Optical pulling force on dielectric particles via metallic slab surface plasmon excitation: a comparison between transmission and reflection schemes.

In this Letter, a simple structure formed by a metallic thin layer covering a high-index substrate is used to design an optical tweezer. Owing to the interaction between the field scattered by the particle with an incident plane wave and the proposed structure, a pulling or attractive component of the optical force emerges. This component results in enhancement thanks to the surface plasmons (SPs) excitation arising from the elliptical polarization of the induced dipole moment on the particle. To further exploit the versatility of the proposed approach, we analyze two basic configurations: the reflection scheme, for which the plane wave impinges from the side where the particle is placed; and the transmission scheme, for which the incidence is made from the substrate side. Our results show that the intensity of the pulling force in the reflection scheme and for finite thickness metal layer reaches values exceeding more than twice those provided by a single metallic interface. We also demonstrate that the transmission scheme is more favorable than the reflection scheme for enhancing pulling force intensities. Our contribution can be valuable for realizing simple plasmonic schemes for improving the pulling force via interactions between the nano-particle and SP fields.

Flow invariants in a channel obstructed by a line of inclined rods.

An experiment is conducted in a rectangular channel obstructed by a transverse line of four inclined cylindrical rods. The pressure on the surface of a central rod and the pressure drop through the channel are measured varying the inclination angle of the rods. Three assemblies of rods with different diameters are tested. The measurements were analyzed applying momentum conservation principles and semi-empirical considerations. Several invariant dimensionless groups of parameters relating the pressure at key locations of the system with characteristic dimensions of the rods are produced. It was found that the independence principle holds for most of the Euler numbers characterizing the pressure at different locations, that is, the group is independent of the inclination angle provided that the inlet velocity projection normal to the rods is used to non-dimensionalize the pressure. The resulting semi-empirical correlations can be useful for designing similar hydraulic units.

The F + HD(v = 0, 1; j = 0, 1) reactions: stereodynamical properties of orbiting resonances.

The excitation functions (reaction cross-section as a function of collision energy) of the F + HD(v = 0, 1; j = 0, 1) benchmark system have been calculated in the 0.01-6 meV collision energy interval using a time-independent hyperspherical quantum dynamics methodology. Special attention has been paid to orbiting resonances, which bring about detailed information on the three-atom interaction during the reactive encounter. The location of the resonances depends on the rovibrational state of the reactants HD(v,j), but is the same for the two product channels HF + D and DF + H, as expected for these resonances that are linked to the van der Waals well at the entrance. The resonance intensities depend both on the entrance and on the exit channels. The peak intensities for the HF + D channel are systematically larger than those for DF + H. Vibrational excitation leads to an increase of the peak intensity by more than an order of magnitude, but rotational excitation has a less drastic effect. It deceases the resonance intensity of the F + HD(v = 1) reaction, but increases somewhat that of F + HD(v = 0). Polarization of the rotational angular momentum with respect to the initial velocity reveals intrinsic directional preferences in the F + HD(v = 0, 1; j = 1) reactions that are manifested in the resonance patterns. The helicities (Ω = 0, Ω = ±1) possible for j = 1 contribute to the resonances, but that from Ω± 1 is, in general, dominant and in some cases exclusive. It corresponds to a preferential alignment of the HD internuclear axis perpendicular to the initial direction of approach and, thus, to side-on collisions. This work also shows that external preparation of the reactants, following the intrinsic preferences, would allow the enhancement or reduction of specific resonance features, and would be of great help for their eventual experimental detection.

Psychosocial Impact of Atopic Dermatitis in Adults: A Qualitative Study. / Impacto psicosocial en adultos con dermatitis atópica: estudio cualitativo.

