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The purpose of this study was to conduct an external validation of a fracture assessment deep learning algorithm (Rayvolve®) using digital radiographs from a real-life cohort of children presenting routinely to the emergency room.This retrospective study was conducted on 2634 radiography sets (5865 images) from 2549 children (1459 boys, 1090 girls; mean age, 8.5 ± 4.5 [SD] years; age range: 0-17 years) referred by the pediatric emergency room for trauma. For each set was recorded whether one or more fractures were found, the number of fractures, and their location found by the senior radiologists and the algorithm. Using the senior radiologist diagnosis as the standard of reference, the diagnostic performance of deep learning algorithm (Rayvolve®) was calculated via three different approaches: a detection approach (presence/absence of a fracture as a binary variable), an enumeration approach (exact number of fractures detected) and a localization approach (focusing on whether the detected fractures were correctly localized). Subgroup analyses were performed according to the presence of a cast or not, age category (0-4 vs. 5-18 years) and anatomical region.Regarding detection approach, the deep learning algorithm yielded 95.7% sensitivity (95% CI: 94.0-96.9), 91.2% specificity (95% CI: 89.8-92.5) and 92.6% accuracy (95% CI: 91.5-93.6). Regarding enumeration and localization approaches, the deep learning algorithm yielded 94.1% sensitivity (95% CI: 92.1-95.6), 88.8% specificity (95% CI: 87.3-90.2) and 90.4% accuracy (95% CI: 89.2-91.5) for both approaches. Regarding age-related subgroup analyses, the deep learning algorithm yielded greater sensitivity and negative predictive value in the 5-18-years age group than in the 0-4-years age group for the detection approach (P0.001 and P = 0.002) and for the enumeration and localization approaches (P = 0.012 and P = 0.028). The high negative predictive value was robust, persisting in all of the subgroup analyses, except for patients with casts (P = 0.001 for the detection approach and P0.001 for the enumeration and localization approaches).The Rayvolve® deep learning algorithm is very reliable for detecting fractures in children, especially in those older than 4 years and without cast.

Un regard anthropologique préalable aux considérations éthiques, déontologiques et juridiques, permet d’identifier omment des pratiques de soins professionnelles ne sont pas immunisées contre une violence ordinaire de genre. Il faut dépasser les stéréotypes classiques sur le féminin et reconnaître la « situation-d’être-femme », en ses conditions sociobiologiques. Le travail d’une philosophe américaine, I.M. Young, permet de décrire les expériences féminines ordinaires et, de là, d’analyser les mécanismes de violence individuelle et organisationnelle. Ainsi, en réponse à ces défis, apparaît la nécessité de construire une éthique nouvelle et double : clinique et organisationnelle.

Experimental studies of the surface reactions of photocatalyzed or photoelectrocatalyzed water oxidation on rutile, anatase, and brookite TiO2 show significant differences between the three polymor...

Zeolites are capable to selectively adsorb molecules and therefore are applicable to chemical separation challenges. In this work, two probe molecules, ethylene (C2H4) and water (H2O) are modeled f...

Cases of coronary and pulmonary artery pseudoaneurysms secondary to COVID-19 have been reported in the literature and are supposed to be secondary to inflammatory and vasculitis processes linked to a viral multisystem inflammatory syndrome. Although the incidence of COVID-19-associated liver injury ranges from 14% to 53% in hospitalized patients, COVID-19-associated hepatic artery pseudoaneurysms have never been reported so far. We present the case of a patient whose follow-up CT after cryoablation of renal cell carcinoma revealed seven fusiform pseudoaneurysms of the two hepatic arteries secondary to COVID-19. Anticoagulant or anti-inflammatory treatments were not introduced. Vascular lesions were unchanged on the 3-month follow-up CT. At 6-month CT, the proximal pseudoaneurysm was replaced by a proximal occlusion of the accessory RHA.

