Polarized infrared absorption spectrum of matrix-isolated methylperoxyl radicals, CH3OO (X)over-tilde 2A ''

We have used a tandem pair of supersonic nozzles to produce clean samples of CH3OO radicals in cryogenic matrices. One hyperthermal nozzle decomposes azomethane (CH3NNCH3) to generate intense pulses of CH3 radicals, While the second nozzle alternately fires a burst Of O-2/Ar at the 20 K matrix. The CH3/O-2/20 K argon radical sandwich acts to produce target methylperoxyl radicals: CH3 + O-2 --> CH3OO. The absorption spectra of the radicals are monitored with a Fourier transform infrared spectrometer. We report 10 of the 12 fundamental infrared bands of the methylperoxyl radical CH3OO, (X) over tilde (2)A", in an argon matrix at 20 K. The experimental frequencies (cm(-1)) and polarizations follow: the a' modes are 3032, 2957, 1448, 1410, 1180, 1109, 90, 492, while the a" modes are 3024 and 1434. We cannot detect the asymmetric CH3 rocking mode, nu(11), nor the torsion, nu(12). The infrared spectra of (CH3OO)-O-18-O-18, (CH3OO)-C-13, and CD3OO have been measured as well in order to determine the isotopic shifts. The experimental frequencies, {nu}, for the methylperoxyl radicals are compared to harmonic frequencies, {omega}, resulting from a UB3LYP/6-311G(d,p) electronic structure calculation. Linear dichroism spectra were measured with photooriented radical samples in order to establish the experimental polarizations of most vibrational bands. The methylperoxyl radical matrix frequencies listed above are within +/-2% of the gas-phase vibrational frequencies. A final set of vibrational frequencies for the H radical, are recommended. See also http://ellison.colorado.edu/methylperoxyl.

Impact and energy absorption of portable water-filled road safety barrier system fitted with foam

Portable water-filled barriers (PWFBs) are roadside appurtenances that are used to prevent errant vehicles from penetrating into temporary construction zones on roadways. A numerical model of the composite PWFB, consisting of a plastic shell, steel frame, water and foam was developed and validated against results from full scale experimental tests. This model can be extended to larger scale impact cases, specifically ones that include actual vehicle models. The cost-benefit of having a validated numerical model is significant and this allows the road barrier designer to conduct extensive tests via numerical simulations prior to standard impact tests Effects of foam cladding as additional energy absorption material in the PWFB was investigated. Different types of foam were treated and it was found that XPS foam was the most suitable foam type. Results from this study will aid PWFB designers in developing new generation of roadside structures which will provide enhanced road safety.

Demonstration of nonlinear absorption in Au semi-continuous film by electrical measurement

We have demonstrated the nonlinear absorption at 532 nm wavelength in an Au semi-continuous film (SF) resulting from smearing of the Fermi distribution and diffusion of conduction electrons into the substrate. The Au SF was irradiated by a pulsed laser with 8 ns pulse width at 532 nm in near resonance with the interband transition of the Au. We determined the temperature increase in the SF for different intensities by electrical measurement. We calculated the temperature increase by using a 1D heat transport equation; comparing the results of the calculation with measured values for the temperature increase, revealed the nonlinear absorption in the Au SF. We employed this deviation from linear behaviour to determine the nonlinear absorption coefficient.

Enhancement of optical absorption in thin-film solar cells through the excitation of higher-order nanoparticle plasmon modes

Recent research in the rapidly emerging field of plasmonics has shown the potential to significantly enhance light trapping inside thin-film solar cells by using metallic nanoparticles. In this article it is demonstrated the plasmon enhancement of optical absorption in amorphous silicon solar cells by using silver nanoparticles. Based on the analysis of the higher-order surface plasmon modes, it is shown how spectral positions of the surface plasmons affect the plasmonic enhancement of thin-film solar cells. By using the predictive 3D modeling, we investigate the effect of the higher-order modes on that enhancement. Finally, we suggest how to maximize the light trapping and optical absorption in the thin-film cell by optimizing the nanoparticle array parameters, which in turn can be used to fine tune the corresponding surface plasmon modes.

Surface plasmon enhancement of optical absorption in thin-film silicon solar cells

Strong electromagnetic field enhancement that occurs under conditions of the surface plasmon excitation in metallic nanoparticles deposited on a semiconductor surface is a very efficient and promising tool for increasing the optical absorption within semiconductor solar cells and, hence, their photocurrent response. The enhancement of the optical absorption in thin-film silicon solar cells via the excitation of localized surface plasmons in spherical silver nanoparticles is investigated. Using the effective medium model, the effect of the nanoparticle size and the surface coverage on that enhancement is analyzed. The optimum configuration and the nanoparticle parameters leading to the maximum enhancement in the optical absorption and the photocurrent response in a single p-n junction silicon cell are obtained. The effect of coupling between the silicon layer and the surface plasmon fields on the efficiency of the above enhancement is quantified as well.

Identifying weak linear features with the "coalescing shortest path image transform"

The detection of line-like features in images finds many applications in microanalysis. Actin fibers, microtubules, neurites, pilis, DNA, and other biological structures all come up as tenuous curved lines in microscopy images. A reliable tracing method that preserves the integrity and details of these structures is particularly important for quantitative analyses. We have developed a new image transform called the "Coalescing Shortest Path Image Transform" with very encouraging properties. Our scheme efficiently combines information from an extensive collection of shortest paths in the image to delineate even very weak linear features. © Copyright Microscopy Society of America 2011.

