A high-level ab initio study of the photodissociation of acetaldehyde.

Acetaldehyde is a very relevant atmospheric species whose photodissociation has been extensively studied in the first absorption band both experimentally and theoretically. Very few works have been reported on acetaldehyde photodissociation at higher excitation energies. In this work, the photodissociation dynamics of acetaldehyde is investigated by means of high-level multireference configuration interaction ab initio calculations. Five different fragmentation pathways of acetaldehyde are explored by calculating the potential-energy curves of the ground and several excited electronic states along the corresponding dissociating bond distances. The excitation energy range covered in the study is up to 10 eV, nearly the ionization energy of acetaldehyde. We intend to rationalize the available experimental results and, in particular, to elucidate why some of the studied fragmentation pathways are experimentally observed in the different excitation energy regions and some others are not. Based on the shape of the calculated potential curves, we are able to explain the main findings of the available experiments, also suggesting possible dynamical dissociation mechanisms in the different energy regions. Thus, the reported potential curves are envisioned as a useful tool to interpret the currently available experiments as well as future ones on acetaldehyde photodissociation at excitation wavelengths in the range studied here.

Photodissociation of the CH2Br radical: A theoretical study.

Bromine atom (Br) reactions lead to ozone depletion in the troposphere and stratosphere. Photodegradation of bromocarbons is one of the main sources of bromine atoms in the atmosphere. Here, we use high-level ab initio methods, including spin-orbit effects, to study the photodissociation of the CH2Br radical. All possible fragmentation pathways, namely CH2Br + hν → CH2 + Br, HCBr + H, and CBr + H2, have been analyzed. Potential-energy curves of the ground and several excited electronic states along the corresponding dissociating bond distance of each pathway have been calculated. Considering the actinic fluxes of solar irradiation in the troposphere and in the stratosphere in the relevant range of frequencies, it is found that the first five excited states of CH2Br can be accessed from the ground state. Analysis of the potential curves shows that the pathways producing CH2 + Br and HCBr + H can proceed through a fast direct dissociation mechanism, while the pathway leading to CBr + H2 involves much slower dissociation mechanisms like internal conversion between electronic states, predissociation, or tunneling through exit barriers. The main implications are that the two faster channels are predicted to be dominant, and the slower pathway is expected to be less relevant. The tropospheric and stratospheric solar actinic fluxes also allow for further dissociation of the HCBr and CBr fragments, generating additional Br atoms, provided that they survive possible collisions with other atmospheric reagents. Finally, we discuss the possible effect of each of the three CH2Br dissociation pathways on the depletion of atmospheric ozone.

An ab initio study of the photodissociation of CH2I and CH2I.

Photodissociation of the CH2I radical and the CH2I+ cation is studied by means of high-level ab initio calculations, including spin-orbit effects. Potential-energy curves (PEC) along the dissociating bond distances involved in some fragmentation pathways of these species are computed for the ground and several excited electronic states. Based on the PECs obtained, the possible photodissociation mechanisms are analyzed and suggested. Significant differences are found between the fragmentation dynamics of the neutral radical and that of the cation. While a relatively simple dissociation dynamics is predicted for CH2I, more complex fragmentation mechanisms involving internal conversion and couplings between different excited electronic states are expected for CH2I+. The species studied here are relevant to atmospheric chemistry, and the present work can help to understand better how their photodissociation may affect chemical processes in the atmosphere.

Multifunctional TiO2 coatings developed by plasma electrolytic oxidation technique on a Ti20Nb20Zr4Ta alloy for dental applications.

A newly developed ß-Ti alloy based on the Ti-Nb-Zr-Ta system (Ti20Nb20Zr4Ta) has been subjected to Plasma Electrolytic Oxidation (PEO) treatment to obtain a multifunctional ceramic-like (TiO2) coating with superior tribocorrosion (wear and corrosion) resistance and improved biocompatibility. For this aim, elements such as Ca, P, and Ag NPs have been incorporated into the oxide film to obtain bioactive and biocide properties. The chemical composition and morphology of the TiO2-PEO coating was characterized, and its multifunctionality was addressed by several means, including antibacterial activity assessment, formation of bone-like apatite, metallic ion release evaluation, in vitro cellular response analysis, and corrosion and tribocorrosion tests in artificial saliva. The developed coatings enhanced the corrosion and tribocorrosion resistance of the bare alloy and exhibited antibacterial ability with low cytotoxicity and negligible ion release. Furthermore, they were able to sustain MC3T3-E1 preosteoblast viability/proliferation and osteogenic differentiation. Altogether, the results obtained demonstrate the potential of the TiO2 coating incorporating Ca, P, and Ag NPs to be used for dental applications.