BACKGROUND AND OBJECTIVE: Atopic dermatitis affects a patient's quality of life in many ways. Analysis of the effects of this disease on the lives of adult patients is therefore important for the purpose of better defining their care needs. PATIENTS AND METHODS: We interviewed 14 adult patients with atopic dermatitis in this qualitative study. The interviews were semistructured according to a simple outline to allow for completeness and flexibility and afford greater depth and richness of information. RESULTS: Atopic dermatitis affected the patients' lives in 6 spheres of activity: economic, occupational, personal, psychosocial, clinical, and relational. A clear finding was that the disease has a considerable psychosocial effect on adult patients, altering their interpersonal relationships and leading to rejection, stigmatization, and social isolation. It limits the patient in various spheres of life and in activities of daily living, causing sleep alterations among other effects. The patients were very concerned about appearance, the itch-scratch cycle, poor understanding and lack of awareness of their disease, the absence of a definitive treatment, and the adverse effects of some treatments. CONCLUSIONS: The quality of life of adults with atopic dermatitis is negatively affected. This disease requires a professional, holistic, multidisciplinary management approach that attempts to mitigate the adverse effects.

Essentiality of the glnA gene in Haloferax mediterranei: gene conversion and transcriptional analysis.

Glutamine synthetase is an essential enzyme in ammonium assimilation and glutamine biosynthesis. The Haloferax mediterranei genome has two other glnA-type genes (glnA2 and glnA3) in addition to the glutamine synthetase gene glnA. To determine whether the glnA2 and glnA3 genes can replace glnA in nitrogen metabolism, we generated deletion mutants of glnA. The glnA deletion mutants could not be generated in a medium without glutamine, and thus, glnA is an essential gene in H. mediterranei. The glnA deletion mutant was achieved by adding 40 mM glutamine to the selective medium. This conditional HM26-ΔglnA mutant was characterised with different approaches in the presence of distinct nitrogen sources and nitrogen starvation. Transcriptomic analysis was performed to compare the expression profiles of the strains HM26-ΔglnA and HM26 under different growth conditions. The glnA deletion did not affect the expression of glnA2, glnA3 and nitrogen assimilation genes under nitrogen starvation. Moreover, the results showed that glnA, glnA2 and glnA3 were not expressed under the same conditions. These results indicated that glnA is an essential gene for H. mediterranei and, therefore, glnA2 and glnA3 cannot replace glnA in the conditions analysed.

Unexpected dynamical effects change the lambda-doublet propensity in the tunneling region for the O(3P) + H2 reaction.

One of the most relevant features of the O(3P) + H2 reaction is that it occurs on two different potential energy surfaces (PESs) of symmetries A' and A'' that correlate reactants and products. The respective saddle points, which correspond to a collinear arrangement, are the same for both PESs, whilst the barrier height rises more abruptly on the 3A' PES than on the 3A'' PES. Accordingly, the reactivity on the 3A'' PES should be always higher than on the 3A' PES. In this work, we present accurate quantum-scattering calculations showing that this is not always the case for rotationless reactants, where dynamical factors near the reaction threshold cause the 3A' PES to dominate at energies around the barrier. Further calculation of cross sections and Λ-doublet populations has allowed us to establish how the reaction mechanism changes from the deep tunneling regime to hyperthermal energies.

The millimeter-wave spectrum and astronomical search of succinonitrile and its vibrational excited states ☠.

CONTEXT: Dinitriles with a saturated hydrocarbon skeleton and a -C≡N group at each end can have large electric dipole moments. Their formation can be related to highly reactive radicals such as CH2CN, C2N or CN. Thus, these saturated dinitriles are potential candidates to be observed in the ISM. AIMS: Our goal is the investigation of the rotational spectrum of one of the simplest dinitriles N≡C-CH2-CH2-C≡N, succinonitrile, whose actual rotational parameters are not precise enough to allow its detection in the ISM. In addition, the rotational spectra for its vibrational exicted states will be analyzed. METHODS: The rotational spectra of succinonitrile was measured in the frequency range 72-116.5 GHz using a new broadband millimeter-wave spectrometer based on radio astronomy receivers with Fast Fourier Transform backends. The identification of the vibrational excited states of succinonitrile was supported by high-level ab initio calculations on the harmonic and anharmonic force fields. RESULTS: A total of 459 rotational transitions with maximum values of J and Ka quantum numbers 70 and 14, respectively, were measured for the ground vibrational state of succinonitrile. The analysis allowed us to accurately determine the rotational, quartic and sextic centrifugal distortion constants. Up to eleven vibrational excited states, resulting from the four lowest frequency vibrational modes ν 13, ν 12, ν 24 and ν 23 were identified. In addition to the four fundamental modes, we observed overtones together with some combination states. The rotational parameters for the ground state were employed to unsuccessfully search for succinonitrile in the cold and warm molecular clouds Orion KL, Sgr B2(N), B1-b and TMC-1, using the spectral surveys captured by IRAM 30m at 3mm and the Yebes 40m at 1.3cm and 7mm.