Exploration of the fundamental equilibrium behaviour of calcium exchange with weak acid cation resins

This study evaluated the complexity of calcium ion exchange with sodium exchanged weak acid cation resin (DOW MAC-3). Exchange equilibria recorded for a range of different solution normalities revealed profiles which were represented by conventional “L” or “H” type isotherms at low values of equilibrium concentration (Ce) of calcium ions, plus a superimposed region of increasing calcium uptake was observed at high Ce values. The loading of calcium ions was determined to be ca. 53.5 to 58.7 g/kg of resin when modelling only the sorption curve created at low Ce values,which exhibited a well-defined plateau. The calculated calcium ion loading capacity for DOWMAC-3 resin appeared to correlate with the manufacturer's recommendation. The phenomenon of super equivalent ion exchange (SEIX) was observed when the “driving force” for the exchange process was increased in excess of 2.25 mmol calcium ions per gram of resin in the starting solution. This latter event was explained in terms of displacement of sodium ions from sodium hydroxide solution which remained in the resin bead following the initial conversion of the as supplied “H+” exchanged resin sites to the “Na+” version required for softening studies. Evidence for hydrolysis of a small fraction of the sites on the sodium exchanged resin surface was noted. The importance of carefully choosing experimental parameters was discussed especially in relation to application of the Langmuir–Vageler expression. This latter model which compared the ratio of the initial calcium ion concentration in solution to resin mass, versus final equilibrium loading of the calcium ions on the resin; was discovered to be an excellent means of identifying the progress of the calcium–sodium ion exchange process. Moreover, the Langmuir–Vageler model facilitated standardization of various calcium–sodium ion exchange experiments which allowed systematic experimental design.

Weak acid extractable metals in Bramble Bay, Queensland, Australia : temporal behaviour, enrichment and source apportionment

Sediment samples were taken from six sampling sites in Bramble Bay, Queensland, Australia between February and November in 2012. They were analysed for a range of heavy metals including Al, Fe, Mn, Ti, Ce, Th, U, V, Cr, Co, Ni, Cu, Zn, As, Cd, Sb, Te, Hg, Tl and Pb. Fraction analysis, enrichment factors and Principal Component Analysis –Absolute Principal Component Scores (PCA-APCS) were carried out in order to assess metal pollution, potential bioavailability and source apportionment. Cr and Ni exceeded the Australian Interim Sediment Quality Guidelines at some sampling sites, while Hg was found to be the most enriched metal. Fraction analysis identified increased weak acid soluble Hg and Cd during the sampling period. Source apportionment via PCA-APCS found four sources of metals pollution, namely, marine sediments, shipping, antifouling coatings and a mixed source. These sources need to be considered in any metal pollution control measure within Bramble Bay.

Low temperature solar cooling system with absorption chiller and desiccant wheel

Nowadays Solar Cooling systems are becoming popular to reduce the carbon footprint of air conditioning. The use of an absorption chiller connected to solar thermal panels is increasing, but little study has been carried out to assess the advantage of join together an absorption chiller and a desiccant wheel to remove the sensible heat and the latent heat in different ways than the current design adopted in the industry. In this work I assess the possibility of implement a desiccant wheel in a conventional solar cooling system and the possibility of recovering the heat rejected by the absorption chiller which is then used for the regeneration of the desiccant wheel. The implementation of a desiccant wheel and the recovery of the heat rejected could provide a significant energy saving when compared to traditional solar cooling system. The results assist in the practical development of a solar cooling system which simultaneously uses absorption and adsorption technology.

Graphene-covered perovskites: An effective strategy to enhance light absorption and resist moisture degradation

The long-term stability of methylammonium lead triiodide (MAPbI3) perovskite in moist environments is a paramount challenge to realise the commercialization of perovskite solar cells. In an attempt to address this concern, we have carried out systematic first-principles studies on the MAPbI3 perovskite with a hydrophobic graphene layer interfaced as a water barrier. We find there is a charge transfer at the graphene/MAPbI3 interface and electrons can be excited from graphene into the perovskite surface, leading to well separated electron–hole pairs, i.e. reduced recombination. By studying the optical properties, we find the hybrid graphene/MAPbI3 nanocomposite displays enhanced light absorption compared with the pristine MAPbI3. Furthermore, from an ab initio molecular dynamics simulation, the graphene/MAPbI3 nanocomposite is confirmed to be able to resist the reaction with water molecules, highlighting a great advantage of this nanocomposite in promoting long-term photovoltaic performance.

Toll-like receptor 4 and CD14 polymorphisms in ankylosing spondylitis: Evidence of a weak association in finns

Objective To investigate the association of CD14 and Toll-like receptor (TLR4) with ankylosing spondylitis (AS). Methods A promoter variant in CD14 and 2 coding polymorphisms in TLR4 were investigated in UK and Finnish families with AS and in a UK case-control study. A metaanalysis of published TLR4 and CD14 studies was performed. Results In the Finnish study the CD74-260bp T variant showed an association (p = 0.006), and the common 2-marker TLR4 haplotype showed a weak association (global p = 0.03), with AS. No associations were seen in the UK based studies or in the metaanalyses. Conclusion CD14 and TLR4 showed an association with AS in the Finns only.