Band structure of photonic crystal fibers with silica rings in triangular lattice

The characteristics of the cladding band structure of air-core photonic crystal fibers with silica rings in triangular lattice are investigated by using a standard plane wave method. The numerical results show that light can be localized in the air core by the photonic band gaps of the fiber. By increasing the air-filling fraction, the band gap edges of the low frequency photonic band gaps shift to shorter wavelength.. whereas the band gap width decreases linearly. In order to make a specified light fall in the low frequency band gaps of the fiber, the interplay of the silica ring spacing and the air-filling fraction is also analyzed. It shows that the silica ring spacing increases monotonously when the air-filling fraction is increased, and the spacing range increases exponentially. This type fiber might have potential in infrared light transmission. (c) 2006 Elsevier B.V. All rights reserved.

Effects of mesostructured silica catalysts on the depolymerization of organosolv lignin fractionated from woody eucalyptus

Isolated and purified organosolv eucalyptus wood lignin was depolymerized at different temperatures with and without mesostructured silica catalysts (i.e., SBA-15, MCM-41, ZrO2-SBA-15 and ZrO2-MCM-41). It was found that at 300 oC for 1 h with a solid/liquid ratio of 0.0175/1 (w/v), the SBA-15 catalyst with high acidity gave the highest syringol yield of 23.0% in a methanol/water mixture (50/50, wt/wt). Doping with ZrO2 over these catalysts did not increase syringol yield, but increased the total amount of solid residue. Gas chromatography-mass spectrometry (GC-MS) also identified other main phenolic compounds such as 1-(4-hydroxy-3,5-dimethoxyphenyl)-ethanone, 1,2-benzenediol, and 4-hydroxy-3,5-dimethoxy-benzaldehyde. Analysis of the lignin residues with Fourier transform-Infrared spectroscopy (FT-IR) indicated decreases in the absorption bands intensities of OH group, C-O stretching of syringyl ring and aromatic C-H deformation of syringol unit, and an increase in band intensities associated with the guaiacyl ring, confirming the type of products formed.

Beyond the ``Coffee Ring'': Re-entrant Ordering in an Evaporation-Driven Self-Assembly in a Colloidal Suspension on a Substrate

We study the phenomenon of evaporation-driven self-assembly of a colloid suspension of silica microspheres in the interior region and away from the rim of the droplet on a glass plate. In view of the importance of achieving a large-area, monolayer assembly, we first realize a suitable choice of experimental conditions, minimizing the influence of many other competing phenomena that usually complicate the understanding of fundamental concepts of such self-assembly processes in the interior region of a drying droplet. Under these simplifying conditions to bring out essential aspects, our experiments unveil an interesting competition between ordering and compaction in such drying systems in analogy to an impending glass transition. We establish a re-entrant behavior in the order disorder phase diagram as a function of the particle density, such that there is an optimal range of the particle density to realize the long-range ordering. The results are explained with the help of simulations and phenomenological theory.

Robust core-shell supramolecular assemblies based on cationic vesicles and ring-shaped {Mo-154} polyoxomolybdate nanoclusters: Template-directed synthesis and characterizations

Substantial progress has been made recently in extending the supramolecular assembly of biomimetic structures to vesicle-based sophisticated nanocomposites and mesostructures. We report herein the successful preparation of unilamellar surfactant vesicles coated with a monolayer of ring-shaped {Mo-154} polyoxometalate (POM) nanoclusters, (NH4)(28)[Mo-154 (NO)(14)O(448)Hi(4)(H2O)(70)].approximate to 350H(2)O, by coulomb attractions using preformed didodecyldimethylammonium bromide (DDAB) surfactant vesicles as templates. The resultant vesicle-templated supramolecular assemblies are robust (they do not disintegrate upon dehydration) both at room-temperature ambient and vacuum conditions, as characterized by conventional transmission electron microscopy (TEM) and atomic force microscopy (AFM). The flexibility of the complex soft assemblies was also revealed by AFM measurements. The effect of POM-vesicle coulomb attractions on the dimensions of the templating vesicles was also investigated by using dynamic light scattering (DLS).Although origins of the structure stability of the as-prepared supramolecular assemblies are not clear yet, the nanometer scale cavities and the related properties of macroions of the POM clusters may play an important role in it.

