Theoretical study of the dynamics, stereodynamics and microscopic mechanism of the O(1D) + CH4(X1A 1) → OH(X2Π) + CH3(X2 A2'') reaction

A previously reported potential energy surface (PES) and a new barrierless PES (both based on ab initio data and describing the CH3 group as a pseudoatom) were used to study the O(1D)+CH4→OH+CH3 reaction with the quasiclassical trajectory (QCT) method. The new PES accurately reproduces the experimental rate constant values, in contrast to the previous PES. The QCT study was mainly performed at the relative translational energy (ET) resulting from the photodissociation of N2O at 193 nm (⟨ET⟩=0.403 eV), although the collision energy obtained from the photodissociation of O3 at 248 nm (⟨ET⟩=0.212 eV) was also considered. Good agreement between theory and experiment was obtained for the OH vibrational populations and for the OH rotational populations for the v′⩾2 vibrational levels, while the rotational distributions for v′=0-1 are more excited than in the experiment. The QCT results at ET=0.403 eV satisfactorily reproduce the experimental kk′ angular distribution of the state-specific channel OH(v′=4, N′=8) and the corresponding E′T distribution. For OH(v′=0, N′=5) the reproduction of these properties is poorer, especially for the E′T distribution. At 0.403 eV the contribution of the abstraction mechanism to the reaction mode is negligible and two insertion like mechanisms (with fast or slow elimination) are found to be predominant, as suggested experimentally. The discrepancies observed between the QCT and experimental results can be explained on the basis of the defective description of the insertion/slow elimination mechanism provided by the model

Practical guide to single-protein AFM nanomechanical spectroscopy mapping: insights and pitfalls as unraveled by all-atom MD simulations on immunoglobulin G

Atomic force microscopy is an invaluable characterization tool in almost every biophysics laboratory. However, obtaining atomic/sub-nanometer resolution on single proteins has thus far remained elusive - a feat long achieved on hard substrates. In this regard, nanomechanical spectroscopy mapping may provide a viable approach to overcome this limitation. By complementing topography with mechanical properties measured locally, one may thus enhance spatial resolution at the single-protein level. In this work, we perform all-atom molecular dynamics simulations of the indentation process on a single immunoglobulin G (IgG) adsorbed on a graphene slab. Our simulations reveal three different stages as a function of strain: a noncontact regime - where the mechanical response is linked to the presence of the water environment - followed by an elastic response and a final plastic deformation regime. In the noncontact regime, we are able to identify hydrophobic/hydrophilic patches over the protein. This regime provides the most local mechanical information that allows one to discern different regions with similar height/topography and leads to the best spatial resolution. In the elastic regime, we conclude that the Young modulus is a well-defined property only within mechanically decoupled domains. This is caused by the fact that the elastic deformation is associated with a global reorganization of the domain. Differences in the mechanical response are large enough to clearly resolve domains within a single protein, such as the three subunits forming the IgG. Two events, unfolding or protein slipping, are observed in the plastic regime. Our simulations allow us to characterize these two processes and to provide a strategy to identify them in the force curves. Finally, we elaborate on possible challenges that could hamper the interpretation of such experiments/simulations and how to overcome them. All in all, our simulations provide a detailed picture of nanomechanical spectroscopy mapping on single proteins, showing its potential and the challenges that need to be overcome to unlock its full potentialJ.G.V. acknowledges funding from a Marie Sklodowska-Curie Fellowship within the Horizon 2020 framework (Grant No. DLV-795286) and the Swiss National Science Foundation (Grant No. CRSK-2 190731/1). R.P. acknowledges support from the Spanish MINECO (Grant No. MAT2017-83273-R) and from the Ministerio de Ciencia e Innovación (MICINN) through the “María de Maeztu” Programme for Units of Excellence in R&D (Grant No. CEX2018-000805-M). R.G. acknowledges funding from the MICINN (Grant No. PID2019-106801GB-I00) and Comunidad de Madrid Grant No. S2018/NMT-4443 (Tec4Bio-CM). We thankfully acknowledge the computer resources, technical expertise, and assistance provided by the Red Española de Supercomputación (RES) at the Minotauro and CTE-Power9 supercomputers (BSC, Barcelona). We thank Dr. Alejandro Martín-González for fruitful discussion

Influence of collision energy on the dynamics of the reaction O(1D) + CH4(X1A 1) → OH(X2Π) + CH3(X2 A2'')