Impact on the incidence of gastrointestinal perforation during the COVID-19 pandemic in the Costa del Sol healthcare system area.

INTRODUCTION AND AIMS: Gastrointestinal perforation is a surgical emergency that is associated with a high mortality rate and requires special care. During the pandemic, there has been competition with COVID-19 patients for health resources, especially ICU bed availability. The primary aim of our study was to compare the incidence of gastrointestinal perforation during the COVID-19 pandemic, with cases registered before the pandemic. MATERIALS AND METHODS: A retrospective, observational, single center, cohort study was conducted that included patients that underwent emergency surgery for gastrointestinal perforation in the periods during the pandemic (6 months) and before the pandemic (12 months). Sociodemographic characteristics, comorbidities, duration of hospital and ICU stay, status at discharge, and perforation site were compared. RESULTS: The study included 67 subjects (33 in the pre-pandemic period and 34 in the pandemic period). There were no significant differences regarding sex, age, or comorbidity. The perforation rate per emergency intervention was 4-times higher during the pandemic. There was an increase in the number of patients that were foreigners (4 [11%]) and nonresidents (6 [17%]). ICU admissions decreased (6 [19%]) but ICU stay increased to 137 h. Hospital stay increased by 5 days and delay in care increased 4.5 h. The number of deaths was higher (from 5 [15.2%] to 10 [29.4%]). Four patients with perforations were positive for COVID-19, were admitted to the ICU, and died. CONCLUSIONS: During the COVID-19 pandemic there was an increase in the incidence of gastrointestinal perforations at our healthcare system area; symptoms were more advanced, and mortality was higher.

Reflectionless Klein tunneling of Dirac fermions: comparison of split-operator and staggered-lattice discretization of the Dirac equation.

Massless Dirac fermions in an electric field propagate along the field lines without backscattering, due to the combination of spin-momentum locking and spin conservation. This phenomenon, known as 'Klein tunneling', may be lost if the Dirac equation is discretized in space and time, because of scattering between multiple Dirac cones in the Brillouin zone. To avoid this, a staggered space-time lattice discretization has been developed in the literature, withonesingle Dirac cone in the Brillouin zone of the original square lattice. Here we show that the staggering doubles the size of the Brillouin zone, which actually containstwoDirac cones. We find that this fermion doubling causes a spurious breakdown of Klein tunneling, which can be avoided by an alternative single-cone discretization scheme based on a split-operator approach.

An ab initio study of the photodissociation of the vinyl radical.

Photodissociation of the vinyl radical through pathways CH2CH → CH2C + H, CH2CH → CHCH + H, and CH2CH → CH2 + CH is investigated by means of high-level ab initio calculations. Potential-energy curves (PECs) along the corresponding dissociating bond distance associated with the ground and several excited electronic states involved in the above fragmentation pathways, as well as the nonadiabatic couplings connecting the different states, are obtained. The findings of several experiments on vinyl photodissociation performed at different excitation wavelengths are analyzed and explained qualitatively in the light of the present PECs. A two-dimensional representation (consisting of radial and angular coordinates to represent one of the H atoms of the CH2 group) is also used to calculate the electronic states. The surfaces obtained reflect a rich variety of conical intersections, exit barriers, and nonadiabatic couplings leading to predissociation in different regions of energy and of the two coordinates, suggesting a complex photodissociation dynamics of the CH2CH → CHCH + H pathway, with rather different fragmentation mechanisms involved. The two-dimensional results also provide interesting information on the mechanism of in-plane hydrogen migration from the CH2 group to the CH one through a high-lying transition state.

Photodissociation of the methyl radical: the role of nonadiabatic couplings in enhancing the variety of dissociation mechanisms.