Nature of crystalline particle assembly in ring shaped colloidal stains from concentrated dispersions

The drying of colloidal droplet suspensions is important in many realms of practical application and has sustained the interest of researchers over two decades. The arrangements of polystyrene and silica beads, both of diameter 1 μm, 10% by volume of solid deposited on normal glass (hydrophilic), and silicone (hydrophobic) surfaces evaporated from a suspension volume of 3 μL, were investigated. Doughnut shape depositions were found, imputing the influence of strong central circulation flows that resulted in three general regions. In the central region which had strong particle build-up, the top most layers of particle arrangement was confirmed to be disordered using power spectrum and radial distribution function analysis. On closer examination, this appeared more like frustrated attempts to crystallize into larger grains rather than beads arranging in a disordered fashion throughout the piling process. With an adapted micro-bulldozing operation to progressively remove layers of particles from the heap, we found that the later efforts to crystallize through lateral capillary inter-particle forces were liable to be undone once the particles contacted the disorganized particles underneath, which were formed out of the jamming of fast particles arriving at the surface. © 2014 Elsevier B.V.

Self-Assembly of Poly(4-vynil-N-alkylpyridinium) Bromide onto Silica: Effect of Side-Chain Length on Structural Aspects at a Molecular Level

Self-assembly of poly(4-vynil-N-alkyl)pyridinium bromide with alkyl side chains of 2, 5, 7, 10, or 16 carbons from ethanolic solutions onto flat silica surfaces was studied by means of ellipsometry, atomic force microscopy (AFM), contact angle measurements, and sum-frequency generation (SFG) vibrational spectroscopy in the CH3 and CH2 stretch region. Ab initio quantum-chemical calculations on the N-alkylpyridinium side-group with restricted Hartree-Fock (RHF) method and 6-311G (d,p) basis set were C one to estimate the charge distribution along the pyridinium ring and the alkyl side-chain. SFG results showed that longer side chains promote the disorientation of the alkyl groups at the surface, corroborating with the contact angle values. AFM images revealed film homogeneity, regardless the alkyl side group. However, after 24 h contact with water, ringlike structures appeared on the film surfaces, when the polycation alkyl side chain had 7 or less carbons, and as the alkyl chain increased to 10 or 16 carbons, the films dewetted because the hydrophobic interactions prevailed over the electrostatic interactions between the pyridinium charged groups and the negatively charged SiO2 surface. Under acid conditions (HCl 0.1 mol.L-1), the film mean thickness values decreased up to 50% of original values when the alkyl side chains were ethyl or pentyl groups due to ion-pair disruption, but for longer groups they remained unchanged. Quantum-chemical optimization and Mulliken electron population showed that (i) from C2 to C15 the positive charge at the headgroup (HG) decreased 0.025, while the charge at combined HG + alpha-CH2 increased 0.037; and (ii) for C6 or longer, the alkyl side group presents a tilt in the geometry, moving away from the plane. Such effects summed up over the whole polymer chain give support to suggest that when the side chains are longer than 7 carbons, the hydrophobic interaction decreases film stability and increases acid resistance.

Nuovi catalizzatori per l'idrogenazione, l'idrogenolisi/ring-opening di composti aromatici policiclici