We studied the effects of collision energy (ET) on the dynamics of the title reaction using the quasiclassical trajectory method on an analytical triatomic potential energy surface we had derived for this system. We compared the dependence of the scalar and two-vector properties of the reaction on ET with experimental data and obtained a quite good agreement. The results can be explained in terms of the coexistence of two microscopic reaction mechanisms: insertion and abstraction. The former mechanism is the most important one, although the contribution of the latter increases with ET

A importância dos meios de comunicação na promoção do direito à educação e à informação

O direito à educação e à informação são direitos fundamentais em democracia. Saber se os direito à educação e à informação e ao conhecimento se concretizam pela consagração constitucional do direito à educação e como é possível encontrá-lo consagrado, quer ao nível do direito interno dos Estados quer ao nível do direito da União Europeia é hoje da maior pertinência, com os direitos fundamentais na agenda política. O objetivo desta análise é demonstrar que o papel da comunicação social é crucial, e que a UE promove ativamente a educação, investigação e inovação. Estas são as vias para promover o desenvolvimento com base no crescimento do emprego e da coesão social. Os meios de comunicação social podem dar um contributo fundamental para enfrentar problemas importantes ligados ao crescimento económico e este vector vem mesmo consagrado no âmbito da estratégia global do programa Europa 2020. Na dimensão nacional portuguesa, o direito à educação e informação é apresentado como um direito cultural da Constituição. Já no direito de vertente europeia, o direito à educação surge em protocolo da Convenção Europeia dos Direitos do Homem de 1950 e é consagrado na Carta dos Direitos Fundamentais da União Europeia. Em qualquer dos casos há uma dimensão positiva neste direito que envolve a intervenção dos Estados, e os meios de comunicação social podem ter um papel relevante neste âmbito. Atendendo aos pressupostos e objetivos delineados acima, e considerando a natureza embrionária deste estudo, foi desenhada uma metodologia que aborda a revisão da literatura sobre os vários temas abordados, com especial enfoque na questão da educação e informação. Dedutivamente, será assim possível inferir o contributo do direito interno e europeu bem como da comunicação social para a concretização deste desiderato. O estado da arte, de pendor teórico-académico, será consolidado através da interpretação normativa sistemática e metodologicamente selecionada dos textos legais e de textos informativos emanados pelos meios de comunicação

Digitalisation as Support in Competences Acquisition: Experiences at the Faculty of Business Administration and Management

[EN] This work presents the design of tasks in two courses at the Faculty of Business Administration and Management between 2020–2021. Because on-campus learning was limited, the tasks were designed to enable students to use digital tools. The learning outcomes were defined to ensure that students acquired both STEAM and soft competences. The STEAM competences in these subjects focused on developing curiosity (S: science), using technology (T), solving problems (E: engineering) and communicating in a visual manner (A: arts). In the first course, the task, which was implemented across two lessons, required the students to review a service. The students used digital tools to trace the customer journey, including pain points (negative opinions about the experience) users indicated, solutions to address those pain points and the main challenges involved in the solutions’ implementation. The use of digital tools added the technology competence to the competences students had already acquired in previous years (science, engineering, arts). In the second course, students worked on their bachelor’s degree theses, which they will be required to present both orally and in writing to three professors of the faculty. The task designed in this subject involved a screencast video produced by each student. Each student’s video was required to follow the format of the actual presentation of his or her thesis. This task added the technology and arts competences to the competences they had acquired in previous courses (science and engineering). This paper presents the results obtained from the two courses. These include the evaluation of learning outcomes in relation to previous years, the advantages and disadvantages of the tools selected in each subject and improvements to be incorporated in future years.This paper was written as part of two innovation and educational improvement projects (PIME) with the support of the Universitat Politècnica de València (Institute of Educational Sciences, ICE). The first project, entitled ‘Applying STEAM strategies in the areas of social sciences and arts through service-learning activities’, is coordinated by Professor María deMiguel-Molina. The second project, entitled ‘Infographics: Using ICT in the visual and creative representation of teaching content’, is coordinated by Professor María-Angeles Carabal-Montagud.Miguel Molina, MBD.; Miguel Molina, MRD.; Catalá Pérez, D.; García Ortega, B. (2022). Digitalisation as Support in Competences Acquisition: Experiences at the Faculty of Business Administration and Management. En Proceedings INNODOCT/21. International Conference on Innovation, Documentation and Education. Editorial Universitat Politècnica de València. 57-64. https://doi.org/10.4995/INN2021.2021.13357576