Solar hydrogen peroxide (H2O2) produced through the selective two-electron (2e−) oxygen reduction pathway is an ideal alternative to liquid fuel in addition to being a versatile chemical. Up to now, low photocatalytic activity, low selectivity and serious competing reactions have been big hurdles in the production of solar H2O2 in an efficient way. Herein, we report that polyterthiophene (pTTh), a metal-free narrow-bandgap polymeric semiconductor, is an efficient photocathode for H2O2 production in alkaline solution. We found that 2e− selectivity for the ORR is dependent on the pH of electrolytes and approaches 100% at pH ∼ 13. A record-high H2O2 concentration of 110 mmol L−1 is achieved, which is two orders of magnitude higher than the previous photosynthesized H2O2. Furthermore, NiFeOx/BiVO4–pTTh dual-photoelectrodes in photoelectrochemical devices enabled bias-free synthesis of solar H2O2 of concentration ∼90 mmol L−1 for several cycles without any noticeable decay. This extremely high 2e− selectivity is attributed to the intrinsic electrochemical properties of pTTh. Theoretical calculations suggested that the selectivity-determining step in the 2e− process is over ∼200 times faster than that in the 4e− pathway. Our work paves an alternative way of generating liquid solar fuel that is very promising for practical applications.

Understanding the detailed kinetics and mechanisms of water oxidation is crucial because water oxidation is the bottleneck reaction in overall water splitting. Here, we investigated photocatalytic water oxidation on NaTaO3-based photocatalysts. With in situ FT-IR spectroscopy, two new water oxidation intermediates with IR absorption peaks centered at 1058 and 935 cm−1 were observed and assigned to Ta(VI)O and Ta(O2) peroxo species, respectively. With H218O as the reactant and NaTa16O3 as the photocatalyst, both 16O18O and 18O2 were evolved continuously from overall water splitting as analyzed by mass spectroscopy (MS), demonstrating that the lattice O atoms in NaTaO3-based photocatalysts participate in the formation of O2 during the reaction. DFT results are consistent with the formation of TaO, 16O18O and 18O18O intermediates and products, while predicting that several water oxidation pathways are thermodynamically accessible for water oxidation on NaTaO3. Based on these observations, we propose a three-step two-site mechanism for photocatalytic water oxidation on NaTaO3-based photocatalysts in which lattice oxygen plays a key role. The elucidation of the present mechanism should help in broadly understanding water oxidation on semiconductor-based photocatalysts.

Selective charge separation among different crystal facets of a semiconductor is an intriguing phenomenon for which there is no firm and full theoretical foundation currently. In this work, we repo...

Si la transfusion d’un patient requiert 2 determinations de son groupe sanguin (GS) ABO RHK, l’arrete du 15 mai 2018 rappelle que « La determination du phenotypage erythrocytaire est effectuee sur la base d’une seule realisation sur un seul echantillon sanguin ». Nous rapportons l’evolution des redondances de GS au CHU de Caen. Dans la mesure ou les resultats immuno-hematologiques des patients de l’etablissement sont integres au dossier transfusionnel informatise depuis juillet 2018, les determinations en exces (au-dela de 2 determinations par patient) sont etudiees et comparees aux donnees anterieures (issues des services de facturation du CHU). En 2020, parmi les 23 407 determinations realisees chez 13 840 patients, 4,8 % sont des determinations en exces, versus 11 % entre les 1/1/2016 et 15/12/2018, tandis que le nombre de determinations a regresse de 12 % et que le nombre de patients transfuses est stable (environ 3500 chaque annee). Le recours au DTI, sur lequel les demandes de GS sont saisies, a permis de limiter les determinations en exces, meme s’il persiste une proportion importance d’examens inutiles, aussi constatee en 2020. La generalisation de l’usage du DTI et l’optimisation des alertes qui y sont parametrees doivent permettre de progresser. Aussi, la procedure « Groupage sanguin » (2019), oriente la prescription des tests IH. L’objectif est dorenavant de la completer afin de guider les prescripteurs vers 1, 2 ou aucune determination du GS selon le contexte clinique du patient. Ainsi, l’effort de pertinence de prescription et de prelevement des examens IH est a poursuivre afin notamment de lutter contre les automatismes a l’origine d’examens inutiles et couteux.

