Metal-Enhanced S(2) Fluorescence from Azulene

In this paper, we report the first observation of metal-enhanced S(2) emission at room and low temperature (77K). The S(2) emission intensity of Azulene is enhanced by close proximity to Silver island films (SiFs). In this regard, a ≈ 2-fold higher S(2) fluorescence intensity of Azulene was observed from SiFs as compared to a glass control sample. This suggests that S(2) excited states can couple to surface plasmons and enhance S(2) fluorescence yields, a helpful observation in our understanding the interactions between plasmons and lumophores, and our continued efforts to develop a unified plasmon-lumophore/fluorophore theory.     

Metal-Assisted and Microwave-Accelerated Evaporative Crystallization

We describe a platform technology, called metal-assisted and microwave-assisted evaporative crystallization (MA-MAEC), based on the combined use of silver nanoparticles and microwave heating for selective and rapid crystallization of small molecules. In this regard, the crystallization of a model small molecule (glycine) was achieved in several seconds. Glycine crystals grown on silver nanostructures with and without microwave heating were found to be larger than those grown on blank glass slides. The MA-MAEC technique has the potential to selectively grow the desired polymorphs of small molecules "on-demand" in a fraction of the time as compared to the conventional evaporative crystallization.     

Atom transfer radical polymerization of 1-phenoxycarbonyl ethyl methacrylate monomer

Atom transfer radical polymerization conditions with copper(I) bromide/2,2^′-bipyridine (Cu/2,2^′-bpy) as the catalyst system were employed for the homopolymerization and random copolymerization of 1-phenoxycarbonyl ethyl methacrylate (PCMA) with methyl methacrylate (MMA). Temperature studies indicated that the polymerizations occurred smoothly in bulk at 110 °C. Poly(PCMA)(polydispersity index=1.27) homopolymer was characterized and then used as macroinitiator for increasing its molecular weight. The homopolymerization of PCMA was also carried out under free radical conditions using 2,2^′-azobisisobutyronitrile as an initiator.The monomer and polymers were characterized by FT-IR and ¹H and ¹³C-NMR techniques. The glass transition temperatures, the solubility parameters and average-molecular weights of the polymers were determined. Thermal stabilities of the polymers were given as compared with each other by using TGA curves. Thermal degradation products of poly(PCMA)s obtained by ATRP and free radical polymerization were compared with each other by using ¹H-NMR technique.     

Voltage-Gated Metal-Enhanced Fluorescence

We demonstrate the influence of electrical current on the ability of surface plasmons to amplify fluorescence signatures. An applied direct current across Silver Island Films (SIFs) of low electrical resistance perturbs the fluorescence enhancement. For a given applied current, surface plasmons in just-continuous films are sparsely available for fluorophore dipole-coupling and hence the enhanced fluorescence is gated as a function of the applied current. For thicker, low resistance films, sufficient charge carriers are now present in the metal that metal-enhanced fluorescence (MEF) is perturbed to a lesser extent, induced surface plasmons readily formed on the surface by the close-proximity dipole.     

Combination of HAADF‐STEM and ADF‐STEM Tomography for Core–Shell Hybrid Materials

Characterization of core–shell type nanoparticles in 3D by transmission electron microscopy (TEM) can be very challenging. Especially when both heavy and light elements coexist within the same nanostructure, artifacts in the 3D reconstruction are often present. A representative example would be a particle comprising an anisotropic metallic (Au) nanoparticle coated with a (mesoporous) silica shell. To obtain a reliable 3D characterization of such an object, a dose‐efficient strategy is proposed to simultaneously acquire high‐angle annular dark‐field scanning TEM and annular dark‐field tilt series for tomography. The 3D reconstruction is further improved by applying an advanced masking and interpolation approach to the acquired data. This new methodology enables us to obtain high‐quality reconstructions from which also quantitative information can be extracted. This approach is broadly applicable to investigate hybrid core–shell materials.     

Intercomparison of techniques for estimation of sedimentation rate in the Sabah and Sarawak coastal waters

A total of eight sediment cores with 50 cm length were taken in the Sabah and Sarawak coastal waters using a gravity corer in 2004 to estimate sedimentation rates using four mathematical models of CIC, Shukla-CIC, CRS and ADE. The average of sedimentation rate ranged from 0.24 to 0.48 cm year^?1, which is calculated based on the vertical profile of ²¹⁰Pb_ex in sediment core. The finding also showed that the sedimentation rates derived from four models were generally shown in good agreement with similar or comparable value at some stations. However, based on statistical analysis of paired sample t-test indicated that CIC model was the most accurate, reliable and suitable technique to determine the sedimentation rate in the coastal area.     

The Binomial-Discrete Poisson-Lindley Model:Modeling and Applications to Count Regression

On the basis of a well-established binomial structure and the so-called Poisson-Lindley distribution,a new two-parameter discrete distribution is introduced.Its...     

YCu3Al2, an example of an AB5 structure type

Yttrium tricopper dialuminium, YCu₃Al₂, is isostructural with hexagonal CaCu₅, in which each Cu atom at the 3g(½,0,½) position in space group P6/mmm (No. 191) is partially replaced by an Al atom. The hydrogen‐uptake properties are usually enhanced in other AB₅ structures by aluminium substitution. YCu₅ does not show any hydrogen absorption, and the goal of the present work is to investigate whether aluminium substitution could expand the metal‐atom lattice enough to provide better interstitial positions for hydrogen storage. However, no enthalpy change was observed up to 773 K under 3 MPa static H₂ pressure by differential thermal analysis (DTA) for the title compound. The compound does not show any significant hydrogen absorption/desorption in the pressure‐composition isotherms (P–C–T diagrams) in the temperature range 298–673 K under 3.3 MPa H₂ pressure.     

A Titanium(IV)‐Based Metal–Organic Framework Featuring Defect‐Rich Ti‐O Sheets as an Oxidative Desulfurization Catalyst

While titanium‐based metal–organic frameworks (MOFs) have been widely studied for their (photo)catalytic potential, only a few Ti^IV MOFs have been reported owing to the high reactivity of the employed titanium precursors. The synthesis of COK‐47 is now presented, the first Ti carboxylate MOF based on sheets of Ti^IVO₆ octahedra, which can be synthesized with a range of different linkers. COK‐47 can be synthesized as an inherently defective nanoparticulate material, rendering it a highly efficient catalyst for the oxidation of thiophenes. Its structure was determined by continuous rotation electron diffraction and studied in depth by X‐ray total scattering, EXAFS, and solid‐state NMR. Furthermore, its photoactivity was investigated by electron paramagnetic resonance and demonstrated by catalytic photodegradation of rhodamine 6G.