Insights into non-thermal plasma chemistry of acetone diluted in N2/O2 mixtures: a real-time MS experiment.

Understanding non-thermal plasma reactivity is a complicated task as many reactions take place due to a large energy spectrum. In this work, we used a well-defined photo-triggered non-filamentous discharge to study acetone decomposition in N2/O2 gas mixtures. The plasma reactor is associated to a compact chemical ionization FTICR mass spectrometer (BTrap) in order to identify and quantify in real-time acetone and by-products in the plasma. Presence of oxygen (1 to 5%) decreased notably acetone degradation. A tremendous change is observed in the by-products distribution concomitantly to a global decrease of their total concentration. While main products observed in oxygen-free gas mix are nitrile compounds, in oxygenated media they are replaced by formaldehyde, methanol and ketene. Methanol is maximum for 1% of O2 whereas formaldehyde and ketene concentration reach their maximum value at the highest oxygen concentration tested (5%). A number of nitrate, nitrite and isocyanate organic compounds (C1 and C2) are observed as well with HNO2, HNO3 and HNCO.

Direct and Real-Time Analysis in a Plasma Reactor Using a Compact FT-ICR MS: Degradation of Acetone in Nitrogen and Byproduct Formation.

Methods for reduction of volatile organic compounds (VOCs) content in air depend on the application considered. For low concentration and low flux, nonthermal plasma methods are often considered as efficient. However, the complex chemistry involved is still not well understood because there is a lack of data sets of byproducts formation. To overcome this issue, rapid analytical methods are needed. We present the coupling of a rapid chemical ionization mass spectrometer (CIMS) for the real-time analysis of the VOCs formed during a degradation experiment. The high-resolution instrument used allows for chemical ionization and direct quantification of nontargeted compounds. This method is successfully applied to degradation experiments of acetone in a phototriggered nitrogen plasma discharge. Two regimes were highlighted: efficient conversion at low concentrations (<100 ppm) and moderate efficiency conversion at higher concentrations (>100 ppm). Those two regimes were clearly delimited as the sum of two exponential curves occurring at respectively low and high concentrations. Many byproducts were detected; in particular, HCN presented a significantly high yield. Nitrile compounds (acetonitrile, propionitrile, ...) are formed as well. To a lower extent, ketene, acetaldehyde, and formaldehyde are observed. The association of the high-resolution mass spectrometer to the plasma reactor will allow further insights into the plasma chemistry and comparison to modelization.

The statistical molecular fragmentation model compared to experimental plasma induced hydrocarbon decays.

We compare the predictions of our recently developed statistical molecular fragmentation (SMF) model with experimental results from plasma induced hydrocarbon decay. The SMF model is an exactly solvable statistical model, able to calculate the probabilities for all possible fragmentation channels as a function of the deposited excitation energy. The weights of the channels are calculated from the corresponding volume of the accessible phase space of the system, taking into account all relevant degeneracies, symmetries and density functions. An experiment designed to study the abatement of propene in N2 using a photo-triggered discharge producing a homogeneous plasma at sub-atmospheric pressure was also performed. Using a 0D model that simulates the complex chemical kinetics in the plasma, it was possible to assess the percentages of the original parent hydrocarbon's fragmentation channels based on the detected species. These results were compared to those obtained from the SMF model. Previous plasma induced hydrocarbon fragmentation experiments for ethene, ethane and propane, were also compared to the predictions of the SMF model. For energies below that of metastable dinitrogen (i.e. below 6.17 eV and 8.4 eV), the SMF model and the experimental fragmentation channels coincide. This study allows one to draw conclusions both on the range of excitation energies transferred to the parent hydrocarbon molecules during plasma discharge and on the probability of the dynamical coupling of two H atoms from neighbouring carbon atoms to form H2 molecules.

Statistical molecular fragmentation: which parameters influence the branching ratios?