Role of the LPA1 receptor in mood and emotional regulation

Depression is a debilitating psychiatric condition characterized by anhedonia and behavioural despair among others symptoms. Despite the high prevalence and devastating impact of depression, underlying neurobiological mechanisms of mood disorders are still not well known. Regardless its complexity, central features of this disease can be modelled in rodents in order to better understand the potential mechanisms underlying. On the other hand, the lack of LPA1 receptor compromises the morphological and functional integrity of the limbic circuit and the neurogenesis in hippocampus, induces cognitive alterations on hippocampal-dependent tasks and dysfunctional coping of chronic stress, provokes exaggerated endocrine responses to emotional stimuli and impairs adaptation of the hypothalamic-pituitary-adrenal axis after chronic stress. Factors, which all have been related with depression. Here, we sought to establish the involvement of the LPA1 receptor in regulation of mood and emotion. To this end, in wild-type and maLPA1-null mice active coping responses to stress were examined using the forced swimming test (FST). To assess hedonic behaviour saccharine preference test and female urine sniffing test were used. Our data indicated that the absence of the LPA1 receptor significantly affected to coping strategies. Thus, while null mice displayed less immobility than wt in FST, exhibited more climbing and less swimming behaviour, responses that could be interpreted as an emotional over-reaction (i.e., a panic-like response) to stress situations. Concerning hedonic behaviour, the lack of the LPA1 receptor diminished saccharin preference and female urine sniffing time. Overall, these data supports the role of LPA1 receptor in mood and emotional regulation. Specially, the lack of this receptor induced emotional dysregulation and anhedonic behaviour, a core symptom of depression.Universidad de Málaga, Campus de Excelencia Andalucía Tech. Andalusian Regional Ministries of Economy, Innovation, Science and Employment (SEJ-1863; CTS643) and of Health (PI-0234-2013; Nicolas Monardes Programme), MINECO (PSI2013-44901-P) and National Institute of Health Carlos III (Sara Borrel)

Uterine sarcomas: clinical practice guidelines for diagnosis, treatment, and follow-up, by Spanish group for research on sarcomas (GEIS)

Adenosarcoma; Guidelines; Uterine sarcomaAdenosarcoma; Pautas; Sarcoma uterinoAdenosarcoma; Pautes; Sarcoma uteríUterine sarcomas are very infrequent and heterogeneous entities. Due to its rarity, pathological diagnosis, surgical management, and systemic treatment are challenging. Treatment decision process in these tumors should be taken in a multidisciplinary tumor board. Available evidence is low and, in many cases, based on case series or clinical trials in which these tumors have been included with other soft tissue sarcoma. In these guidelines, we have tried to summarize the most relevant evidence in the diagnosis, staging, pathological disparities, surgical management, systemic treatment, and follow-up of uterine sarcomas

Application of electric fields to clean ultrafiltration membranes fouled with whey model solutions

In this work, the effectiveness of electric fields to clean two ZrO2 TiO2 ultrafiltration (UF) membranes fouled with three types of whey model solutions was investigated. Membranes tested had different molecular weight cut-offs (MWCOs) (15 and 50 kDa). Whey model solutions consisted of aqueous solutions of bovine serum albumin (BSA) at 10 g/L, a mixture of BSA (10 g/L) and CaCl2 (1.65 g/L) and whey protein concentrate (WPC) (total protein content 45%) solutions at different concentrations (22.2, 33.3 and 150.0 g/L). The hydraulic cleaning efficiency (HCE) achieved by means of the application of the electric fields was evaluated as a function of the membrane MWCO and the operating conditions of the cleaning technique (applied potential, temperature of the cleaning solution and concentration of NaCl). The results demonstrated that the presence of NaCl favoured the removal of protein deposits on the membrane layer. On the other hand, the higher the temperature of the cleaning solution and the applied potential were, the higher HCE was achieved. Regarding the membrane MWCO, the permselective properties of the 15 kDa membrane were completely recovered after the cleaning procedure by electric field for all the feed fouling solutions tested, whereas this technique could not completely remove the protein deposits on the 50 kDa membrane when BSA solutions were used as feed.The authors of this work wish to gratefully acknowledge the financial support from the Spanish Ministry of Science and Innovation through the project CTM2010-20186 and the company MAGNETO Special Anodes B.V. for supplying the Ti-Ir electrode.Corbatón Báguena, MJ.; Alvarez Blanco, S.; Vincent Vela, MC.; Ortega Navarro, EM.; Pérez-Herranz, V. (2016). Application of electric fields to clean ultrafiltration membranes fouled with whey model solutions. Separation and Purification Technology. 159:92-99. https://doi.org/10.1016/j.seppur.2015.12.039S929915