We present mesoscale characterization of carrier transport in W/Mo-doped ms-BiVO4 (BVO) to supplement our earlier study of electron and hole transport in bulk BVO. The mesoscale kinetic Monte Carlo (KMC) approach, supported by first principles-determined electron and hole hopping rates, captures the complex dynamics of electron carriers arising from light absorption and from metal doping. The computations and simulations support the observation that, for the doping level used in experiment, doping atoms do not affect significantly the transport dynamics of the charge carriers compared to stoichiometric BVO. W/Mo doping increases the electron carrier concentration and consequently the electrode conductivity. We used a density functional theory DFT + U method to characterize the electronic structure of doped BVO. Each W and Mo atom brings one more valence electron than a V atom. These excess electrons are mobile. We adopted the theories and methods of our earlier investigations on BVO. The DFT + U theory affords an accurate description of small electron polarons with electrons localized on W or Mo or V, as well as of the hopping barriers from W/Mo-to-V or V-to-V. Calculations on a 3 × 3 × 1 supercell of W/Mo-doped ms-BVO indicate that the excess electron from W or Mo does not reside on the doping atom. There is a shallow interaction region around the doping atom where the excess electron localized on a V atom is more stable than when localized on the doping atom and slightly more stable than when the excess electron is localized far away from the doping atom. This region is two nearest V atom-wide for W and three nearest atom-wide for Mo. The depths of these stabilization regions are very small, ∼−0.65 kBT (at 300 K) for W and ∼−0.73 kBT for Mo. Calculated V-to-V hopping barriers in the doped material are little affected within the region and not affected outside the region. Using our recently developed lattice-based kinetic Monte Carlo code adapted to account for doping atoms and their energy stabilization regions, we calculated the diffusivity of electrons for carrier density relevant to experiment as well as the conductivity. The stabilization regions have little effect on the diffusivity compared to the stoichiometric system because of the smallness of the stabilization. The diffusivity is found to decrease slightly with an increasing number of carriers, but the conductivity of a system with electron polarons arising from doping together with light absorption increases compared to that of the un-doped system. This work will set the foundation to study electron transport in gradient (W/Mo)-doped systems and other mixed phase systems.

Neutral oxygen vacancies (Ovʼs) in semiconductor oxides give rise to excess electrons that have the potential to affect the binding of adsorbates to the surface through surface-to-adsorbate charge transfer, and, as a result, to alter the overpotential (OP) of reactions on oxygen-deficient materials compared to stoichiometric materials. We report a systematic computational investigation of the effects of Ovʼs on the oxygen evolution reaction (OER) overpotential for β-Ga2O3, a d10 semiconductor that has been shown to exhibit high activity for water splitting. We investigated 18 β-Ga2O3 surfaces/slabs, with and without Ovʼs and observed a clear dependence of OER activity on Ovʼs. A general finding emerged that the excess electrons associated with Ovʼs are found to participate in charge transfer to OER intermediates, making their bonds to the surface more ionic and stronger, depending on the amount of charge transfer. The OER reaction step free energies are significantly affected and the ensuing overpotential...