The fragmentation of molecules under conditions that result in yields of products that are thermodynamically controlled can be readily studied with statistical models. We explore which parameters influence the branching ratios using our recently developed Statistical Molecular Fragmentation model (SMF) and apply it to the decomposition of propane. We find that the fragmentation process has low sensitivity to the differences between the molecular descriptions given by commonly used ab initio methods (B3LYP, CCSD(T) and composite methods with different atom-centered basis sets). However, the branching ratios are most influenced by the vibrational frequencies of the molecules and radicals present in the decomposition pathways.

A Statistical Model and DFT Study of the Fragmentation Mechanisms of Metronidazole by Advanced Oxidation Processes.

The degradation pathway of the antibiotic metronidazole (MNZ) in wastewater was investigated computationally with a physical statistical method and a quantum chemical approach. In both cases, density functional theory (DFT) at the M06-2X/6-311+G(d,p) level was used to calculate the structures and property parameters of all molecules. On one hand, decay of the isolated MNZ molecule excited at a given excitation energy was studied using the statistical molecular fragmentation (SMF) model. On the other hand, the reaction mechanisms of MNZ oxidized by hydroxyl radicals (•OH) in advanced oxidation processes (AOPs) were analyzed. Both studies show that the main reaction sites in MNZ are, by decreasing importance, -NO2, -CH2OH, and -CH2CH2OH. The main degradation reactions are (i) alcohol group oxidation including the abstraction of hydrogen on C in the -CH2OH group and oxidation of the hydroxyl group to the aldehyde and further to the carboxylic acid and (ii) addition-elimination reactions happening on the imidazole ring which finally replace the nitro by hydroxyl radicals. The results gained are in a good agreement with the available experimental data on MNZ degradation by AOPs. The structures of intermediates, transition states, and free energy surfaces are helpful in elucidating the details of the elimination mechanism, supplementing current experimental knowledge.

Gas Analysis by Electron Ionization Combined with Chemical Ionization in a Compact FTICR Mass Spectrometer.

In this Article, a compact Fourier transform ion cyclotron resonance (FTICR) mass spectrometer based on a permanent magnet is presented. This instrument has been developed for real-time analysis of gas emissions. The instrument is well-suited to industrial applications or analysis of toxic and complex samples where the concentrations can vary rapidly on a wide range. The novelty of this instrument is the ability to use either electron ionization (EI) or chemical ionization (CI) individually or both of them alternatively. Also in CI mode, different precursor ions can be used alternatively. Volatile organic compounds (VOCs) from the ppb level to very high concentrations (% level) can be detected by CI or EI. The magnet is composed of three Halbach arrays, and the nominal field achieved is 1.5 T. The ICR cell is a 3 cm side length cubic cell. The mass range is 12-200 u with a broad band detection. The mass accuracy of 0.005 u and the resolving power allow the separation of isobaric ions such as C3H8+ and CO2+. Gas introduction via controlled gas pulses, electron ionization, ion-molecule reactions, ion selection, and detection are all performed in the ICR cell. The potential of the instrument will be illustrated by an analysis of a gas mixture containing trace components at ppm level (VOCs) and components in the 0.5-100% range (N2, alkanes, and CO2).

Compact FTICR Mass Spectrometry for Real Time Monitoring of Volatile Organic Compounds.

In this paper, we present a compact Fourier transform ion cyclotron resonance mass spectrometer (FTICR-MS) designed for real time analysis of volatile organic compounds (VOCs) in air or in water. The spectrometer is based on a structured permanent magnet made with NdFeB segments. Chemical ionization is implemented inside the ICR cell. The most widely used reaction is the proton transfer reaction using H3O⁺ precursor ions, but other ionic precursors can be used to extend the range of species that can be detected. Complex mixtures are studied by switching automatically from one precursor to another. The accuracy obtained on the mass to charge ratio (Δm/z 5 × 10−3), allows a precise identification of the VOCs present and the limit of detection is 200 ppb without accumulation. The time resolution is a few seconds, mainly limited by the time necessary to come back to background pressure after the gas pulses. The real time measurement will be illustrated by the monitoring of VOCs produced during the thermal degradation of a polymer and by an example where three different precursor ions are used alternatively to monitor a gas sample.