The removal of aromatic hydrocarbons from diesel has received considerable attention after environmental regulations that require petroleum refiners to raise cetane number and to limit aromatics in diesel fuel in order to improve combustion efficiency and reduce particulate and NOx emissions. An alternative is blending with Fischer–Tropsch (FT) gas-to-liquid diesel fuel; however, this option may not be economically viable solution in case of extensive blend. Another alternative is to incorporate in the diesel pool a greater fraction of the so-called light cycle oil (LCO). Due to its high aromatics content and its low cetane number (typically between 20 and 30), the incorporation of LCO may have a negative impact on the quality of diesel. Current technologies for LCO improvement are based on hydrogenation to adjust both sulphur and cetane number but while an important fraction of the aromatics present in LCO can be saturated in a deep hydrogenation process, the cetane number may still be lower than the target values specified in diesel legislations, so further upgrading is needed. An interesting technology for improving the cetane number of diesels and maintaining meanwhile high diesel yields is achieved by combining a complete hydrogenation process with a selective ring opening (SRO) reaction of the naphthenic rings. The SRO can be defined as naphthene ring-opening to form compounds with high cetane number, but without any carbon losses. Controlling the interconversion of six- and five- membered rings via an acid-catalyzed ring-contraction step is also of great importance, since selective conversion of six-membered to five-membered naphthene rings greatly influences ring-opening rates and selectivity. High intrinsic activity may be enhanced by deposition of noble metals on acidic, high surface area supports, because it is possible to arrange close proximity of the metal and acid sites. Moreover, in large-pore supports, the diffusion resistance of liquid reactants into the pores is minimized. In addition to metal centres, the acid sites of support also plays role in aromatics hydrogenation. However, the functions of different kinds of acid sites (Brønsted vs. Lewis acidity), and their optimal concentrations and strengths, remain unclear. In the present study we investigated the upgrading of an aromatic-rich feedstock over different type of metal supported on mesoporous silica-alumina. The selective hydrogenolysis and ring opening of tetrahydronaphthalene (THN or tetralin) was carried out as representative of LCO fractions after deep hydrogenation process. In this regards the aim of this study is to evaluate both the effect of metals and that of the supports characterized by different acid distribution and strength, on conversion and selectivity. For this purpose a series of catalysts were prepared by impregnation. The catalysts were characterized and conversion tests of THN were performed in a lab-scale plant operating in the pressure range from 7.0-5.0 MPa and in the temperature range from 300 to 360°C.

A molecular dynamics study of swift heavy ion irradiation of amorphous silica: the role of thermal effects

Irradiation with swift heavy ions (SHI), roughly defined as those having atomic masses larger than 15 and energies exceeding 1 MeV/amu, may lead to significant modification of the irradiated material in a nanometric region around the (straight) ion trajectory (latent tracks). In the case of amorphous silica, SHI irradiation originates nano-tracks of higher density than the virgin material (densification). As a result, the refractive index is increased with respect to that of the surroundings. Moreover, track overlapping leads to continuous amorphous layers that present a significant contrast with respect to the pristine substrate. We have recently demonstrated that SHI irradiation produces a large number of point defects, easily detectable by a number of experimental techniques (work presented in the parallel conference ICDIM). The mechanisms of energy transfer from SHI to the target material have their origin in the high electronic excitation induced in the solid. A number of phenomenological approaches have been employed to describe these mechanisms: coulomb explosion, thermal spike, non-radiative exciton decay, bond weakening. However, a detailed microscopic description is missing due to the difficulty of modeling the time evolution of the electronic excitation. In this work we have employed molecular dynamics (MD) calculations to determine whether the irradiation effects are related to the thermal phenomena described by MD (in the ps domain) or to electronic phenomena (sub-ps domain), e.g., exciton localization. We have carried out simulations of up to 100 ps with large boxes (30x30x8 nm3) using a home-modified version of MDCASK that allows us to define a central hot cylinder (ion track) from which heat flows to the surrounding cold bath (unirradiated sample). We observed that once the cylinder has cooled down, the Si and O coordination numbers are 4 and 2, respectively, as in virgin silica. On the other hand, the density of the (cold) cylinder increases with respect to that of silica and, furthermore, the silica network ring size decreases. Both effects are in agreement with the observed densification. In conclusion, purely thermal effects do not explain the generation of point defects upon irradiation, but they do account for the silica densification.

Biochemical evolution III: Polymerization on organophilic silica-rich surfaces, crystal–chemical modeling, formation of first cells, and geological clues

Catalysis at organophilic silica-rich surfaces of zeolites and feldspars might generate replicating biopolymers from simple chemicals supplied by meteorites, volcanic gases, and other geological sources. Crystal–chemical modeling yielded packings for amino acids neatly encapsulated in 10-ring channels of the molecular sieve silicalite-ZSM-5-(mutinaite). Calculation of binding and activation energies for catalytic assembly into polymers is progressing for a chemical composition with one catalytic Al–OH site per 25 neutral Si tetrahedral sites. Internal channel intersections and external terminations provide special stereochemical features suitable for complex organic species. Polymer migration along nano/micrometer channels of ancient weathered feldspars, plus exploitation of phosphorus and various transition metals in entrapped apatite and other microminerals, might have generated complexes of replicating catalytic biomolecules, leading to primitive cellular organisms. The first cell wall might have been an internal mineral surface, from which the cell developed a protective biological cap emerging into a nutrient-rich “soup.” Ultimately, the biological cap might have expanded into a complete cell wall, allowing mobility and colonization of energy-rich challenging environments. Electron microscopy of honeycomb channels inside weathered feldspars of the Shap granite (northwest England) has revealed modern bacteria, perhaps indicative of Archean ones. All known early rocks were metamorphosed too highly during geologic time to permit simple survival of large-pore zeolites, honeycombed feldspar, and encapsulated species. Possible microscopic clues to the proposed mineral adsorbents/catalysts are discussed for planning of systematic study of black cherts from weakly metamorphosed Archaean sediments.