We report first principles and mesoscale kinetic simulations of intrinsic electron and hole transport in stoichiometric monoclinic BiVO4 (BVO). A main finding is that hole transport is bimodal: there are fast hole hops within VO4 tetrahedra that are not ‘transport-efficient’ and slower hole hops across VO4 tetrahedra that are ‘transport-efficient’. This bimodality in hole transport may explain the slow transport/high recombination characteristics of BVO. In this work, polaron hops were described via the two-state Marcus/Holstein model of VV–VIV and OI–OII interchanges for electron and hole polarons respectively. The relevant parameters in the theory were obtained using the density functional theory DFT+U method. Hopping activation energies were combined with Einstein diffusion theory to yield mobility as well as with kinetic Monte Carlo (KMC) modeling. All unique nearest neighbor electron and hole hopping processes were characterized. For V-to-V hops of electron polarons, we obtained activation energies of ∼0.37 eV that compare well with the experimental activation energy of ∼0.30 eV for drift mobility. Electron polarons remain localized on single sites along the hopping pathways before hopping via tunneling, suggestive of small non-adiabatic coupling and a diabatic character consistent with V-to-V electron transfer through space (no bridge linkers). These simulations yield a small electron transport anisotropy, with transport in the (a,b) plane being faster than along the c direction by a factor of ∼2. For hole polarons our calculations support the character of small polarons localized on O atoms as well. Some nearest neighbor hole hops have a diabatic character, while other nearest neighbor hops are adiabatic and phonon-assisted with an Arrhenius thermal dependence. Hops through O–V–O bridges and through space have low activation barriers (∼0.17 eV and ∼0.25 eV) while hops through O–Bi–O bridges have higher activation barriers (∼0.37 eV and higher). The mobility is gated by the slower transport across VO4 tetrahedra through O–Bi–O bridges owing to the underlying BVO lattice network. Hole mobility is determined to be about one order of magnitude larger than electron mobility consistent with THz spectroscopy measurements. This work sets the foundation to address facet selectivity of charge carriers in shape and size-tailored crystals.

Artificial photosynthesis requires the practical use of efficient, robust, and economical water-oxidation catalysts (WOCs) for chemical-fuel production. The synthesis of amorphous cobalt oxide nanoparticles (ca. 2nm) is reported as a WOC with a turnover frequency up to 8.6s(-1) in the photocatalytic Ru(bpy)(3)(2+)-Na2S2O8 system (bpy=2,2-bipyridyl). This activity is unprecedented in heterogeneous cobalt-based WOCs and is even comparable to that of a state-of-the-art homogeneous cobalt-based polyoxometalate catalyst. With the help of experimental and computational X-ray absorption spectroscopy, the atomic structure of the synthesized amorphous cobalt oxide nanoparticles was characterized, and it consists of a one-dimensional chain of dimeric edge-sharing CoO6 octahedra. Theoretical calculations suggest that this structure was able to promote O-O bond coupling, unlike crystalline cobalt oxide WOCs, which led to the enhanced water-oxidation activity.

We present a study of the effects of oxygen vacancies (Ovac) on the oxygen evolution reaction (OER) on the TiO2-terminated (001) surface of cubic BaTiO3 (cBTO-TiO2) using spin-polarized DFT+U calculations and the standard (cation-based) four proton-coupled-electron-transfer methodology. We find that the excess electrons associated with Ovac’s are involved in charge transfer (CT) to the intermediate adsorbate species HO*, O*, and HOO* and/or new surface oxygen hole states that we identified. The CT is responsible for an increase in these species’ binding energies to the oxygen-deficient surface (cBTO-TiO2–x) to an extent consistent with their electronegativity. The much stronger stabilization of HO* and O* compared to HOO* results in an increased overpotential ηOER on the reduced oxide. This result is at odds with experiment that shows a significantly increased efficiency for oxygen-deficient BTO, suggesting that a different mechanism and/or surface must be involved under the experimental conditions. We al...