The nonadiabatic photodissociation dynamics of the CH3 (and CD3) radical from the 3pz and 3s Rydberg states is investigated by applying a one-dimensional (1D) wave packet model that uses recently calculated ab initio 1D electronic potential-energy curves and nonadiabatic couplings. Calculated predissociation lifetimes are found to be too long as compared to the experimental ones. The 1D dynamical model, however, is able to predict qualitatively and explain the fragmentation mechanisms that produce the hydrogen-fragment translational energy distributions (TED) measured experimentally for the ground vibrational resonance of the 3pz and 3s Rydberg states (CH3(v = 0, 3pz) and CH3(v = 0, 3s)). The CH3(v = 0, 3pz) TED found experimentally displays a rather large energy spreading, while the experimental CH3(v = 0, 3s) TED is remarkably more localized in energy. The present model also predicts a widely spread CH3(v = 0, 3pz) TED, produced by a complex dissociation mechanism which involves predissociation to one dissociative valence state through a nonadiabatic coupling, as well as transfer of population to a second valence state through three conical intersections. Also in agreement with experiment, the model predicts a rather localized CH3(v = 0, 3s) TED because the conical intersections no longer operate in this photodissociation process, and predissociation occurs only into a single valence state. Another complex dissociation mechanism is predicted by the model for initial CH3(v > 0, 3s) and CD3(v > 0, 3s) resonances. In this case the mechanism is gradually activated, as vibrational excitation increases, by the interplay between the two nonadiabatic couplings connecting the 3s and 3px,y Rydberg states with the dissociative 2A1 valence state, and produces complex TEDs with signals from several resonances of both 3s and 3px,y. Thus the present 1D quantum model reveals a rich photodissociation dynamics of methyl, where a variety of complex fragmentation mechanisms is favored by the presence of different nonadiabatic couplings between the electronic states involved.

Capsular type diversity of Mannheimia haemolytica determined by multiplex real-time PCR and indirect hemagglutination in clinical isolates from cattle, sheep, and goats in Spain.

This study compares the utility of a commercially available multiplex q-PCR assay for serotyping A1, A2, and A6 M. haemolytica serotypes with indirect hemagglutination, for determining the relative distribution of M. haemolytica capsular types associated with respiratory disorders in cattle, sheep, and goats. For the 129 isolates analyzed, both q-PCR and IHA assays exhibited nearly complete agreement for capsular types A1 (k = 0.965) and A2 (k = 0.888) and substantial agreement for A6 (k = 0.801). Despite the overall good performance of the commercial q-PCR, its effectiveness differed between the host origin of the isolates. The serotype was identified by q-PCR in 83.3 % of cattle, 77.8 % of goat, and 53.8 % of sheep isolates. Combining the results of both methods, A1 was the most prevalent in cattle and sheep (55.6 % and 22.25 %, respectively) but was not detected in goats, A2 was the most prevalent in goats (61.1 %) and the second most prevalent in cattle (16.7 %) and sheep (20.5 %). The prevalence of A6 was 7.4 %, 5.1 %, and 16.7 % in cattle, sheep, and goats, respectively. Other capsular types determined exclusively by IHA were A16 in cattle, A9 in goats, and A7, A8, A9, and A13 in sheep. Capsular type diversity was greater in sheep (H = 0.601) than in cattle (H = 0.408) and goat (H = 0.330) isolates. The commercial multiplex q-PCR is a valuable tool, alternative to IHA, for identifying isolates of capsular types A1, A2, and A6, the most frequent serotypes of M. haemolytica associated with respiratory disease in ruminants. However, when testing sheep isolates it should be complemented with immunological assays due to the wider range of serotypes implicated.