Simulating high-pressure surface reactions with molecular beams

Using a reactive molecular beam with high kinetic energy ($E_{kin}$) it is possible to speed gas-surface reactions involving high activation barriers ($E_{act}$), which would require elevated pressures ($P_0$) if a random gas with a Maxwell-Boltzmann distribution is used. By simply computing the number of molecules that overcome the activation barrier in a random gas at $P_0$ and in a molecular beam at $E_{kin}$=$E_{act}$, we establish an $E_{kin}$-$P_0$ equivalence curve, through which we postulate that molecular beams are ideal tools to investigate gas-surface reactions that involve high activation energies. In particular, we foresee the use of molecular beams to simulate gas surface reactions within the industrial-range ($>$ 10 bar) using surface-sensitive Ultra-High Vacuum (UHV) techniques, such as X-ray photoemission spectroscopy (XPS). To test this idea, we revisit the oxidation of the Cu(111) surface combining O$_2$ molecular beams and XPS experiments. By tuning the kinetic energy of the O$_2$ beam in the range 0.24-1 eV we achieve the same sequence of surface oxides obtained in Ambient Pressure Photoemission (AP-XPS) experiments, in which the Cu(111) surface was exposed to a random O$_2$ gas up to 1 mbar. We observe the same surface oxidation kinetics as in the random gas, but with a much lower dose, close to the expected value derived from the equivalence curve

A relação entre do direito à educação e a comunicação no Estado de Direito

Tem o direito à educação como direito fundamental acompanhado na comunicação a evolução do Estado democrático? É possível encontrar o direito à educação consagrado quer ao nível do direito interno dos Estados, nos textos constitucionais, quer ao nível do direito internacional seja em organizações gerais, como as Nações Unidas (ONU), ou regionais, como a União Europeia (UE). A faceta de consagração foi já conseguida. Mas será essa vertente jurídica suficiente e, mais ainda, resultará ela clara na comunicação que chega ao cidadão comum? No caso específico nacional da Constituição da República Portuguesa de 1976 o direito à educação é apresentado como uma liberdade e também como um direito cultural, inserido nos direitos económicos, sociais e culturais. Já no direito internacional mundial, o direito à educação surge presentemente como um dos objectivos da Agenda 2030 da ONU, e é consagrado na União Europeia nos textos dos tratados institutivos e na Carta dos Direitos Fundamentais da União Europeia. No âmbito da ONU, os 17 Objetivos de Desenvolvimento Sustentável com 169 metas adoptadas em 2015 demonstram a escala desta Agenda universal a concretizar até 2030. No Objetivo 4 vem Assegurar a educação inclusiva, equitativa e de qualidade, e promover oportunidades de aprendizagem ao longo da vida para todos. O direito à educação, bem como o direito à formação profissional e contínua – a long life education – merecem a atenção de documentos recentes da União Europeia que, sem terem a dignidade de actos legislativos, moldam lentamente a orientação dos Estados-Membros no seu desempenho e são veículos de comunicação das linhas de acção da UE. O direito à educação como direito fundamental é ele próprio um veículo de consagração dos direitos fundamentais no seu todo. O desenvolvimento de uma política de sensibilização e educação do público em matéria de direitos fundamentais pelos Estados e organizações internacionais que tenham uma prática nesta matéria, permite grandes conquistas no domínio dos direitos fundamentais, que devem passar pela publicitação. Valorizado, então, pela União Europeia, o direito à educação surge como relevante nas mais variadas matérias. O sistema de ensino, desde a primeira infância ao ensino superior, será responsável por manter as competências (conhecimentos, aptidões e atitudes) essenciais ao exercício dos ideais democráticos. O valor do Estado de direito mantém-se. Mas verifica-se que, nele, a concretização do direito à educação não está ainda alcançado na sua plenitude. A ideia do Estado de direito é uma fonte para os princípios gerais de direito de tutela jurisdicional daí decorrentes que vigoram nos ordenamentos jurídicos dos Estados da União Europeia de hoje; nem sempre expresso é um princípio inspirador mas resulta como denominador comum que igualmente se encontra presente nas tradições constitucionais comuns aos Estados-Membros. E será também pela política da educação e formação que se manterão os valores comuns e os princípios gerais do direito. O foco de intervenção do Estado e da comunidade internacional constituiu ainda uma necessidade e prioridade. Este estudo pretende debruçar-se sobre os documentos legislativos que consagram a questão no sentido de verificar a preocupação com a concretização deste direito. De pendor teórico académico, é consolidado através da interpretação normativa sistemática e metodologicamente selecionada dos textos legais nacionais, internacionais e do direito da União Europeia. A análise dos progressos alcançados historicamente rumo aos objectivos de consolidação do direito à educação levam à recomendação dos Estados, na sua vertente interna e como membros de organizações internacionais, que valorizem a educação como veículo de comunicação dos valores democráticos