A. Otero-de-la-Roza acknowledges support from the Spanish government for a Ramón y Cajal fellowship (No. RyC-2016-20301) and for financial support (Project Nos. PGC2018-097520-A-100 and RED2018-102612-T)., Aprà, E., Bylaska, E.J., De Jong, W.A., Govind, N., Kowalski, K., Straatsma, T.P., Valiev, M., Van Dam, H.J.J., Alexeev, Y., Anchell, J., Anisimov, V., Aquino, F.W., Atta-Fynn, R., Autschbach, J., Bauman, N.P., Becca, J.C., Bernholdt, D.E., Bhaskaran-Nair, K., Bogatko, S., Borowski, P., Boschen, J., Brabec, J., Bruner, A., Cauët, E., Chen, Y., Chuev, G.N., Cramer, C.J., Daily, J., Deegan, M.J.O., Dunning, T.H., Jr., Dupuis, M., Dyall, K.G., Fann, G.I., Fischer, S.A., Fonari, A., Früchtl, H., Gagliardi, L., Garza, J., Gawande, N., Ghosh, S., Glaesemann, K., Götz, A.W., Hammond, J., Helms, V., Hermes, E.D., Hirao, K., Hirata, S., Jacquelin, M., Jensen, L., Johnson, B.G., Jónsson, H., Kendall, R.A., Klemm, M., Kobayashi, R., Konkov, V., Krishnamoorthy, S., Krishnan, M., Lin, Z., Lins, R.D., Littlefield, R.J., Logsdail, A.J., Lopata, K., Ma, W., Marenich, A.V., Martin Del Campo, J., Mejia-Rodriguez, D., Moore, J.E., Mullin, J.M., Nakajima, T., Nascimento, D.R., Nichols, J.A., Nichols, P.J., Nieplocha, J., Otero-De-La-Roza, A., Palmer, B., Panyala, A., Pirojsirikul, T., Peng, B., Peverati, R., Pittner, J., Pollack, L., Richard, R.M., Sadayappan, P., Schatz, G.C., Shelton, W.A., Silverstein, D.W., Smith, D.M.A., Soares, T.A., Song, D., Swart, M., Taylor, H.L., Thomas, G.S., Tipparaju, V., Truhlar, D.G., Tsemekhman, K., Van Voorhis, T., Vázquez-Mayagoitia, A., Verma, P., Villa, O., Vishnu, A., Vogiatzis, K.D., Wang, D., Weare, J.H., Williamson, M.J., Windus, T.L., Woliński, K., Wong, A.T., Wu, Q., Yang, C., Yu, Q., Zacharias, M., Zhang, Z., Zhao, Y., Harrison, R.J.

We describe a new computer implementation of electron transfer (ET) theory in extended systems treated by periodic density functional theory (DFT), including the calculation of the electronic coupling transition element VAB. In particular, the development opens up the full characterization of electron transfer in the solid state. The approach is valid for any single-determinant wavefunction with localized character representing the electronic structure of the system, from Hartree–Fock (HF) theory, to density functional theory (DFT), hybrid DFT theory, DFT+U theory, and constrained DFT (cDFT) theory. The implementation in CP2K reuses the high-performance functions of the code. The computational cost is equivalent to only one iteration of an HF calculation. We present test calculations for electron transfer in a number of systems, including a 1D-model of ferric oxide, hematite Fe2O3, rutile TiO2, and finally bismuth vanadate BiVO4.

The proton pathway of [FeFe]-hydrogenase is essential for enzymatic H2 production and oxidation and is composed of four residues and a water molecule. A computational analysis of this pathway in the [FeFe]-hydrogenase from Clostridium pasteurianum revealed that the solvent-exposed residue of the pathway (Glu282) forms hydrogen bonds to two residues outside of the pathway (Arg286 and Ser320), implying that these residues could function in regulating proton transfer. In this study, we show that substituting Arg286 with leucine eliminates hydrogen bonding with Glu282 and results in an ∼3-fold enhancement of H2 production activity when methyl viologen is used as an electron donor, suggesting that Arg286 may help control the rate of proton delivery. In contrast, substitution of Ser320 with alanine reduces the rate ∼5-fold, implying that it either acts as a member of the pathway or influences Glu282 to permit proton transfer. Interestingly, quantum mechanics/molecular mechanics and molecular dynamics calculations indicate that Ser320 does not play a structural role or indirectly influence the barrier for proton movement at the entrance of the channel. Rather, it may act as an additional proton acceptor for the pathway or serve in a regulatory role. While further studies are needed to elucidate the role of Ser320, collectively these data provide insights into the complex proton transport process.