Orbiting resonances in the F + HD (v = 0, 1) reaction at very low collision energies. A quantum dynamical study.

Time-independent, fully converged, quantum dynamical calculations have been performed for the F + HD (v = 0, j = 0) and F + HD (v = 1, j = 0) reactions on an accurate potential energy surface down to collision energies of 0.01 meV. The two isotopic exit channels, HF + D and DF + H, have been investigated. The calculations reproduce satisfactorily the Feshbach resonance structures for collision energies between 10 and 40 meV, previously reported in the literature for the HF + D channel. Contrary to the results of a former literature work, vibrational excitation of HD is found to enhance reactivity in all cases down to the lowest collision energy investigated. Shape-type orbiting resonances are found for collision energies lower than 2 meV. The resonances appear as peaks in the reaction cross sections that are associated to specific values of the total angular momentum, J. In contrast with the Feshbach resonances at higher energies, the orbiting resonance structure, which is caused by the van der Waals well of the entrance channel, is identical for the HF + D and DF + H exit channels. The orbiting resonance peaks for F + HD (v = 0) are very small, but those for F + HD (v = 1) could be observed, in principle, with a combination of Raman pumping and merged beams methods.

Broad band high resolution rotational spectroscopy for Laboratory Astrophysics.

We present a new experimental setup devoted to the study of gas phase molecules and processes using broad band high spectral resolution rotational spectroscopy. A reactor chamber has been equipped with radio receivers similar to those used by radio astronomers to search for molecular emission in space. The whole Q (31.5-50 GHz) and W bands (72-116.5 GHz) are available for rotational spectroscopy observations. The receivers are equipped with 16×2.5 GHz Fast Fourier Transform spectrometers with a spectral resolution of 38.14 kHz allowing the simultaneous observation of the complete Q band and one third of the W band. The whole W band can be observed in three settings in which the Q band is always observed. Species such as CH3CN, OCS, and SO2 are detected, together with many of their isotopologues and vibrationally excited states, in very short observing times. The system permits automatic overnight observations and integration times as long as 2.4×105 seconds have been reached. The chamber is equipped with a radiofrequency source to produce cold plasmas and with four ultraviolet lamps to study photochemical processes. Plasmas of CH4, N2, CH3CN, NH3, O2, and H2, among other species, have been generated and the molecular products easily identified by their rotational spectrum, and mass spectrometry and optical spectroscopy. Finally, the rotational spectrum of the lowest energy conformer of CH3CH2NHCHO (N-Ethylformamide), a molecule previously characterized in microwave rotational spectroscopy, has been measured up to 116.5 GHz allowing the accurate determination of its rotational and distortion constants and its search in space.

Nystatin antifungal micellar systems on endotracheal tubes: development, characterization and in vitro evaluation.

Decontamination of patients' clinical devices in intensive care units is generally performed with an antifungal suspension. Nystatin is a widely-used high spectrum antifungal due to its low systemic absorption. However, nystatin has high hydrophobicity which hinders the contact with the internal lumen of the devices. In this work, hydrophilic micellar systems of nystatin were developed with sodium deoxycholate on silicone endotracheal tubes. The physical characteristics of the micellar system at different nystatin:deoxycholate ratios were studied using scanning electron microscopy, X-ray powder diffraction and differential scanning calorimetry. The electron microscopy results reveal that the deoxycholate micellar system altered the surface morphology, and the size of the aggregates was observed to be smaller. The hydrophilic structures of deoxycholate produce systems with a high surface area containing nystatin molecules on their interior. The X-ray and differential scanning calorimetry assays revealed a typical change in the crystallinity of micellar systems when the deoxycholate proportion increases. The endothermic peak of nystatin was not observed in the micellar systems as a consequence of the reduced crystallinity. Nystatin was homogenously dispersed in the surfactant matrix. Micellar systems with 1:0.8 nystatin:deoxycholate ratio (MS-N:DC [1:0.8]) showed increased antifungal activity compared to nystatin raw material. Micellar systems also achieved an over 40% inhibition of Candida albicans biofilm formation. The results obtained in this study conclude that the higher hydrophilic characteristic of the surfactant deoxycholate enhances nystatin penetration into the surface of the endotracheal tubes.