Nanosized Na-EMT and Li-EMT zeolites: selective sorption of water and methanol studied by a combined IR and TG approach.

Nanosized EMT-type zeolite crystals in sodium (Na-EMT) and ion-exchanged lithium (Li-EMT) forms were prepared. The sorption behavior of Li(Na)-EMT samples towards water, methanol and a mixture of both (50 : 50) was studied by combined thermogravimetric and infrared spectroscopic methods. The stability of the samples prior to and after the sorption measurements in two subsequent cycles was confirmed by X-ray diffraction, N2 sorption and NMR spectroscopy. The high sorption capacity of the Li-EMT sample towards water was demonstrated. It was found that the methanol is replaced by water faster in the Li-EMT sample in comparison to the Na-EMT sample. At low temperature, the methanol shows weak adsorption on each cationic site and no side products during desorption for both samples were obtained.

Optogenetic Tools for Confined Stimulation in Deep Brain Structures.

Optogenetics has emerged in the past decade as a technique to modulate brain activity with cell-type specificity and with high temporal resolution. Among the challenges associated with this technique is the difficulty to target a spatially restricted neuron population. Indeed, light absorption and scattering in biological tissues make it difficult to illuminate a minute volume, especially in the deep brain, without the use of optical fibers to guide light. This work describes the design and the in vivo application of a side-firing optical fiber adequate for delivering light to specific regions within a brain subcortical structure.

Impact of CB1 Receptor Deletion on Visual Responses and Organization of Primary Visual Cortex in Adult Mice.

PURPOSE: The endocannabinoids (eCBs) and their receptors are expressed in the cortex of developing animals where they act as a neuromodulating system during critical stages of brain development such as cell proliferation and migration, and axon guidance. Little is known on the impact of the cannabinoid system on cortical map formation and receptive field properties of cortical sensory neurons. The present study evaluates in vivo the functional organization of the primary visual cortex (V1) of mice lacking cannabinoid CB1R receptor (cnr1-/-). METHODS: Using optical imaging of intrinsic signals, azimuth, and elevation maps of cnr1-/- mice were compared with their wild-type littermates (cnr1+/+). RESULTS: Topographic maps were affected in mutant mice as they exhibited narrower visual field and changes in the shape of V1. CB1R exerted its action in an axis dependent manner as all changes were observed in the azimuth axis. Spatial frequency and contrast sensitivity were also compared between the two groups. Both properties were affected by the chronic lacking of CB1R as mutant mice exhibited a significantly lower contrast sensitivity as well as lower spatial frequency selectivity. CONCLUSIONS: Taken together, these results suggest an important role for CB1R in cortical map formation. Our results also clearly demonstrate the impact of CB1R in the development of visual properties of primary visual cortex neurons. Because psychoactive effects of cannabis consumption on visual experience are mediated mainly through CB1R, our results could possibly explain neuronal mechanisms involved in those perceptual changes.

Simultaneous Electrophysiological Recording and Micro-injections of Inhibitory Agents in the Rodent Brain.

Here we describe a method for the construction of a single-use "injectrode" using commercially accessible and affordable parts. A probing system was developed that allows for the injection of a drug while recording electrophysiological signals from the affected neuronal population. This method provides a simple and economical alternative to commercial solutions. A glass pipette was modified by combining it with a hypodermic needle and a silver filament. The injectrode is attached to commercial microsyringe pump for drug delivery. This results in a technique that provides real-time pharmacodynamics feedback through multi-unit extracellular signals originating from the site of drug delivery. As a proof of concept, we recorded neuronal activity from the superior colliculus elicited by flashes of light in rats, concomitantly with delivery of drugs through the injectrode. The injectrode recording capacity permits the functional characterization of the injection site favoring precise control over the localization of drug delivery. Application of this method also extends far beyond what is demonstrated here, as the choice of chemical substance loaded into the injectrode is vast, including tracing markers for anatomic experiments.

Spatiotemporal Profile of Voltage-Sensitive Dye Responses in the Visual Cortex of Tree Shrews Evoked by Electric Microstimulation of the Dorsal Lateral Geniculate and Pulvinar Nuclei.

