The crystal structure and vibrational spectroscopy of jarosite and alunite minerals

The alunite supergroup of minerals is a large hydroxy-sulfate mineral group, which has seen renewed interest following their discovery on Mars. Numerous reviews exist concerning nomenclature, formation, and natural occurrence of this mineral group. Sulfate minerals in general are widely studied and their vibrational spectra are well characterized. However, no specific review concerning alunite and jarosite spectroscopy and crystal structure has been forthcoming. This review focuses on the controversial aspects of the crystal structure and vibrational spectroscopy of jarosite and alunite minerals. Inconsistencies regarding band assignments especially in the 1000–400 cm−1 region plague these two mineral groups and result in different band assignments among the various spectroscopic studies. There are significant crystallographic and magnetic structure ambiguities with regards to ammonium and hydronium end-members, namely, the geometry these two ions assume in the structure and the fact that hydronium jarosite is a spin glass. It was also found that the synthetic causes for the super cell in plumbojarosite, minamiite, huangite, and walthierite are not known.

Bond dissociation energies of organic molecules

In this Account we have compiled a list of reliable bond energies that are based on a set of critically evaluated experiments. A brief description of the three most important experimental techniques for measuring bond energies is provided. We demonstrate how these experimental data can be applied to yield the heats of formation of organic radicals and the bond enthalpies of more than 100 representative organic molecules.

Generation and characterization of ionic and neutral dihydroxy boron B(OH)(2)(+/0) in the gas phase

The dicoordinated borinium ion, dihydroxyborinium, B(OH)(2)(+) is generated from methyl boronic acid CH3B(OH)(2) by dissociative electron ionization and its connectivity confirmed by collisional activation. Neutralization-reionization (NR) experiments on this ion indicate that the neutral B(OH)(2) radical is a viable species in the gas phase. Both vertical neutralization of B(OH)(2)(+) and reionization of B(OH)(2) in the NR experiment are, however, associated with particularly unfavorable Franck-Condon factors. The differences in adiabatic and vertical electron transfer behavior can be traced back to a particular pi stabilization of the cationic species compared to the sp(2)-type neutral radical. Thermochemical data on several neutral and cationic boron compounds are presented based on calculations performed at the G2 level of theory.

Painting anatase (TiO2) nanocrystals on long nanofibers to prepare photocatalysts with large active surface for dye degradation and organic synthesis

Anatase TiO2 nanocrystals were painted on H-titanate nanofibers by using an aqueous solution of titanyl sulfate. The anatase nanocrystals were bonded solidly onto the titanate fibers through formation of coherent interfaces at which the oxygen atoms were shared by the nanocrystals and the fiber. This approach allowed us to create large anatase surfaces on the nanofibers, which are active in photocatalytic reactions. This method was also applied successfully to coat anatase nanocrystals on surfaces of fly ash and layered clay. The painted nanofibers exhibited a much higher catalytic activity for the photocatalytic degradation of sulforhodamine B and the selective oxidation of benzylamine to the corresponding imine (with a product selectivity >99%) under UV irradiation than both the parent H-titanate nanofibers and a commercial TiO2 powder, P25. We found that gold nanoparticles supported on H-titanate nanofibers showed no catalytic activity for the reduction of nitrobenzene to azoxybenzene, whereas the gold nanoparticles supported on the painted nanofibers and P25 could efficiently reduce nitrobenzene to azoxybenzene as the sole product under visible light irradiation. These results were different from those from the reduction on the gold nanoparticles photocatalyst on ZrO2, in which the azoxybenzene was the intermediate and converted to azobenzene quickly. Evidently, the support materials significantly affect the product selectivity of the nitrobenzene reduction. Finally, the new photocatalysts could be easily dispersed into and separated from a liquid because of their fibril morphology, which is an important advantage for practical applications.

Direct and quantitative detection of bacteriophage by “hearing” surface detachment using a quartz crystal microbalance

We show that it is possible to detect specifically adsorbed bacteriophage directly by breaking the interactions between proteins displayed on the phage coat and ligands immobilized on the surface of a quartz crystal microbalance (QCM). This is achieved through increasing the amplitude of oscillation of the QCM surface and sensitively detecting the acoustic emission produced when the bacteriophage detaches from the surface. There is no interference from nonspecifically adsorbed phage. The detection is quantitative over at least 5 orders of magnitude and is sensitive enough to detect as few as 20 phage. The method has potential as a sensitive and low-cost method for virus detection.

Halogen bond mediated crystal engineering of metal complexes

This project explored the potential for halogen bonds to predictably organise metal-containing molecular building blocks in crystalline materials. A novel method for the halogen bond mediated crystal engineering of metal complexes was discovered, which led to the preparation of new materials with potential applications in molecular switching devices and advanced memory storage systems.