Stability of CH3NCO in astronomical ices under energetic processing. A laboratory study.

Methyl isocyanate (CH3NCO) was recently found in hot cores and suggested on comet 67P/CG. The incorporation of this molecule into astrochemical networks requires data on its formation and destruction. In this work, ices of pure CH3NCO and of CH3NCO(4-5%)/H2O mixtures deposited at 20 K were irradiated with a UV D2 lamp (120-400 nm) and bombarded by 5 keV electrons to mimic the secondary electrons produced by cosmic rays (CRs). The destruction of CH3NCO was studied using IR spectroscopy. After processing, the νa-NCO band of CH3NCO disappeared and IR bands corresponding to CO, CO2, OCN- and HCN/CN- appeared instead. The products of photon and electron processing were very similar. Destruction cross sections and half-life doses were derived from the measurements. Water ice provides a good shield against UV irradiation (half-life dose of ~ 64 eV molecule-1 for CH3NCO in water-ice), but not so good against high-energy electrons (half-life dose ~ 18 eV molecule-1). It was also found that CH3NCO does not react with H2O over the 20-200 K temperature range. These results indicate that hypothetical CH3NCO in the ices of dense clouds should be stable against UV photons and relatively stable against CRs over the lifetime of a cloud (~ 107 yr), and could sublime in the hot core phase. On the surface of a Kuiper belt object (the original location of comet 67P/CG) the molecule would be swiftly destroyed, both by photons and CRs, but embedded below just 10 µm of water-ice, the molecule could survive for ~ 109 yr.

Plasma generation and processing of interstellar carbonaceous dust analogs.

Interstellar (IS) dust analogs, based on amorphous hydrogenated carbon (a-C:H) were generated by plasma deposition in RF discharges of CH4 + He mixtures. The a-C:H samples were characterized by means of secondary electron microscopy (SEM), infrared (IR) spectroscopy and UV-visible reflectivity. DFT calculations of structure and IR spectra were also carried out. From the experimental data, atomic compositions were estimated. Both IR and reflectivity measurements led to similar high proportions (≈ 50%) of H atoms, but there was a significant discrepancy in the sp2/sp3 hybridization ratios of C atoms (sp2/sp3 = 1.5 from IR and 0.25 from reflectivity). Energetic processing of the samples with 5 keV electrons led to a decay of IR aliphatic bands and to a growth of aromatic bands, which is consistent with a dehydrogenation and graphitization of the samples. The decay of the CH aliphatic stretching band at 3.4 µm upon electron irradiation is relatively slow. Estimates based on the absorbed energy and on models of cosmic ray (CR) flux indicate that CR bombardment is not enough to justify the observed disappearance of this band in dense IS clouds.

Precisely controlled fabrication, manipulation and in-situ analysis of Cu based nanoparticles.

The increasing demand for nanostructured materials is mainly motivated by their key role in a wide variety of technologically relevant fields such as biomedicine, green sustainable energy or catalysis. We have succeeded to scale-up a type of gas aggregation source, called a multiple ion cluster source, for the generation of complex, ultra-pure nanoparticles made of different materials. The high production rates achieved (tens of g/day) for this kind of gas aggregation sources, and the inherent ability to control the structure of the nanoparticles in a controlled environment, make this equipment appealing for industrial purposes, a highly coveted aspect since the introduction of this type of sources. Furthermore, our innovative UHV experimental station also includes in-flight manipulation and processing capabilities by annealing, acceleration, or interaction with background gases along with in-situ characterization of the clusters and nanoparticles fabricated. As an example to demonstrate some of the capabilities of this new equipment, herein we present the fabrication of copper nanoparticles and their processing, including the controlled oxidation (from Cu0 to CuO through Cu2O, and their mixtures) at different stages in the machine.

