A novel HS-SBSE system coupled with gas chromatography and mass spectrometry for the analysis of organochlorine pesticides in water samples

A methodology to analyze organochlorine pesticides (OCPs) in water samples has been accomplished by using headspace stir bar sorptive extraction (HS-SBSE). The bars were in house coated with a thick film of PDMS in order to properly work in the headspace mode. Sampling was done by a novel HS-SBSE system whereas the analysis was performed by capillary GC coupled mass spectrometric detection (HS-SBSE-GC-MS). The extraction optimization, using different experimental parameters has been established by a standard equilibrium time of 120 min at 85 degrees C. A mixture of ACN/toluene as back extraction solvent promoted a good performance to remove the OCPs sorbed in the bar. Reproducibility between 2.1 and 14.8% and linearity between 0.96 and 1.0 were obtained for pesticides spiked in a linear range between 5 and 17 ng/g in water samples during the bar evaluation.

Transcranial DC Stimulation Coupled With TENS for the Treatment of Chronic Pain A Preliminary Study

Objective: Based on evidence showing that electrical stimulation of the nervous system is an effective method to decrease chronic neurogenic pain, we aimed to investigate whether the combination of 2 methods of electrical stimulation-a method of peripheral stimulation [transcutaneous electrical nerve stimulation (TENS)] and a method of noninvasive brain stimulation (transcranial direct current stimulation (tDCS)]-induces greater pain reduction as compared with tDCS alone and sham stimulation. Methods: We performed a preliminary, randomized, sham-controlled, crossover, clinical study in which 8 patients were randomized to receive active tDCS/active TENS (""tDCS/TENS"" group), active tDCS/sham TENS (""tDCS"" group), and sham tDCS/sham TENS (""sham"" group) stimulation. Assessments were performed immediately before and after each condition by a blinded rater. Results: The results showed that there was a significant difference in pain reduction across the conditions Of stimulation (P = 0.006). Post hoc tests showed significant pain reduction as compared with baseline after the tDCS/TENS condition [reduction by 36.5% (+/- 10.7), P = 0.004] and the tDCS condition [reduction by 15.5% (+/- 4.9), P = 0.014], but not after sham stimulation (P = 0.35). In addition, tDCS/TENS induced greater pain reduction than tDCS (P = 0.02). Conclusions: The results of this pilot study suggest that the combination of TENS with tDCS has a superior effect compared with tDCS alone.

Evaluation of comprehensive two-dimensional gas chromatography coupled to rapid scanning quadrupole mass spectrometry for quantitative analysis

Comprehensive two-dimensional gas chromatography (GC x GC) is a powerful technique that provides excellent separation and identification of analytes in highly complex samples with considerable increase in GC peak capacities. However, since second dimension analyses are very fast, detectors with a rapid acquisition rate are required. Over the last years, quite a number of studies have discussed the potential and limitations of the combination GC x GC with a variety of quadrupole mass spectrometers. The present research focuses on the evaluation of qMS effectiveness at a 10,000-amu/s scan speed and 20-Hz scan frequency for the identification (full scan mode acquisition-TIC) and quantification (extracted ion chromatogram) of target pesticide residues in tomato samples. The following MS parameters have been evaluated: number of data points per peak, mass spectrum quality, peak skewing, and sensitivity. The validated proposed GC x GC/qMS method presented satisfactory results in terms of repeatability (coefficient of variation lower than 15%), accuracy (84-117%), and linearity (ranging from 25 to 500 ng/g), while significant enhancement in sensitivity was observed (a factor of around 10) under scan conditions. (C) 2012 Elsevier B.V. All rights reserved.

Coupled Boltzmann calculation of mixed axion/neutralino cold dark matter production in the early universe

We calculate the relic abundance of mixed axion/neutralino cold dark matter which arises in R-parity conserving supersymmetric (SUSY) models wherein the strong CP problem is solved by the Peccei-Quinn (PQ) mechanism with a concommitant axion/saxion/axino supermultiplet. By numerically solving the coupled Boltzmann equations, we include the combined effects of 1. thermal axino production with cascade decays to a neutralino LSP, 2. thermal saxion production and production via coherent oscillations along with cascade decays and entropy injection, 3. thermal neutralino production and re-annihilation after both axino and saxion decays, 4. gravitino production and decay and 5. axion production both thermally and via oscillations. For SUSY models with too high a standard neutralino thermal abundance, we find the combined effect of SUSY PQ particles is not enough to lower the neutralino abundance down to its measured value, while at the same time respecting bounds on late-decaying neutral particles from BBN. However, models with a standard neutralino underabundance can now be allowed with either neutralino or axion domination of dark matter, and furthermore, these models can allow the PQ breaking scale f(a) to be pushed up into the 10(14) - 10(15) GeV range, which is where it is typically expected to be in string theory models.