Commissioning of a new commercial plastic scintillator system for radiotherapy

Introduction Since 1992 there have been several articles published on research on plastic scintillators for use in radiotherapy. Plastic scintillators are said to be tissue equivalent, temperature independent and dose rate independent [1]. Although their properties were found to be promising for measurements in megavoltage X-ray beams there were some technical difficulties with regards to its commercialisation. Standard Imaging has produced the first commercial system which is now available for use in a clinical setting. The Exradin W1 scintillator device uses a dual fibre system where one fibre is connected to the Plastic Scintillator and the other fibre only measures Cerenkov radiation [2]. This paper presents results obtained during commissioning of this dosimeter system. Methods All tests were performed on a Novalis Tx linear accelerator equipped with a 6 MV SRS photon beam and conventional 6 and 18 MV X-ray beams. The following measurements were performed in a Virtual Water phantom at a depth of dose maximum. Linearity: The dose delivered was varied between 0.2 and 3.0 Gy for the same field conditions. Dose rate dependence: For this test the repetition rate of the linac was varied between 100 and 1,000 MU/min. A nominal dose of 1.0 Gy was delivered for each rate. Reproducibility: A total of five irradiations for the same setup. Results The W1 detector gave a highly linear relationship between dose and the number of Monitor Units delivered for a 10 9 10 cm2 field size at a SSD of 100 cm. The linearity was within 1 % for the high dose end and about 2 % for the very low dose end. For the dose rate dependence, the dose measured as a function of repetition the rate (100–1,000 MU/min) gave a maximum deviation of 0.9 %. The reproducibility was found to be better than 0.5 %. Discussion and conclusions The results for this system look promising so far being a new dosimetry system available for clinical use. However, further investigation is needed to produce a full characterisation prior to use in megavoltage X-ray beams.

Direct and quantitative detection of bacteriophage by "hearing" surface detachment using a quartz crystal microbalance

We show that it is possible to detect specifically adsorbed bacteriophage directly by breaking the interactions between proteins displayed on the phage coat and ligands immobilized on the surface of a quartz crystal microbalance (QCM). This is achieved through increasing the amplitude of oscillation of the QCM surface and sensitively detecting the acoustic emission produced when the bacteriophage detaches from the surface. There is no interference from nonspecifically adsorbed phage. The detection is quantitative over at least 5 orders of magnitude and is sensitive enough to detect as few as 20 phage. The method has potential as a sensitive and low-cost method for virus detection.

Syntheses of NCN and NC3N from ionic precursors in the gas phase and an unusual rearrangement of neutral NC3N : A joint experimental and theoretical study

Neutral NCN is made in a mass spectrometer by charge stripping of NCN-., while neutral dicyanocarbene NCCCN can be formed by neutralization of either the corresponding anionic and cationic species, NCCCN-. and NCCCN+.. Theoretical calculations at the RCCSD(T)/aug-cc-pVTZ//B3LYP/6-31+G(d) level of theory indicate that the (3)Sigma (-)(g) State of NCCCN is 18 kcal mol(-1) more stable than the (1)A(1) state. While the majority of neutrals formed from either NCCCN-. or NCCCN+. correspond to NCCCN, a proportion of the neutral NCCCN molecules have sufficient excess energy to effect rearrangement, as evidenced by a loss of atomic carbon in the neutralization reionization (NR) spectra of either NCCCN+. and NCCCN-.. C-13 labeling studies indicate that loss of carbon occurs statistically following or accompanied by scrambling of all three carbon atoms. A theoretical study at the B3LYP/6-31+G(d)//B3LYP/6-31+G(d) level of theory indicates that C loss is a consequence of the rearrangement sequence NCCCN --> CNCCN --> CNCNC and that C scrambling occurs within singlet CNCCN via the intermediacy of a four-membered C-2v-symmetrical transition structure.

Failure of discontinuous railhead edges due to plastic strain accumulation

Railhead is perhaps the highest stressed civil infrastructure due to the passage of heavily loaded wheels through a very small contact patch. The stresses at the contact patch cause yielding of the railhead material and wear. Many theories exist for the prediction of these mechanisms of continuous rails; this process in the discontinuous rails is relatively sparingly researched. Discontinuous railhead edges fail due to accumulating excessive plastic strains. Significant safety concern is widely reported as these edges form part of Insulated Rail Joints (IRJs) in the signalling track circuitry. Since Hertzian contact is not valid at a discontinuous edge, 3D finite element (3DFE) models of wheel contact at a railhead edge have been used in this research. Elastic–plastic material properties of the head hardened rail steel have been experimentally determined through uniaxial monotonic tension tests and incorporated into a FE model of a cylindrical specimen subject to cyclic tension load- ing. The parameters required for the Chaboche kinematic hardening model have been determined from the stabilised hysteresis loops of the cyclic load simulation and imple- mented into the 3DFE model. The 3DFE predictions of the plastic strain accumulation in the vicinity of the wheel contact at discontinuous railhead edges are shown to be affected by the contact due to passage of wheels rather than the magnitude of the loads the wheels carry. Therefore to eliminate this failure mechanism, modification to the contact patch is essential; reduction in wheel load cannot solve this problem.