Demonstration of Single-Barium-Ion Sensitivity for Neutrinoless Double-Beta Decay Using Single-Molecule Fluorescence Imaging.

A new method to tag the barium daughter in the double-beta decay of ^{136}Xe is reported. Using the technique of single molecule fluorescent imaging (SMFI), individual barium dication (Ba^{++}) resolution at a transparent scanning surface is demonstrated. A single-step photobleach confirms the single ion interpretation. Individual ions are localized with superresolution (∼2 nm), and detected with a statistical significance of 12.9σ over backgrounds. This lays the foundation for a new and potentially background-free neutrinoless double-beta decay technology, based on SMFI coupled to high pressure xenon gas time projection chambers.

Using radio astronomical receivers for molecular spectroscopic characterization in astrochemical laboratory simulations: A proof of concept.

We present a proof of concept on the coupling of radio astronomical receivers and spectrometers with chemical reactors and the performances of the resulting setup for spectroscopy and chemical simulations in laboratory astrophysics. Several experiments including cold plasma generation and UV photochemistry were performed in a 40 cm long gas cell placed in the beam path of the Aries 40 m radio telescope receivers operating in the 41-49 GHz frequency range interfaced with fast Fourier transform spectrometers providing 2 GHz bandwidth and 38 kHz resolution. The impedance matching of the cell windows has been studied using different materials. The choice of the material and its thickness was critical to obtain a sensitivity identical to that of standard radio astronomical observations. Spectroscopic signals arising from very low partial pressures of CH3OH, CH3CH2OH, HCOOH, OCS, CS, SO2 (<10-3 mbar) were detected in a few seconds. Fast data acquisition was achieved allowing for kinetic measurements in fragmentation experiments using electron impact or UV irradiation. Time evolution of chemical reactions involving OCS, O2 and CS2 was also observed demonstrating that reactive species, such as CS, can be maintained with high abundance in the gas phase during these experiments.

Laboratory study of methyl isocyanate ices under astrophysical conditions.

Methyl isocyanate has been recently detected in comet 67P/ Churyumov-Gerasimenko (67P/CG) and in the interstellar medium. New physicochemical studies on this species are now necessary as tools for subsequent studies in astrophysics. In this work, infrared spectra of solid CH3NCO have been obtained at temperatures of relevance for astronomical environments. The spectra are dominated by a strong, characteristic multiplet feature at 2350-2250 cm-1, which can be attributed to the antisymmetric stretching of the NCO group. A phase transition from amorphous to crystalline methyl isocyanate is observed at ~ 90 K. The band strengths for the absorptions of CH3NCO in ice at 20 K have been measured. Deuterated methyl isocyanate is used to help with the spectral assignment. No X-ray structure has been reported for crystalline CH3NCO. Here we advance a tentative theoretical structure, based on Density Functional Theory (DFT) calculations, derived taking as a starting point the crystal of isocyanic acid. A harmonic theoretical spectrum is calculated then for the proposed structure, and compared with the experimental data. A mixed ice of H2O and CH3NCO was formed by simultaneous deposition of water and methyl isocyanate at 20 K. The absence of new spectral features indicates that methyl isocyanate and water do not react appreciably at 20 K, but form a stable mixture. The high CH3NCO/H2O ratio reported for comet 67P/CG, and the characteristic structure of the 2350-2250 cm-1 band, make of it a very good candidate for future astronomical searches.

Influence of vibration in the reactive scattering of D + MuH: the effect of dynamical bonding.