Anion doping of semiconductors with nitrogen is a strategy often adopted to narrow the band gap of semiconductors and increase the range of light absorption. However, the influence of nitrogen doping on the electron mobility in the semiconductor is not fully understood and characterized. In this work, we used magnesium tantalate MgTa2O6 as a model system and hybrid density-functional theory calculations to characterize the mobility of electrons using the small polaron model in the presence of nitrogen-doping defects as well as oxygen-vacancy defects. We found that electron mobility is not significantly affected when MgTa2O6 is doped with a molar ratio N/O of ∼2%. However, in the presence of oxygen vacancies combined with nitrogen doping with the same molar ratio N/O of ∼2%, the barrier to electron hopping in the vicinity of the defects is much lower than that in pristine MgTa2O6 and in MgTa2O6 with oxygen-vacancy defects only. These results suggest that nitrogen doping combined with anion vacancy not only...

Oxygen vacancies are a double-edged sword for photoelectrochemical (PEC) devices and a comprehensive understanding on their role in PEC processes is important. Although there is existing work that illustrates their effect on PEC processes, clarifying the influence of surface and bulk oxygen vacancies, respectively, on the PEC performance is challenging. Herein, we present the fabrication of WO3 photoanodes with tunable bulk and surface oxygen vacancy with a novel two-step flame heating approach that is proving to be a powerful platform for this purpose. We found that both the conductivity and trapping state density of the WO3 photoanode increase with bulk oxygen vacancy density, leading to a volcano-like relationship between the kinetics of charge separation/transport and bulk oxygen vacancy density. Moreover, both the interfacial charge transfer rate constant and the charge recombination rate constant on the surface of the WO3 photoanode increase with surface oxygen vacancy density, which also leads to a volcano-like relationship between the charge injection efficiency and surface oxygen vacancy density. By tuning the surface and bulk oxygen vacancy density simultaneously, the PEC performance of the WO3 photoanode was increased by ca. 10 times, which illustrates the strength of delicate oxygen vacancy engineering in optimizing PEC devices.

The development of efficient CO2 reduction catalysts is a challenge for artificial photosynthesis. We report here graphitic carbon nitride (g-C3N4) embedded with transition metals as a new class of CO2 reduction catalysts in aqueous environment. Bimetallic (NiMn or NiCu)-C3N4 catalysts are found to be more efficient than their mono-metal counterparts due to metal synergistic effects, delivering high Faradic efficiency for CO evolution of around 90 % over a wide potential range (−0.6 V to −0.9 V vs. reversible hydrogen electrode) with a low overpotential of 0.39 V. The high activity originates from the atomic modification of g-C3N4 matrix with metal atoms. And g-C3N4 not only serves as a coordination framework but also provides a favorable local environment for CO2 reduction. The present study contributes to our understanding of structure and activity trends of this kind of materials, and points to strategies for the rational design of more efficient CO2 reduction catalysts.

We describe a new way to decompose one-electron orbitals of a molecule into atom-centered or fragment-centered orbitals by an approach that we call "maximal orbital analysis" (MOA). The MOA analysis is based on the corresponding orbital transformation (COT) that has the unique mathematical property of maximizing any sub-trace of the overlap matrix, in Hilbert metric sense, between two sets of nonorthogonal orbitals. Here, one set comprises the molecule orbitals (Hartree-Fock, Kohn-Sham, complete-active-space, or any set of orthonormal molecular orbitals), the other set comprises the basis functions associated with an atom or a group of atoms. We show in prototypical molecular systems such as a water dimer, metal carbonyl complexes, and a mixed-valent transition metal complex, that the MOA orbitals capture very well key aspects of wavefunctions and the ensuing chemical concepts that govern electronic interactions in molecules. © 2019 Wiley Periodicals, Inc.