High-voltage insulation organic-inorganic nanocomposites by plasma polymerization

In organic-inorganic nanocomposites, interfacial regions are primarily influenced by the dispersion uniformity of nanoparticles and the strength of interfacial bonds between the nanoparticles and the polymer matrix. The insulating performance of organic-inorganic dielectric nanocomposites is highly influenced by the characteristics of interfacial regions. In this study, we prepare polyethylene oxide (PEO)-like functional layers on silica nanoparticles through plasma polymerization. Epoxy resin/silica nanocomposites are subsequently synthesized with these plasma-polymerized nanoparticles. It is found that plasma at a low power (i.e., 10 W) can significantly increase the concentration of C-O bonds on the surface of silica nanoparticles. This plasma polymerized thin layer can not only improve the dispersion uniformity by increasing the hydrophilicity of the nanoparticles, but also provide anchoring sites to enable the formation of covalent bonds between the organic and inorganic phases. Furthermore, electrical tests reveal improved electrical treeing resistance and decreased dielectric constant of the synthesized nanocomposites, while the dielectric loss of the nanocomposites remains unchanged as compared to the pure epoxy resin.

Tuning of magnetization in vertical graphenes by plasma-enabled chemical conversion of organic precursors with different oxygen content

Different magnetization in vertical graphenes fabricated by plasma-enabled chemical conversion of organic precursors with various oxygen atom contents and bonding energies was achieved. The graphenes grown from fat-like precursors exhibit magnetization up to 8 emu g−1, whereas the use of sugar-containing precursors results in much lower numbers. A relatively high Curie temperature exceeding 600 K was also demonstrated.

Self-organized vertically aligned single-crystal silicon nanostructures with controlled shape and aspect ratio by reactive plasma etching

The formation of vertically aligned single-crystalline silicon nanostructures via "self-organized" maskless etching in Ar+ H 2 plasmas is studied. The shape and aspect ratio can be effectively controlled by the reactive plasma composition. In the optimum parameter space, single-crystalline pyramid-like nanostructures are produced; otherwise, nanocones and nanodots are formed. This generic nanostructure formation approach does not involve any external material deposition. It is based on a concurrent sputtering, etching, hydrogen termination, and atom/radical redeposition and can be applied to other nanomaterials.

Diffusivity of adatoms on plasma-exposed surfaces determined from the ionization energy approximation and ionic polarizability

Microscopic surface diffusivity theory based on atomic ionization energy concept is developed to explain the variations of the atomic and displacement polarizations with respect to the surface diffusion activation energy of adatoms in the process of self-assembly of quantum dots on plasma-exposed surfaces. These polarizations are derived classically, while the atomic polarization is quantized to obtain the microscopic atomic polarizability. The surface diffusivity equation is derived as a function of the ionization energy. The results of this work can be used to fine-tune the delivery rates of different adatoms onto nanostructure growth surfaces and optimize the low-temperature plasma based nanoscale synthesis processes.

Nonlinear geometric and material computational technique : higher-order element with refined plastic hinge approach

This paper addresses of the advanced computational technique of steel structures for both simulation capacities simultaneously; specifically, they are the higher-order element formulation with element load effect (geometric nonlinearities) as well as the refined plastic hinge method (material nonlinearities). This advanced computational technique can capture the real behaviour of a whole second-order inelastic structure, which in turn ensures the structural safety and adequacy of the structure. Therefore, the emphasis of this paper is to advocate that the advanced computational technique can replace the traditional empirical design approach. In the meantime, the practitioner should be educated how to make use of the advanced computational technique on the second-order inelastic design of a structure, as this approach is the future structural engineering design. It means the future engineer should understand the computational technique clearly; realize the behaviour of a structure with respect to the numerical analysis thoroughly; justify the numerical result correctly; especially the fool-proof ultimate finite element is yet to come, of which is competent in modelling behaviour, user-friendly in numerical modelling and versatile for all structural forms and various materials. Hence the high-quality engineer is required, who can confidently manipulate the advanced computational technique for the design of a complex structure but not vice versa.