indium-doped zinc oxide (In:ZnO) film formed via ion-beam (IB) irradiation as a liquid crystal (LC) alignment layer. The In:ZnO film was deposited using solution processing and cured at various temperatures. Uniform LC alignment was observed at all curing temperatures in cross-polarised optical microscopy images. A regular pre-tilt angle supported these results and showed homogeneous LC alignment. Several surface analyses were conducted to evaluate the effect of IB irradiation on the In:ZnO film surface. X-ray diffraction analysis showed an amorphous structure both before and after IB irradiation, and physical surface reformation was observed using atomic force microscopy. Root mean square surface roughness was reduced and a smooth surface was achieved after IB irradiation. X-ray photoelectron spectroscopy was used to detect chemical surface reformation. It was found that the IB irradiation broke the metal-oxide bonds and increased the occurrence of oxygen vacancies, which affected the van der Waals forces between the LC molecules and the In:ZnO film surface. Electrical performance was observed to identify the possibility of using the In:ZnO film in LC applications. Enhanced electro-optical performance was measured and zero residual DC voltage which was verified using a capacitance-voltage curve was achieved.     

Two-dimensionally well-ordered multilayer structures in thin films of a brush polypeptide

In this study, we report the first production of two-dimensionally well-ordered molecular multilayers (i.e., with a well-defined molecular lamellar structure) based on the antiparallel beta-sheet chain conformation in thin films of a brush polypeptide, poly(S-n-hexadecyl-dl-homocysteine) (PHHC), through the use of a simple spin-coating process and the quantitative structural and property analysis of the thin films using a grazing incidence X-ray scattering technique combined with Fourier transform infrared spectroscopy and differential scanning calorimetry. These analyses provide detailed information about the structure and molecular conformation of the self-assembled lamellae in the PHHC thin film, which is not easily obtained using conventional techniques. Moreover, we used the in situ measurements carried out at various temperatures and the data analyses to establish mechanisms for the evolution of the self-assembled lamellar structures in the film and for their melting. In addition, we propose molecular structure models of the PHHC polymer molecules in the thin film at various temperatures.     

Electrodiffusion of ions inside living cells

Electrodiffusion of ions, both inside and outside biologicalcells, are of utmost importance to proper cellular functions.Experiments indicate that both ion concentrations and electropotentialcan jump discontinuously across the cell membranes. We studya system of nonlinear partial differential equations modellingsuch phenomena. Jump conditions for species concentrations andelectropotential across cell membranes are imposed. Under zero-fluxboundary conditions for one-dimensional domains, the solutionsare proved to exist for all times. With further assumptions,these transient solutions will converge to the unique steady-statesolution. Numerical experiments in one- and two-dimensionaldomains are also performed in order to study some unresolvedtheoretical issues.