The primary visual cortex (V1) receives its main thalamic drive from the dorsal lateral geniculate nucleus (dLGN) through synaptic contacts terminating primarily in cortical layer IV. In contrast, the projections from the pulvinar nucleus to the cortex are less clearly defined. The pulvinar projects predominantly to layer I in V1, and layer IV in extrastriate areas. These projection patterns suggest that the pulvinar nucleus most strongly influences (drives) activity in cortical areas beyond V1. Should this hypothesis be true, one would expect the spatiotemporal responses evoked by pulvinar activation to be different in V1 and extrastriate areas, reflecting the different connectivity patterns. We investigated this issue by analyzing the spatiotemporal dynamics of cortical visual areas' activity following thalamic electrical microstimulation in tree shrews, using optical imaging and voltage-sensitive dyes. As expected, electrical stimulation of the dLGN induced fast and local responses in V1, as well as in extrastriate and contralateral cortical areas. In contrast, electrical stimulation of the pulvinar induced fast and local responses in extrastriate areas, followed by weak and diffuse activation in V1 and contralateral cortical areas. This study highlights spatiotemporal cortical activation characteristics induced by stimulation of first (dLGN) and high-order (pulvinar) thalamic nuclei. SIGNIFICANCE STATEMENT: The pulvinar nucleus represents the main extrageniculate thalamic visual structure in higher-order mammals, but its exact role remains enigmatic. The pulvinar receive prominent inputs from virtually all visual cortical areas. Cortico-thalamo-cortical pathways through the pulvinar nuclei may then provide a complementary route for corticocortical information flow. One step toward the understanding of the role of transthalamic corticocortical pathways is to determine the nature of the signals transmitted between the cortex and the thalamus. By performing, for the first time, high spatiotemporal mesoscopic imaging on tree shrews (the primate's closest relative) through the combination of voltage-sensitive dye recordings and brain stimulation, we revealed clear evidence of distinct thalamocortical functional connectivity pattern originating from the geniculate nucleus and the pulvinar nuclei.

Spatiotemporal profiles of receptive fields of neurons in the lateral posterior nucleus of the cat LP-pulvinar complex.

The pulvinar is the largest extrageniculate thalamic visual nucleus in mammals. It establishes reciprocal connections with virtually all visual cortexes and likely plays a role in transthalamic cortico-cortical communication. In cats, the lateral posterior nucleus (LP) of the LP-pulvinar complex can be subdivided in two subregions, the lateral (LPl) and medial (LPm) parts, which receive a predominant input from the striate cortex and the superior colliculus, respectively. Here, we revisit the receptive field structure of LPl and LPm cells in anesthetized cats by determining their first-order spatiotemporal profiles through reverse correlation analysis following sparse noise stimulation. Our data reveal the existence of previously unidentified receptive field profiles in the LP nucleus both in space and time domains. While some cells responded to only one stimulus polarity, the majority of neurons had receptive fields comprised of bright and dark responsive subfields. For these neurons, dark subfields' size was larger than that of bright subfields. A variety of receptive field spatial organization types were identified, ranging from totally overlapped to segregated bright and dark subfields. In the time domain, a large spectrum of activity overlap was found, from cells with temporally coinciding subfield activity to neurons with distinct, time-dissociated subfield peak activity windows. We also found LP neurons with space-time inseparable receptive fields and neurons with multiple activity periods. Finally, a substantial degree of homology was found between LPl and LPm first-order receptive field spatiotemporal profiles, suggesting a high integration of cortical and subcortical inputs within the LP-pulvinar complex.

Enhancement of nanograting formation assisted by silver ions in a sodium gallophosphate glass.

We investigated the influence of silver ions during the direct femtosecond laser-induced formation of nanogratings (NGs) at the surface of a tailored sodium gallophosphate glass. We observed that the silver ions had a remarkable influence because the silver-containing glass showed (1) lower fluence thresholds for the formation of the NGs; (2) much smoother NG shapes; and (3) a bifunctional behavior because fluorescence from laser-induced silver clusters occurs prior to the formation of the NGs. We demonstrate for the first time, to our knowledge, the formation of NGs assisted by noble metal ions, such as ions playing a kind of catalytic-like role that enhances and improves the NG formation and its incubation process. Our innovative approach provides promising potential for further improvements in processes for NG formation.