Utilidad del sistema Myo Plus en pacientes amputados transradiales / Use of the Myo Plus system in transradial amputation patients

Las amputaciones de miembro superior son infrecuentes pero provocan una gran discapacidad. Suelen ser de etiología traumática y en varones jóvenes menores de 40 años y activos. La frecuencia de la amputación de nivel transradial es del 35% de los casos, siendo la prótesis mioeléctrica la que aporta mayor funcionalidad. Un 25% de los pacientes abandona el uso de la prótesis, siendo la complejidad de su uso, mediante 2 electrodos convencionales, una de las causas más frecuentes del abandono. El sistema Myo Plus, con 8 canales de electromiografía, facilita al paciente el control protésico utilizando el miembro fantasma y consiguiendo los patrones de cierre, apertura y pronosupinación de la mano en un tiempo menor al convencional y más fácilmente. Además, conlleva un menor tiempo de rehabilitación, disminuyendo los costes y los desplazamientos innecesarios, sin incrementar el tiempo de fabricación del encaje (AU)

Upper limb amputations are uncommon but cause severe disability. It is usually of traumatic origin and in young males less than 40 years-old, and active. The frequency of amputation at transradial level is around 35% of cases, with the myoelectric prosthesis achieving greater functionality. Around 25% of the patients give up using of the prosthesis, due to its complexity of use by means of 2 conventional electrodes, one of the most common causes for giving up. The Myo Plus system with an 8-channel electromyograph helps the patient to control the prosthesis using the phantom limb and achieving the closing, opening, and pronation-supination patterns of the hand in a time less than the conventional one and more easily. It also leads to less rehabilitation time, decreasing costs and unnecessary travel, without increasing the time for the manufacture of the socket (AU)

[Use of the Myo Plus system in transradial amputation patients]. / Utilidad del sistema Myo Plus en pacientes amputados transradiales.

Upper limb amputations are uncommon but cause severe disability. It is usually of traumatic origin and in young males less than 40 years-old, and active. The frequency of amputation at transradial level is around 35% of cases, with the myoelectric prosthesis achieving greater functionality. Around 25% of the patients give up using of the prosthesis, due to its complexity of use by means of 2 conventional electrodes, one of the most common causes for giving up. The Myo Plus system with an 8-channel electromyograph helps the patient to control the prosthesis using the phantom limb and achieving the closing, opening, and pronation-supination patterns of the hand in a time less than the conventional one and more easily. It also leads to less rehabilitation time, decreasing costs and unnecessary travel, without increasing the time for the manufacture of the socket.

Strength of association between isolation of Pasteurella multocida and consolidation lesions in ovine pneumonic pasteurellosis.

This study investigated the association of Pasteurella multocida isolation and the molecular characteristics of the isolates with the presence of pneumonic lesions in lambs at slaughter to assess its importance as a causative agent of pneumonic pasteurellosis compared with Mannheimia haemolytica. P. multocida was isolated from the 13.9% and 2.7%, and M. haemolytica from the 36.4% and 26.8%, of lungs with and without lesions, respectively (P < 0.05). Both microorganisms were frequently coisolated (23.2% and 12.5% from lungs with and without lesions, respectively). Isolation of P. multocida alone exhibited greater strength of association with pneumonic lesions (OR 11.4; 95% CI 3.2-40.6) than that exhibited by M. haemolytica alone (OR 3.0; 95% CI 1.6-5.4). Cluster analysis grouped the lungs into four clusters characterized by the isolation of M. haemolytica or P. multocida alone (clusters 1 and 4), coisolation of both microorganisms (cluster 3), and isolation of neither (cluster 2). Cluster 4 lungs exhibited higher frequencies of pneumonic lesions (87.5%) and severe (20.8%) and moderate (25.0%) lesions. Lungs coinfected with both pathogens (cluster 3) did not exhibit a higher frequency of severe and moderate consolidation lesions (6.1% and 14.3%, respectively), suggesting that P. multocida and M. haemolytica do not act synergically to cause more severe pneumonic infections. The greater strength of association of P. multocida isolation with pneumonic lesions together with the higher severity of the lesions caused could indicate a greater role played by this pathogen in the aetiopathogenesis of pneumonic pasteurellosis in sheep than is commonly assumed.

Interference of a resonance state with itself: a route to control its dynamical behaviour.

