Quantum-cascade laser photoacoustic detection of methane emitted from natural gas powered engines

In this work we present a laser photoacoustic arrangement for the detection of the important greenhouse gas methane. A quantum-cascade laser and a differential photoacoustic cell were employed. A detection limit of 45 ppbv in nitrogen was achieved as well as a great selectivity. The same methodology was also tested in the detection of methane issued from natural gas powered vehicles (VNG) in Brazil, which demonstrates the excellent potential of this arrangement for greenhouse gas detection emitted from real sources.     

Structures of Two (<Emphasis Type="Italic">E</Emphasis>)-3-Substituted Cinnamoylbenzotriazole 1-Oxides

Abstract  

The molecule of (E)-3-(3-MeOC₆H₄CH=CHCO)-benzotriazole 1-oxide, 2, has a very near planar structure, while the 2-nitrophenyl ring is rotated out of the plane of the remaining atoms in (E)-3-(2-O₂NC₆H₄CH=CHCO)-benzotriazole 1-oxide, 1. The nitrogen oxide bond lengths in 1 and 2 are 1.258 (6) and 1.2683 (15) ?, respectively, and are in the region found for related compounds. There are no strong intermolecular hydrogen-bonds in either compound, instead there are weak C–H···O intermolecular hydrogen-bonds and π···π stacking interactions in 1, and C–H···O, C–H···π, and π···π stacking interactions in 2. Different three-dimensional arrays are generated in each case. Compound 1 crystallises in the orthorhombic space group Pna2₁, with a = 25.061 (2) ?, b = 3.6997 (2) ?, c = 14.2623 (12) ? and Z = 4. Compound 2 crystallises in the triclinic space group P-1, with a = 5.7297 (3) ?, b = 10.8440 (6) ?, c = 11.4965 (6) ?, α = 89.689 (3)°, β = 76.019 (3)°, γ = 75.047 (3)°, Z = 2.     

Phase-matching properties of PPKTP, MgO:PPSLT and MgO:PPcLN for ultrafast optical parametric oscillation in the visible and near-infrared ranges with green pump

Ultrashort pulses with wavelength tuning in the visible and near-infrared (VNIR) ranges (here approximately 680 to 2000 nm) have wide application in many biomedical devices especially in imaging and spectroscopy. The theoretical studies here consider the phase-matching conditions of three periodically poled crystals (PPKTP, MgO:PPcLN and MgO:PPSLT) to use for femtosecond optical parametric oscillators (OPO) to generate wavelength tunability in this range. The basic optical properties and the wavelength tuning ranges are calculated with respect to different grating periods and temperature variation. Dispersive properties of crystals relevant to the ultrafast operation regime are also discussed. The excitation wavelength used here for the analysis is 520 nm which is the second harmonic wavelength of Yb-doped ultrashort pulse solid state lasers. The concept of the tunable femtosecond OPOs with green excitation presented here can be a better alternative to the widely used expensive Ti:Sapphire lasers.     

Influence of low intensity laser therapy (AsGa) on the cicatrization process of mechanic tendon injury in wistar rats

The aim of this study was to compare the effect of the low level Laser therapy (AsGa) in the experimental tendon injury. Low level Laser therapy has been used in several studies to observe the regenerative quality and tecidual cicatrization. Forty Wistar rats (male) were divided into 4 groups: control group (C-group); injury group (L-group); treated group with Laser therapy 3 J/cm² (3J-group); and treated group with Laser therapy 6 J/cm² (6J-group). Groups L, 3J, and 6J were submitted to a mechanic Achilles tendon injury with a Kocher Forceps for 10 s. The animals were sacrificed after ten days of treatment. Histopathological evaluation using hematoxylin-eosin and Picro-Sirius staining showed a decreased (p < 0.05) of collagen in L-group (353.12 ± 9.85 ??m²/field) compared to C-group (215.13 ± 22.63 ??m²/field). Animals treated with Laser showed a significant increase in collagen fibers despite the applied dosage (3J-group: 375.89 ± 26.99 ??m²/field; 6J group: 400.34 ± 62.92 ??m²/field; p < 0.05). These data suggest that low-level Laser therapy was efficient for the treatment of mechanics Achilles tendon injury in Wistar rats.     

Kinetics and product distribution of p‐nitrophenyl phosphate dianion solvolysis in ternary DMSO/alcohol/water mixtures are compatible with metaphosphate formation

The rate of solvolysis of p‐nitrophenyl phosphate (PNPP) dianion in DMSO/water strongly decreases by increasing water concentration. Addition of linear alcohols (methanol, propanol, butanol, pentanol, and hexanol) at constant DMSO/water molar ratio produced an even sharper rate decrease. Alkyl phosphate formation, resulting from PNPP solvolysis in ternary DMSO/water/alcohol mixtures, increased with alcohol concentration and was essentially temperature independent. Methanol and hexanol were the poorest nucleophiles under all conditions. Activation energies and enthalpies for solvolysis in ternary mixtures were similar and entropies varied with alcohol concentration. Taken together these results can be best interpreted in terms of a dissociative mechanism with the intervention of metaphosphate. Copyright © 2011 John Wiley & Sons, Ltd.     