Vapor responsive one-dimensional photonic crystals from zeolite nanoparticles and metal oxide films for optical sensing.

The preparation of responsive multilayered structures with quarter-wave design based on layer-by-layer deposition of sol-gel derived Nb(2)O(5) films and spin-coated MEL type zeolite is demonstrated. The refractive indices (n) and thicknesses (d) of the layers are determined using non-linear curve fitting of the measured reflectance spectra. Besides, the surface and cross-sectional features of the multilayered structures are characterized by scanning electron microscopy (SEM). The quasi-omnidirectional photonic band for the multilayered structures is predicted theoretically, and confirmed experimentally by reflectance measurements at oblique incidence with polarized light. The sensing properties of the multilayered structures toward acetone are studied by measuring transmittance spectra prior and after vapor exposure. Furthermore, the potential of the one-dimensional photonic crystals based on the multilayered structure consisting of Nb(2)O(5) and MEL type zeolite as a chemical sensor with optical read-out is discussed.

Tissue oxygen saturation mapping with magnetic resonance imaging.

A quantitative estimate of cerebral blood oxygen saturation is of critical importance in the investigation of cerebrovascular disease. While positron emission tomography can map in vivo the oxygen level in blood, it has limited availability and requires ionizing radiation. Magnetic resonance imaging (MRI) offers an alternative through the blood oxygen level-dependent contrast. Here, we describe an in vivo and non-invasive approach to map brain tissue oxygen saturation (StO2) with high spatial resolution. StO2 obtained with MRI correlated well with results from blood gas analyses for various oxygen and hematocrit challenges. In a stroke model, the hypoxic areas delineated in vivo by MRI spatially matched those observed ex vivo by pimonidazole staining. In a model of diffuse traumatic brain injury, MRI was able to detect even a reduction in StO2 that was too small to be detected by histology. In a F98 glioma model, MRI was able to map oxygenation heterogeneity. Thus, the MRI technique may improve our understanding of the pathophysiology of several brain diseases involving impaired oxygenation.

Survival after avalanche-induced cardiac arrest.

AIM: Criteria to prolong resuscitation after cardiac arrest (CA) induced by complete avalanche burial are critical since profound hypothermia could be involved. We sought parameters associated with survival in a cohort of victims of complete avalanche burial. METHODS: Retrospective observational study of patients suffering CA on-scene after avalanche burial in the Northern French Alps between 1994 and 2013. Criteria associated with survival at discharge from the intensive care unit (ICU) were collected on scene and upon admission to Level-1 trauma center. Neurological outcome was assessed at 3 months using cerebral performance category score. RESULTS: Forty-eight patients were studied. They were buried for a median time of 43 min (25-76 min; 25-75th percentiles) and had a pre-hospital body core temperature of 28.0°C (26.0-30.7). Eighteen patients (37.5%) had pre-hospital return of spontaneous circulation and 30 had refractory CA. Rewarming of 21 patients (43.7%) was performed using extracorporeal life support. Eight patients (16.7%) survived and were discharged from the ICU, three (6.3%) had favorable neurological outcome at 3 months. Pre-hospital parameters associated with survival were the presence of an air pocket and rescue collapse. On admission, survivors had lower serum potassium concentrations than non-survivors: 3.2 mmol/L (2.7-4.0) versus 5.6 mmol/L (4.2-8.0), respectively (P<0.01). They also had normal values for prothrombin and activated partial thromboplastin compared to non-survivors. CONCLUSIONS: Our findings indicate that survival after avalanche burial and on-scene CA is rarely associated with favorable neurological outcome. Among criteria associated with survival, normal blood coagulation on admission warrants further investigation.

Zeolite films as building blocks for antireflective coatings and vapor responsive Bragg stacks.