It is demonstrated both numerically and mathematically that the dynamical behavior of an isolated resonance state, which comprises the resonance decay lifetime and the asymptotic fragment state distribution produced upon resonance decay, can be extensively controlled by means of quantum interference induced by a laser field in the weak-field regime. The control scheme applied is designed to induce interference between amplitudes excited at two different energies of the resonance line shape, namely the resonance energy and an additional energy. This scheme exploits the resonance property of possessing a nonzero energy width, which makes it possible that a resonance state may interfere with itself, and thus allows interference between the amplitudes excited at the two energies of the resonance width. The application of this scheme opens the possibility of a universal control of both the duration and the fragment product distribution outcome of any resonance-mediated molecular process.

Molecular signatures of atherosclerotic plaques: An up-dated panel of protein related markers.

Atherosclerosis remains the leading cause of ischemic syndromes such as myocardial infarction or brain stroke, mainly promoted by plaque rupture and subsequent arterial blockade. Identification of vulnerable or high-risk plaques constitutes a major challenge, being necessary to identify patients at risk of occlusive events in order to provide them with appropriate therapies. Clinical imaging tools have allowed the identification of certain structural indicators of prone-rupture plaques, including a necrotic lipidic core, intimal and adventitial inflammation, extracellular matrix dysregulation, and smooth muscle cell depletion and micro-calcification. Additionally, alternative approaches focused on identifying molecular biomarkers of atherosclerosis have also been applied. Among them, proteomics has provided numerous protein markers currently investigated in clinical practice. In this regard, it is quite uncertain that a single molecule can describe plaque rupture, due to the complexity of the process itself. Therefore, it should be more accurate to consider a set of markers to define plaques at risk. Herein, we propose a selection of 76 proteins, from classical inflammatory to recently related markers, all of them identified in at least two proteomic studies analyzing unstable atherosclerotic plaques. Such panel could be used as a prognostic signature of plaque instability.

[Measurement of out-of-field dose to the uterus during proton therapy of the head and neck]. / Mesure de la dose délivrée hors champ à l'utérus lors d'un traitement ORL par protons.

The decision to irradiate during pregnancy is based on a risk benefit compromise of two kinds: maternal risk and fetal risk. The aim of this work is to determine the foetal risk, and uterine dose measurement in proton therapy. Foetal exposure during treatment is linked to two sources: the treatment phase, and the repositioning phase. An Alderson-Rando anthropomorphic ghost (170cm, 74kg) was positioned on the table in the treatment position. A tissue-equivalent proportional counter (TEPC), adapted to the analysis of complex radiation fields (neutron and photonics), was used to determine the irradiation related to the treatment phase. An AT1123 radiation survey meter was used to measure photons generated by X-ray radiation. I dosimetry was proposed using radio-photoluminescent dosimeters, allowing for a daily check of the dose received in the uterus. The treatment phase produces higher uterine doses than the positioning phase, but these remain very low. The equivalent dose received in the uterus for the entire treatment is estimated at 840 µSv. Using a methodology for measuring the out-of-field dose with pencil beam scanning proton therapy, the foetal dose in the first trimester was well below the acceptance dose of 100 mGy determined by the International Commission on Radiological Protection.

Delaying the Decay of a Superposition of Resonance States.

A weak-field coherent control scheme is applied in order to enhance the decay lifetime of a superposition of overlapping resonance states. The scheme uses a pump laser field consisting of two pulses delayed in time, each of them exciting a different energy at which several resonances of the Ne-Br2(B) complex overlap. Simultaneous excitation of these two energies induces interference between the overlapping resonances, which causes an enhancement of the lifetime of the superposition created. By variation of the delay time between the pulses, the mechanism of resonance interference can be controlled and optimized to achieve a maximum lifetime enhancement. The optimal delay time between pulses leading to maximum superposition lifetime can be quantitatively predicted with a simple law. The effect of the interference mechanism on the lifetime enhancement is investigated. It is found that interference induces a transfer of amplitude between the different resonances back and forth, which delays significantly the natural resonance decay, increasing the global lifetime of the superposition. Due to the simplicity of the control scheme, a wide applicability is envisioned.

[Proton therapy for head and neck squamous cell carcinomas: From physics to clinic]. / Protonthérapie des carcinomes épidermoïdes des voies aérodigestives supérieures : de la physique à la clinique.

