Modeling the similarities and differences between the sodalite cages (β-cages) in the generic materials

Initially in this review the sodalite framework [T₁₂O₂₄]^6– (T=Al, Si] is modeled with regular tetrahedra and disordered T atoms. Equations are given for calculating atomic coordinates from the unit cell parameter a and the T—O distancet; the expansion or contraction of the sodalite-cage is related quantitatively to changes ina through the cooperative twists of TO₄ tetrahedra about 4 axes and changes in < TOT bridge angles. The fully expanded cage has=0° and the maximum value ofa. The equations are general for any framework formed by isomorphous substitution of T by atoms other than Al, Si and for any SiAl ratio. The model and equations are extended to the zeolite A framework, which can be built from fully expanded sodalite cages. With the cooperative tilt of the TO₄ tetrahedra of zeolite A, described by Depmeier, the major variable features of the zeolite A framework are explained quantitatively. The faujasite framework has twisted-cages (>0), as in sodalite examples, and is quantitatively modeled most conveniently from sodalite examples with similar-cage contents. The review is extended to structures with T-ordering and distorted tetrahedra. Methods are given for estimating a for sodalites from a knowledge of the cavity contents, especially the sizes of cations and anions, and so on, present. Ways of predicting cavity sites in zeolite A as a function of cation size are presented, and the principal cavity sites in the faujasite-cage region are discussed. Finally the review considers isomorphous replacement of T atoms (Si or Al) by B, Be, Fe, Ga, Ge, and P; many of these substituted frameworks are stabilized by templates, or guest molecules, which reside in the cavities. Templates also stabilize Si, Al frameworks with high SiAl ratios. The modeling approach reviewed here is tested on a range of isomorphously substituted frameworks isotypic with sodalite; observed and calculated values of twist and 12O₂₄]^12– with distorted tetrahedra; these are structures with Al-O-Al bridges, which violate Loewenstein's Rule.     

Effects of ZnS:Mn concentrated vinyl ester matrices under flexural loading on the triboluminescent yield

This paper investigates the feasibility of using zinc sulfide manganese (ZnS:Mn) concentrated vinyl ester resin as a photon emitter for damage monitoring of polymer composites under flexural loading. Unreinforced vinyl ester resins doped with optical emitting materials (ZnS:Mn phosphors) in ratios of 5–50% by weight were cast, and subjected to flexural loading using standard 3-point bend tests. The intent of this work was to observe the transient response of triboluminescence (TL) throughout the failure cycle. Results indicate TL crystals emit light at various intensities corresponding to crystal concentration and imminent matrix fracture. Consequently, concentrated samples showed nearly 50% reductions of mechanical moduli. Scanning electron microscopy (SEM) revealed particulate inclusions with shearing bands and semblance of particle to resin adhesion. Despite significant parasitic effect to mechanical properties, the triboluminescent properties occur at yielding and point of matrix fracture.     

Quantum annealing of the graph coloring problem

Quantum annealing extends simulated annealing by introducing artificial quantum fluctuations. The path-integral Monte Carlo version chosen is population-based and designed to be implemented on a classical computer. Its first application to the graph coloring problem is presented in this paper. It is shown by experiments that quantum annealing can outperform classical thermal simulated annealing for this particular problem. Moreover, quantum annealing proved competitive when compared with the best algorithms on most of the difficult instances from the DIMACS benchmarks. The quantum annealing algorithm has even found that the well-known benchmark graph dsjc1000.9 has a chromatic number of at most 222. This is an improvement on its best upper-bound from a large body of literature.     

Progress in triboluminescence-based smart optical sensor system

Extensive research work has been done in recent times to apply the triboluminescence (TL) phenomenon for damage detection in engineering structures. Of particular note are the various attempts to apply it in the detection of impact damages in composites and aerospace structures. This is because TL-based sensor systems have a great potential for wireless, in-situ and distributed (WID) structural health monitoring when fully developed. This review article highlights development and the current state-of-the-art in the application of TL-based sensor systems. The underlying mechanisms believed to be responsible for triboluminescence, particularly in zinc sulfide manganese, a highly triboluminescent material, are discussed. The challenges militating against the full exploitation and field application of TL sensor systems are also identified. Finally, viable solutions and approaches to address these challenges are enumerated.     

Synthesis and characterization of silicalite-1/carbon-graphite membranes

Silicalite-1/carbon-graphite composite membranes have been prepared using a standard hydrothermal synthesis method and characterized by XRD, SEM, TGA, BET and permeation experiments. Single gas permeation fluxes and binary mixtures separation and selectivity data are reported for methane, ethane and propane using the composite membranes. Carbon-graphite oxidized for 4 h prior to membrane preparation had the most promising separation properties. The permeation fluxes for the binary mixtures reflect that of the single component flux ratios. At 20 degrees C the membranes show high separation selectivity toward lighter component in binary mixtures. Single gas permeances for methane and ethane were found to decrease with increasing temperatures while that of propane fluctuates.     