(Table 1) Results from XRD analysis as well as sediment type and selected results from ring shear experiments

The location of the seaward tip of a subduction thrust controls material transfer at convergent plate margins, and hence global mass balances. At approximately half of those margins, the material of the subducting plate is completely underthrust so that no accretion or even subduction erosion takes place. Along the remaining margins, material is scraped off the subducting plate and added to the upper plate by frontal accretion. We here examine the physical properties of subducting sediments off Costa Rica and Nankai, type examples for an erosional and an accretionary margin, to investigate which parameters control the level where the frontal thrust cuts into the incoming sediment pile. A series of rotary-shear experiments to measure the frictional strength of the various lithologies entering the two subduction zones were carried out. Results include the following findings: (1) At Costa Rica, clay-rich strata at the top of the incoming succession have the lowest strength (µres = 0.19) while underlying calcareous ooze, chalk and diatomite are strong (up to µres = 0.43; µpeak = 0.56). Hence the entire sediment package is underthrust. (2) Off Japan, clay-rich deposits within the lower Shikoku Basin inventory are weakest (µres = 0.13-0.19) and favour the frontal proto-thrust to migrate into one particular horizon between sandy, competent turbidites below and ash-bearing mud above. (3) Taking in situ data and earlier geotechnical testing into account, it is suggested that mineralogical composition rather than pore-pressure defines the position of the frontal thrust, which locates in the weakest, clay mineral-rich (up to 85 wt.%) materials. (4) Smectite, the dominant clay mineral phase at either margin, shows rate strengthening and stable sliding in the frontal 50 km of the subduction thrust (0.0001-0.1 mm/s, 0.5-25 MPa effective normal stress). (5) Progressive illitization of smectite cannot explain seismogenesis, because illite-rich samples also show velocity strengthening at the conditions tested.

Catalyst studies on the ring opening of tetrahydrofuran-dimethanol to 1,2,6-hexanetriol

The metal catalyzed hydrogenolysis of the biomass-derived THF-dimethanol to 1,2,6-hexanetriol using heterogeneous catalysts was investigated. Bimetallic Rh-Re catalysts (4 wt% Rh and a Re/Rh (mol. ratio of 0.5) on a silica support gave the best performance and 1,2,6-hexanetriol was obtained in 84% selectivity at 31% conversion (120 C, 80 bar, 4 h); the selectivity reaches a maximum of 92% at 80 C. The product distribution at prolonged reaction times or higher temperatures or both shows the formation of diols and mono-alcohols, indicating that the 1,2,6-hexanetriol is prone to subsequent hydrodeoxygenation reactions. Different silica supports were investigated and optimal results were obtained with an amorphous silica featuring an intermediate surface area and an average mesopore size of about 6 nm. TPR and XPS surface analysis support the presence of mixed Rh and Re particles. The redox Reδ+/ReTotal surface ratio correlates with the conversion in a volcano type dependency. Both gas phase as well as Rh200Re1OH cluster DFT calculations support an acid-metal bifunctional mechanism and explain the products distribution. © 2013 Elsevier B.V. All rights reserved.

Cavity ring‑up spectroscopy for dissipative and dispersive sensing in a whispering gallery mode resonator

In whispering gallery mode resonator sensing applications, the conventional way to detect a change in the parameter to be measured is by observing the steady-state transmission spectrum through the coupling waveguide. Alternatively, sensing based on cavity ring-up spectroscopy, i.e. CRUS, can be achieved transiently. In this work, we investigate CRUS using coupled mode equations and find analytical solutions with a large spectral broadening approximation of the input pulse. The relationships between the frequency detuning, coupling gap and ring-up peak height are determined and experimentally verified using an ultrahigh Q-factor silica microsphere. This work shows that distinctive dispersive and dissipative transient sensing can be realised by simply measuring the peak height of the CRUS signal, which may improve the data collection rate.