Intensity-modulated radiation therapy (IMRT) is presently the recommended technique for the treatment of locally advanced head and neck carcinomas. Proton therapy would allow to reduce the volume of irradiated normal tissue and, thus, to decrease the risk of late dysphagia, xerostomia, dysgeusia and hypothyroidism. An exhaustive research was performed with the search engine PubMed by focusing on the papers about the physical difficulties that slow down use of proton therapy for head and neck carcinomas. Range uncertainties in proton therapy (±3 %) paradoxically limit the use of the steep dose gradient in distality. Calibration uncertainties can be important in the treatment of head and neck cancer in the presence of materials of uncertain stoichiometric composition (such as with metal implants, dental filling, etc.) and complex heterogeneities. Dental management for example may be different with IMRT or proton therapy. Some uncertainties can be somewhat minimized at the time of optimization. Inter- and intrafractional variations and uncertainties in Hounsfield units/stopping power can be integrated in a robust optimization process. Additional changes in patient's anatomy (tumour shrinkage, changes in skin folds in the beam patch, large weight loss or gain) require rescanning. Dosimetric and small clinical studies comparing photon and proton therapy have well shown the interest of proton therapy for head and neck cancers. Intensity-modulated proton therapy is a promising treatment as it can reduce the substantial toxicity burden of patients with head and neck squamous cell carcinoma compared to IMRT. Robust optimization will allow to perform an optimal treatment and to use proton therapy in current clinical practice.

Data supporting the morphological/topographical properties and the degradability on PET/PLA and PET/chitosan blends.

These data display evidence of the fracture through the morphologies and the topographical features as well as roughness data of different ratios of R(recycled)-PET/PLA, PET(virgin)/PLA, PET(virgin)/Chitosan and R(recycled)-PET/chitosan. Also, data of the morphologies after degradation under accelerated weathering test and degradation mechanisms are revealed. The data supplement the article "Comparative assessment of miscibility and degradability on PET/PLA and PET/chitosan blends".

Pasteurella multocida isolates associated with ovine pneumonia are toxigenic.

The P. multocida toxin (PMT), a dermonecrotic protein encoded by the toxA gene, is the major virulence factor of capsular type D P. multocida strains causing progressive atrophic rhinitis (PAR) in pigs. A high frequency of P. multocida isolates harboring the toxA gene has been found among ovine pneumonic isolates, although the ability of these isolates to express PMT has never been examined. In this study we have investigated the ability of ovine toxA+ P. multocida isolates (n = 57) to express a functional toxin by detection of PMT toxin antigen using an ELISA test and its cytopathic effect in a Vero cell assay. PMT antigen was expressed in the great majority (54/57; 94.7%) of toxA+ isolates. Moreover, the 100% toxA+ ovine isolates analyzed produced a cytopathic effect in Vero cells within 24-48 h post-inoculation, identical to that described for porcine toxigenic P. multocida isolates. These results show for the first time that, in addition to isolates associated with PAR, isolates of P. multocida associated with pneumonia in sheep are also toxigenic. In addition, we found a total agreement (Kappa = 1; C.I. 0.75-1.25) between the detection of the toxA gene and the toxigenic capability of P. multocida isolates, indicating the PCR detection of toxA would be a suitable predictive marker of the toxigenic fitness of P. multocida.

Weak-field coherent control of photodissociation in polyatomic molecules.

A coherent control scheme is suggested to modify the output of photodissociation in a polyatomic system. The performance of the scheme is illustrated by applying it to the ultrafast photodissociation of CH3I in the A-band. The control scheme uses a pump laser weak field that combines two pulses of a few femtoseconds delayed in time. By varying the time delay between the pulses, the shape of the laser field spectral profile is modulated, which causes a change in the initial relative populations excited by the pump laser to the different electronic states involved in the photodissociation. Such a change in the relative populations produces different photodissociation outputs, which is the basis of the control achieved. The degree of control obtained over different photodissociation observables, like the branching ratio between the two dissociation channels of CH3I yielding I(2P3/2) and I*(2P1/2) and the fragment angular distributions associated with each channel, is investigated. These magnitudes are found to oscillate strongly with the time delay, with the branching ratio changing by factors between two and three. Substantial variations of the angular distributions also indicate that the scheme provides a high degree of control. Experimental application of the scheme to general polyatomic photodissociation processes should be straightforward.