Design of fast, efficient electrocatalysts for energy production and energy utilization requires a systematic approach to predict and tune the energetics of reaction intermediates and the kinetic barriers between them as well as to tune reaction conditions (e.g., concentration of reactants, acidity of the reaction medium, and applied electric potential). Thermodynamics schemes based on the knowledge of pKa values, hydride donor ability, redox potentials, and other relevant thermodynamic properties have been demonstrated to be very effective for exploring possible reaction pathways. We seek to identify high-energy intermediates, which may represent a catalytic bottleneck, and low-energy intermediates, which may represent a thermodynamic sink. In this study, working on a well-established Ni-based bioinspired electrocatalyst for H2 production, we performed a detailed kinetic analysis of the catalytic pathways to assess the limitations of our current (standard state) thermodynamic analysis with respect to pre...

Background Though the Expanded Disability Status Scale (EDSS) is commonly used to assess disability level in relapsing-remitting multiple sclerosis (RRMS), the criteria defining disability progression are used for patients with a wide range of baseline levels of disability in relatively short-term trials. As a result, not all EDSS changes carry the same weight in terms of future disability, and treatment benefits such as decreased risk of reaching particular disability milestones may not be reliably captured. The objectives of this analysis are to assess the probability of confirmed disability worsening to specific EDSS milestones (i.e., EDSS scores ≥3.0, ≥4.0, or ≥6.0) at 288 weeks in the Tysabri Observational Program (TOP) and to examine the impact of relapses occurring during natalizumab therapy in TOP patients who had received natalizumab for ≥24 months. Methods TOP is an ongoing, open-label, observational, prospective study of patients with RRMS in clinical practice. Enrolled patients were naive to natalizumab at treatment initiation or had received ≤3 doses at the time of enrollment. Intravenous natalizumab (300 mg) infusions were given every 4 weeks, and the EDSS was assessed at baseline and every 24 weeks during treatment. Results Of the 4161 patients enrolled in TOP with follow-up of at least 24 months, 3253 patients with available baseline EDSS scores had continued natalizumab treatment and 908 had discontinued (5.4% due to a reported lack of efficacy and 16.4% for other reasons) at the 24-month time point. Those who discontinued due to lack of efficacy had higher baseline EDSS scores (median 4.5 vs. 3.5), higher on-treatment relapse rates (0.82 vs. 0.23), and higher cumulative probabilities of EDSS worsening (16% vs. 9%) at 24 months than those completing therapy. Among 24-month completers, after approximately 5.5 years of natalizumab treatment, the cumulative probabilities of confirmed EDSS worsening by 1.0 and 2.0 points were 18.5% and 7.9%, respectively (24-week confirmation), and 13.5% and 5.3%, respectively (48-week confirmation). The risks of 24- and 48-week confirmed EDSS worsening were significantly higher in patients with on-treatment relapses than in those without relapses. An analysis of time to specific EDSS milestones showed that the probabilities of 48-week confirmed transition from EDSS scores of 0.0–2.0 to ≥3.0, 2.0–3.0 to ≥4.0, and 4.0–5.0 to ≥6.0 at week 288 in TOP were 11.1%, 11.8%, and 9.5%, respectively, with lower probabilities observed among patients without on-treatment relapses (8.1%, 8.4%, and 5.7%, respectively). Conclusions In TOP patients with a median (range) baseline EDSS score of 3.5 (0.0–9.5) who completed 24 months of natalizumab treatment, the rate of 48-week confirmed disability worsening events was below 15%; after approximately 5.5 years of natalizumab treatment, 86.5% and 94.7% of patients did not have EDSS score increases of ≥1.0 or ≥2.0 points, respectively. The presence of relapses was associated with higher rates of overall disability worsening. These results were confirmed by assessing transition to EDSS milestones. Lower rates of overall 48-week confirmed EDSS worsening and of transitioning from EDSS score 4.0–5.0 to ≥6.0 in the absence of relapses suggest that relapses remain a significant driver of disability worsening and that on-treatment relapses in natalizumab-treated patients are of prognostic importance.