The infrared fundamental intensities of some cyanopolyynes

Some cyanopolyynes, HCnN (n = 1, 3, ... , 17), are investigated by means of calculations at the MP2/cc-pVTZ and CCSD/cc-pVDZ levels. Although the MP2/cc-pVTZ results for geometries and molecular dipole moments are encouraging, the CCSD/cc-pVDZ level was superior for the study of infrared fundamental intensities. The main bands are also analyzed with a charge-charge flux-dipole flux (CCFDF) partition model based on quantities given by the Quantum Theory of Atoms in Molecules (QTAIM). The intensity of vibrations corresponding to the stretching of CH bonds (3471-3473 cm(-1)) increases in line with the number of carbon atoms (from 61 to 146 km mol(-1) between HCN and HC13N). This increase is due to the charge flux contribution while the other contributions remain roughly unaltered except for HCN. Moreover, the hydrogen atom loses an almost constant amount of electronic charge during the CH bond enlargement and a small fraction of this charge spreads to atoms farther and farther away from hydrogen as the molecule size increases. The band associated with the doubly degenerate CH bending vibrations (643-732 cm(-1)) presents approximately the same intensity in all the studied cyanopolyynes (from 67 to 76 km mol(-1)). The CCFDF/QTAIM contributions are also nearly the same for these bending modes in HC5N and larger systems. The intensity of the mode mostly identified as CN stretching (around 2378-2399 cm(-1) except for HCN) increases from HCN up to HC7N (from 0.3 to 83 km mol(-1)) and nearly stabilizes around 80-90 km mol(-1) for larger systems. The CCFDF/QTAIM contributions for this mode also change significantly up to HC7N and remain almost constant in larger systems. We also observed the appearing of a very relevant band between 2283 and 2342 cm(-1). This mode is mainly associated with the symmetric stretching of CC triple bonds near the molecule center and exhibits large charge fluxes while the other contributions are almost negligible in the largest cyanopolyynes. The two vibrational bands associated with the smallest frequencies are also studied and extrapolation equations are suggested to predict their positions in larger cyanopolyynes. (C) 2012 Elsevier B.V. All rights reserved.

Self-potential signals from an analog biogeobattery mode

A tank experiment was conducted to check if self-potential (SP) signals can be generated when buried organic matter is wire-connected to a near-surface, oxygen-rich, sediment layer. This experiment demonstrated that once wired, there was a flux of electrons (hence an electric current) between the lower and upper layers of the sandbox with the system responding as a large-scale microbial fuel cell (a type of bioelectrochemical system). An electric current was generated by this process in the wire and the SP method was used to monitor the associated electric potential distribution at the top of the tank.. The electric field was controlled by the flux of electrons through the wire, the oxidation of the organic matter, the reduction of oxygen used as a terminal electron acceptor, and the distribution of the DC resistivity in the tank. The current density through the wire was limited by the availability of oxygen and not by the oxidation of the organic matter. This laboratory experiment incorporated key elements of the biogeobattery observed in some organic-rich contaminant plumes. This analogy includes the generation of SP signals associated with a flux of electrons, the capacity of buried organic matter in sustaining anodic reactions, network resistance connecting terminal redox reactions spatially separated in space, and the existence of anodic secondary coupled reactions. A resistivity tomogram of the tank, after almost a year in operation, suggests that oxidative processes triggered by this geobattery can be imaged with this method to determine the radius of influence of the bioelectrochemical system.

Lamb mode diversity imaging fornon-destructivetesting of plate-likestructures

Several Lamb wave modes can be coupled to a particular structure, depending on its geometry and transducer used to generate the guided waves. Each Lamb mode interacts in a particular form with different types of defects, like notches, delamination, surface defects, resulting in different information which can be used to improve damage detection and characterization. An image compounding technique that uses the information obtained from different propagation modes of Lamb waves for non-destructive testing of plate-like structures is proposed. A linear array consisting of 16 piezoelectric elements is attached to a 1 mm thickness aluminum plate, coupling the fundamental A0 and SO modes at the frequencies of 100 kHz and 360 kHz, respectively. For each mode two images are obtained from amplitude and phase information: one image using the Total Focusing Method (TFM) and one phase image obtained from the Sign Coherence Factor (SCF). Each TFM image is multiplied by the SCF image of the respective mode to improve contrast and reduce side and grating lobes effects. The high dispersive characteristic of the A0 mode is compensated for adequate defect detection. The information in the SCF images is used to select one of the TFM mode images, at each pixel, to obtain the compounded image. As a result, dead zone is reduced, resolution and contrast are improved, enhancing damage detection when compared to the use of only one mode. (C) 2013 Elsevier Ltd. All rights reserved. (AU)