The dynamics of the D + MuH(v = 1) reaction has been investigated using time-independent quantum mechanical calculations. The total reaction cross sections and rate coefficients have been calculated for the two exit channels of the reaction leading, respectively, to DMu + H and DH + Mu. Over the 100-1000 K temperature range investigated the rate coefficients for the DMu + H channel are of the order of 10(-10) cm(3) s(-1) and those for the DH + Mu channel vary between 1 × 10(-12) and 8 × 10(-11) cm(3) s(-1). These results point to a virtually barrierless reaction for the DMu + H channel and to the presence of a comparatively small barrier for the DH + Mu channel and are consistent with the profiles of their respective collinear vibrationally adiabatic potentials (VAPs). The effective barrier in the VAP of the DH + Mu channel is located in the reactant valley and, consequently, translation is found to be more efficient than vibration for the promotion of the reaction over a large energy interval in the post threshold region. Below this barrier, the DH + Mu channel can be accessible through an indirect mechanism implying crossing from the DMu + H pathway. The most salient feature found in the present study is revealed in the total reaction cross section for the DMu + H channel, which shows a sharp resonance caused by the presence of a deep well in the vibrationally adiabatic potential. This well has a dynamical origin, reminiscent of that found recently in the vibrationally bonded BrMuBr complex [Fleming, et al., Angew. Chem., Int. Ed., 2014, 53, 1], and is due to the stabilizing effect of the light Mu atom oscillating between the heavier H and D isotopes and to the bond softening associated with vibrational excitation of MuH.

The High Resolution Infrared Spectrum of HCl.

The chloroniumyl cation, HCl+, has been recently identified in space from Herschel's spectra. A joint analysis of extensive vis-UV spectroscopy emission data together with a few high-resolution and high-accuracy millimiter-wave data provided the necessary rest frequencies to support the astronomical identification. Nevertheless, the analysis did not include any infrared (IR) vibration-rotation data. Furthermore, with the end of the Herschel mission, infrared observations from the ground may be one of the few available means to further study this ion in space. In this work, we provide a set of accurate rovibrational transition wavenumbers as well as a new and improved global fit of vis-UV, IR and millimiter-wave spectroscopy laboratory data, that will aid in future studies of this molecule.

Chemistry in glow discharges of H2 / O2 mixtures. Diagnostics and modelling.

The chemistry of low pressure H2 + O2 discharges with different mixture ratios has been studied in a hollow cathode DC reactor. Neutral and positive ion distributions have been measured by mass spectrometry, and Langmuir probes have been used to provide charge densities and electron temperatures. A simple zero order kinetic model including neutral species and positive and negative ions, which takes into account gas-phase and heterogeneous chemistry, has been used to reproduce the global composition of the plasmas over the whole range of mixtures experimentally studied, and allows for the identification of the main physicochemical mechanisms that may explain the experimental results. To our knowledge, no combined experimental and modelling studies of the heavy species kinetics of low pressure H2 + O2 plasmas including ions has been reported before. As expected, apart from the precursors, H2O is detected in considerable amounts. The model also predicts appreciable concentrations of H and O atoms and the OH radical. The relevance of the metastable species O(1D) and O2(a1Δg) is analysed. Concerning the charged species, positive ion distributions are dominated by H3O+ for a wide range of intermediate mixtures, while H3+ and O2+ are the major ions for the higher and lower H2/O2 ratios, respectively. The mixed ions OH+, H2O+ and HO2+ are also observed in small amounts. Negative ions are shown to have a limited relevance in the global chemistry; their main contribution is the reduction of the electron density available for electron impact processes.

Influence of the Reactants Rotational Excitation on the H + D2(v = 0, j) Reactivity.

We have analyzed the influence of the rotational excitation on the H + D2(v = 0, j) reaction through quantum mechanical (QM) and quasiclassical trajectories (QCT) calculations at a wide range of total energies. The agreement between both types of calculations is excellent. We have found that the rotational excitation largely increases the reactivity at large values of the total energy. Such an increase cannot be attributed to a stereodynamical effect but to the existence of recrossing trajectories that become reactive as the target molecule gets rotationally excited. At low total energies, however, recrossing is not significant and the reactivity evolution is dominated by changes in the collision energy; the reactivity decreases with the collision energy as it shrinks the acceptance cone. When state-to-state results are considered, rotational excitation leads to cold product's rovibrational distributions, so that most of the energy is released as recoil energy.