Charge separation among different crystal facets of a semiconductor has been observed experimentally, but the underlying reasons behind this phenomenon are unknown. In this work, the activation energies of carrier hopping and the mobility of electron/hole transport along seven low-index crystal orientations of bulk BiVO4 have been calculated using a small polaron model. The calculated mobility and our previous experimental results reveal that there is a parallel relationship between the carrier mobility along the crystal axis and the carrier preferred accumulation on the corresponding crystal facets. It is proposed that the mobility of electrons (or holes) along the crystal axis [hkl] might be essentially related to the charge separation among the indices of corresponding facets (hkl); namely, the mobility of electrons (or holes) along the crystal axis [hkl] is the largest among all possible crystal axes, and the photogenerated electrons (or holes) tend to be accumulated on the indices of the corresponding facet (hkl) when the surface factors like surface band bending, surface energetic differences, etc. are not considered.

Simulation of charge transport in organic semiconducting materials requires the development of strategies for very fast yet accurate estimation of electronic coupling matrix elements for electron transfer between organic molecules (transfer integrals, Hab). A well-known relation that is often exploited for this purpose is the approximately linear dependence of electronic coupling with respect to the overlap of the corresponding diabatic state wave functions for a given donor-acceptor pair. Here we show that a single such relation can be established for a large number of different π-conjugated organic molecules. In our computational scheme the overlap of the diabatic state wave function is simply estimated by the overlap of the highest singly occupied molecular orbital of donor and acceptor, projected on a minimum valence shell Slater-type orbital (STO) basis with optimized Slater decay coefficients. After calibration of the linear relation, the average error in Hab as obtained from the STO orbital overlap is a factor of 1.9 with respect to wave function-theory validated DFT calculations for a diverse set of π-conjugated organic dimers including small arenes, arenes with S, N, and O heteroatoms, acenes, porphins, and buckyballs. The crucial advantage of the scheme is that the STO orbital overlap calculation is analytic. This leads to speedups of 6 orders of magnitude with respect to reference DFT calculations, with little loss of accuracy in the regime relevant to charge transport in organics.

Introduction Au cours des dernieres annees, les etablissements de sante se sont dotes d’outils permettant d’informatiser tout ou partie de l’acte transfusionnel. Nous rapportons l’experience du CHU de Caen engagee en 2001 et 2014, et son impact au regard de la securite transfusionnelle. Materiel et methode L’application (Cursus-Demserv, societe Guyot Walser Informatique-GWI), en interface avec celle de l’etablissement francais du sang Normandie depuis 2014, permet de saisir les demandes d’examens immuno-hematologiques et d’en consulter les principaux resultats, de saisir les ordonnances de produits sanguins labiles et d’en assurer la tracabilite via les normes requises. Resultats et discussion Alors que l’application est utilisee dans la plupart des secteurs de soins de l’etablissement, sont notamment relevees l’appropriation rapide de l’outil par les medecins, sages-femmes et infirmiers, l’absence de difficultes techniques et l’assistance reguliere des responsables informatiques du CHU et de GWI, mais aussi une utilisation parfois non pertinente telles que la tracabilite informatique du PSL apres sa pose ou la redondance du groupe sanguin (GS) dans 2,8 % des pres de 9000 resultats de GS (au-dela de la deuxieme determination), tandis que l’impossibilite de reception electronique de l’ordonnance de PSL par l’EFS est consideree comme un defaut majeur par les prescripteurs. Conclusion Si le recours a une telle application permet de renforcer la securite transfusionnelle et singulierement le lien patient-PSL, elle implique une vigilance rapprochee aupres des professionnels afin d’optimiser son utilisation et sa maitrise. Aussi, en complement des dernieres publications, une evolution reglementaire est attendue afin de definir notamment la validite des resultats IH electroniques, les normes d’enregistrement et transfert d’un etablissement a l’autre de leurs comptes-rendus et l’evolution informatique des bonnes pratiques et des composants du dossier transfusionnel du patient.