Zeolite films (LTL, BEA and MFI) are prepared with a thickness in the range 50-170 nm through a multistep spin-on deposition method. The optical properties of the zeolite films including refractive index, extinction coefficient and thickness are determined from the reflectance spectra using a nonlinear curve fitting method. The total free pore volume of the films using the Bruggeman effective medium theory is calculated. The potential of the zeolite films for broadband antireflection (AR) application is demonstrated. Five times reduction of the reflectance of a silicon substrate covered with the double AR films comprising of MFI type zeolite (120 nm) deposited on Nb2O5 (60 nm) is achieved. Additionally, the MFI zeolite film is used as a building block of vapor responsive Bragg stacks with a strong response towards acetone. The reversible response of the Bragg stacks towards acetone without additional annealing opens up the possibility of preparing sensors with optical read-out by incorporation of sensitive and transducer elements into a single device.

Repetitive and retinotopically restricted activation of the dorsal lateral geniculate nucleus with optogenetics.

Optogenetics allows the control of cellular activity using focused delivery of light pulses. In neuroscience, optogenetic protocols have been shown to efficiently inhibit or stimulate neuronal activity with a high temporal resolution. Among the technical challenges associated with the use of optogenetics, one is the ability to target a spatially specific population of neurons in a given brain structure. To address this issue, we developed a side-illuminating optical fiber capable of delivering light to specific sites in a target nucleus with added flexibility through rotation and translation of the fiber and by varying the output light power. The designed optical fiber was tested in vivo in visual structures of ChR2-expressing transgenic mice. To assess the spatial extent of neuronal activity modulation, we took advantage of the hallmark of the visual system: its retinotopic organization. Indeed, the relative position of ganglion cells in the retina is transposed in the cellular topography of both the dorsal lateral geniculate nucleus (LGN) in the thalamus and the primary visual cortex (V1). The optical fiber was inserted in the LGN and by rotating it with a motor, it was possible to sequentially activate different neuronal populations within this structure. The activation of V1 neurons by LGN projections was recorded using intrinsic optical imaging. Increasing light intensity (from 1.4 to 8.9 mW/mm²) led to increasing activation surfaces in V1. Optogenetic stimulation of the LGN at different translational and rotational positions was associated with different activation maps in V1. The position and/or orientation of the fiber inevitably varied across experiments, thus limiting the capacity to pool data. With the optogenetic design presented here, we demonstrate for the first time a transitory and spatially-concise activation of a deep neuronal structure. The optogenetic design presented here thus opens a promising avenue for studying the function of deep brain structures.

Identification and quantification of 14 phthalates and 5 non-phthalate plasticizers in PVC medical devices by GC-MS.

A GC/MS method was developed for the identification and quantification of 14 phthalates: 8 phthalates classified H360 (DBP, DEHP, BBP, DMEP, DnPP, DiPP, DPP and DiBP), 3 phthalates proposed to be forbidden in medical devices (DnOP, DiNP and DiDP) and 3 other phthalates none regulated (DMP, DCHP and DEP) which may interfere with hormone function. In order to identify and quantify other plasticizers that are commonly used in PVC medical devices such as DEHP substitute, 5 non-phthalate plasticizers (ATBC, DEHA, DEHT, TOTM, and DINCH) were included in this study. Analyses are carried out on a GC/MS system with electron impact ionization mode (EI). The separation of plasticizers is obtained on a cross-linked 5%-phenyl/95%-dimethylpolysiloxane capillary column 30m×0.25mm (i.d.)×0.25µm film thickness using a gradient temperature. Compounds quantification is performed by external calibration using an internal standard. Validation elements on standard solutions were determined using the ISO 12787 standard approach. Plasticizers are extracted from PVC medical devices using THF for dissolving the PVC part of the sample followed by precipitation of the PVC by addition of ethanol. The supernatant is injected into a GC/MS system after dilution in ethanol. Different validation elements, including extraction recoveries for all compounds or for DEHP a cross-validation of the extraction process using the European pharmacopoeia monograph 3.1.14 as reference method, are discussed. Results obtained on 61 medical devices in PVC and 12 raw materials used as plasticizers are given.