Integer quantum Hall effect on an interface with disclinations

The Hall conductivity of an electron gas on an interface showing topological defects as disclinations in the presence of an orthogonal constant magnetic field is investigated. This kind of defect induces either positive or negative singular curvature in the medium. It is shown that the positive curvature decreases the quantum Hall plateau widths and shifts the steps in the Hall conductivity to lower magnetic fields. In contrast, the negative one leaves to the existence of two types of plateaus, one with higher widths and the other one with lower widths in comparison to the flat case. In this case, the shift in the steps of the Hall conductivity goes to higher magnetic fields. We also investigate the Hall conductivity for electrons around a cylindrically symmetric distribution of disclinations and it turns out that it is the same as that corresponding to a single effective disclination.     

Diffusion Driven Accelerated Stress Corrosion Cracking in an Acrylic Polymer

The dynamic evolution and mechanism of accelerated stress corrosion cracking (aSCC) in anacrylic (PMMA–poly methyl 2-methylpropenoate) polymer sample have been exploited quantitatively, in absence of external mechanical load. Unusually fast propagation of solvent induced cracks in micro-machined sections of the material has been monitored by microscopic video imaging of a test device. Crack emanation from milled micro-channels was precisely triggered by brief surface wetting with acetone solvent. The crack propagation period persists over a time span of approximately 1 min, comprises a final crack length of 0.2–0.3 mm, and an associated crack growth rate that decreases from $2 \times 10^{-5}$ to $10^{-6}$ m/s. The temporal crack evolution scales in accord with 1-dim solvent diffusion along the flaw, super imposed with the residual stress field. Optically recorded birefringence, as well as finite element structure mechanic simulation, identified residual tensile stress in the crack zone as the driving force. The residual stress intensity factor $\Delta K$ was determined to 1–2 MPa  ${\rm m}^{1/2}$ . The aSCC (accelerated stress corrosion cracking) in the material originates from a detrimental combination of residual stress, induced by surface milling; stress induced fast diffusion of the acetone solvent into the material and an associated degradation of structure-mechanic parameters.     

Sol MWD During Styrene,Vinyl Acetate,Methyl Methacrylate,and Butyl Acrylate Homopolymerization: A Numerical Study Using the NFT Approach

Complete parameter sensitivity analyses using the numerical fractionation technique are presented for the cases of homopolymerization with chain transfer to polymer and termination by combination. Also, using reported values for the kinetic rate constants associated with the linear and non‐linear homopolymerizations of styrene, vinyl acetate, methyl methacrylate and butyl acrylate, overall molecular weight distributions and averages of the MWD were calculated using the NFT. Good agreement with the expected behavior, with MMA and STY not gelling while BA and VAc do, was obtained. It is concluded that the NFT produces coherent and reliable performance for known polymerization systems, whether linear or non‐linear.

     

Rapid tool for assessment of C13 norisoprenoids in wines

Two novel methodologies for quantification of C₁₃ norisoprenoids in wines were developed. The first methodology, method A (reference method) was based on the headspace solid-phase microextraction combined with gas chromatography–quadrupole mass spectrometry operating in selected ion monitoring mode (HS-SPME–GC–qMS–SIM). This methodology allowed to select the GC conditions for an adequate chromatographic resolution of wine components. The second methodology, method B (rapid method) was based on the HS-SPME–GC–qMS–SIM, using GC conditions that allowed to obtain a C₁₃ norisoprenoid volatile signature. In the later, the GC capillary column of 30 m at 220 °C was used acting as a transfer line of the components sorbed by the SPME coating fibre to the mass spectrometer, which acts as a sensor for m/z fragments 142 and 192. It does not require any pre-treatment of the sample, and the C₁₃ norisoprenoid composition of the wine was evaluated based on the chromatographic profile and specific m/z fragments, without complete chromatographic separation of its components. For quantification purposes, external calibration curves were constructed with β-ionone chemical standard. Calibration curves with regression coefficient (r²) of 0.9940 and 0.9968, RSD of 1.08% and 12.51%, and detection limits of 1.10 and 1.57 μg L⁻¹ were obtained for methods A and B, respectively. These methodologies were applied to seventeen white and red table wines. Two vitispirane isomers (158–1529 μg L⁻¹) and 1,1,6-trimethyl-1,2-dihydronaphthalene (TDN) (6.42–39.45 μg L⁻¹) were quantified. The data obtained for vitispirane isomers and TDN using the two methods were highly correlated (r² of 0.9756 and 0.9630, respectively). Associated to the fast and robust character of the proposed rapid method B and considering the extraction time, it is important to focus its selectivity and potential applicability if specific m/z fragments would be established for new analytes.