Monte Carlo and molecular dynamics simulations of methane in potassium montmorillonite clay hydrates at elevated pressures and temperatures

The structure and dynamics of methane in hydrated potassium montmorillonite clay have been studied under conditions encountered in sedimentary basin and compared to those of hydrated sodium montmorillonite clay using computer simulation techniques. The simulated systems contain two molecular layers of water and followed gradients of 150 bar km(-1) and 30 K km(-1) up to a maximum burial depth of 6 km. Methane particle is coordinated to about 19 oxygen atoms, with 6 of these coming from the clay surface oxygen. Potassium ions tend to move away from the center towards the clay surface, in contrast to the behavior observed with the hydrated sodium form. The clay surface affinity for methane was found to be higher in the hydrated K-form. Methane diffusion in the two-layer hydrated K-montmorillonite increases from 0.39 x 10(-9) m2 s(-1) at 280 K to 3.27 x 10(-9) m2 s(-1) at 460 K compared to 0.36 x 10(-9) m2 s(-1) at 280 K to 4.26 x 10(-9) m2 s(-1) at 460 K in Na-montmorillonite hydrate. The distributions of the potassium ions were found to vary in the hydrates when compared to those of sodium form. Water molecules were also found to be very mobile in the potassium clay hydrates compared to sodium clay hydrates.     

Synthesis,crystal structure,and density functional theory study of a zinc(II) complex containing terpyridine and pyridine-2,6-dicarboxylic acid ligands: Analysis of the interactions with amoxicillin

An octahedral zinc(II) complex of 2,2′:6′,2″-terpyridine (Tpy) and pyridine-2,6-dicarboxylate (Pydc), [Zn(II)(Tpy)(Pydc)·4H₂O] was synthesized and its structure was determined by a single-crystal X-ray diffraction. The ligand pyridine-2,6-dicarboxylate coordinated to the zinc(II) ion via two pairs of carboxylate oxygens and one nitrogen atom, whereas 2,2′:6′,2″-terpyridine also contributed three coordination bonds through its nitrogen atoms. [Zn(II)(Tpy)(Pydc)·4H₂O] showed luminescence properties between 412 and 435 nm in DMSO. The solid-state octahedral geometry of [Zn(II)(Tpy)(Pydc)·4H₂O] was also preserved in solution as confirmed by the observed UV λ_ex = 346. Experimental and theoretical studies indicated that [Zn(II)(Tpy)(Pydc)·4H₂O] interacted with amoxicillin. Density functional theory calculations at B3LYP/LanL2dz level of theory suggested that [Zn(II)(Tpy)(pydc)·4H₂O] dimer interacts with (2S,5R,6R)-6-{[(2R)-2-amino-2-(4-hydroxyphenyl)-acetyl]amino}-3,3-dimethyl-7-oxo-4-thia-1-azabicyclo[3.2.0]heptane-24-carboxylic acid (amoxicillin) via highest occupied molecular orbital and lowest unoccupied molecular orbital, π–π interaction, hydrogen bond interaction, and van der Waals forces, thus influencing [Zn(II)(Tpy)(Pydc)·4H₂O] properties.     

A comparative physicochemical study of unsymmetrical indium phthalocyanines in the presence of magnetic nanoparticles or quantum dots

Asymmetric indium phthalocyanine (3, containing an NH₂ group) was conjugated (via an amide bond) to magnetic nanoparticle (MNP) functionalized with carboxylic acid or glutathione-capped CdTe/ZnSe/ZnO quantum dots to form 3-MNPs or 3-QDs. Techniques such as time-resolved fluorescence measurements, transmission electron microscopy, XPS, elemental analysis, FTIR, NMR (¹H, ¹³C, and cozy), electronic spectroscopy, as well as mass spectroscopy were employed to characterize 3 and its nanoconjugates. The phthalocyanine conjugated to quantum dot (3-QDs) possesses the lowest Ф_pd higher Ф_? and Ф_T as well as longer triplet lifetimes compares to 3-MNPs and free phthalocyanine.     

Atomistic simulation of mineral surfaces: Studies of surface stability and growth

Atomistic simulation represents a valuable methodology for interpreting and predicting surface structures. The emphasis of our work is to develop and apply this approach to understanding the role of surface defects and additives in modifying the structure and stability of mineral surfaces. The basis of our approach is energy minimisation which allows us to evaluate the most stable surface configurations. The utility and limitations of this approach will be illustrated via a number of examples. These include describing the factors governing the stability of mineral surfaces and applying these considerations to understanding the surfaces of olivine and spinel. In addition, we are beginning to address the water-solid interface. We find a wide variation in the reactivity of the different surfaces of rock-salt oxides from (100) which show only physisorption, through stepped surfaces which show dissociative adsorption to (111) which forms the hydroxide. One way of determining the interaction between surfaces and additives is the modification of crystal growth thus we are also concerned with attempting to model the growth process. However, the low index surfaces often grow via screw dislocations. Therefore preliminary work on modelling the interaction of screw dislocations with surfaces of MgO will be described.