Enzymatic functionalization of carbon-hydrogen bonds

The development of new catalytic methods to functionalize carbon–hydrogen (C–H) bonds continues to progress at a rapid pace due to the significant economic and environmental benefits of these transformations over traditional synthetic methods. In nature, enzymes catalyze regio- and stereoselective C–H bond functionalization using transformations ranging from hydroxylation to hydroalkylation under ambient reaction conditions. The efficiency of these enzymes relative to analogous chemical processes has led to their increased use as biocatalysts in preparative and industrial applications. Furthermore, unlike small molecule catalysts, enzymes can be systematically optimized via directed evolution for a particular application and can be expressed in vivo to augment the biosynthetic capability of living organisms. While a variety of technical challenges must still be overcome for practical application of many enzymes for C–H bond functionalization, continued research on natural enzymes and on novel artificial metalloenzymes will lead to improved synthetic processes for efficient synthesis of complex molecules. In this critical review, we discuss the most prevalent mechanistic strategies used by enzymes to functionalize non-acidic C–H bonds, the application and evolution of these enzymes for chemical synthesis, and a number of potential biosynthetic capabilities uniquely enabled by these powerful catalysts (110 references)

Catches in ghost-fishing octopus and fish traps in the northeastern Atlantic Ocean (Algarve, Portugal)

Ghost fishing is the term used to describe the continued capture of fish and other living organisms after a fisherman has lost all control over the gear. Traps may be lost for a variety of reasons including theft, vandalism, abandonment, interactions with other gear, fouling on the bottom (i.e., traps and ropes are caught on rocky substrate), bad weather, and human error (Laist, 1995). Annual trap loss can be as high as 20% to 50% of fished traps in some fisheries (Al-Masroori et al., 2004). Because lost traps can continue to fish for long periods, albeit with decreasing efficiency over time (e.g., Smolowitz, 1978; Breen, 1987, 1990; Guillory, 1993), ghost fishing is a concern in fisheries worldwide

Estimação em Pequenos Domínios com modelos que combinam Informação Seccional e Cronológica

O objectivo principal deste artigo consiste na proposta de um novo estimador para parâmetros de interesse em pequenos domínios com dados de nível área

Estimação jackknife ponderada do erro quadrático médio de predição do EBLUP temporal

A metodologia baseada na melhor predição linear empírica não enviesada (Empirical Best Linear Unbiased Prediction), consagrada com o acrónimo EBLUP, é muito utilizada na estimação de parâmetros para pequenos domínios. Apesar da relativa facilidade de dedução dos EBLUPs, mesmo num contexto de um modelo longitudinal, a medição da sua qualidade é um problema complexo devido à di culdade de estimação do erro quadrático médio de predição (EQMP) de tais preditores. Neste trabalho utiliza-se um estimador de parâmetros de interesse em pequenos domínios assistido pelo modelo temporal de Rao-Yu (Rao e Yu, 1994). O EBLUP temporal é apresentado e é revisitada a aproximação analítica assimptótica do EQMP do EBLUP temporal proposta por Rao e Yu (1994). Sob o modelo de Rao-Yu, é proposta uma metodologia jackknife ponderada para estimar o EQMP do EBLUP, desenvolvida a partir dos trabalhos de Chen e Lahiri (2008). Foi realizado um estudo por simulação com o objectivo de comparar o desempenho do estimador proposto com o obtido por via da aproximação analítica do EQMP

Addressing hospitalisations with non-error-free data by generalised SEIR modelling of COVID-19 pandemic

Mendes, J. M., & Coelho, P. S. (2021). Addressing hospitalisations with non-error-free data by generalised SEIR modelling of COVID-19 pandemic. Scientific Reports, 11(1), 1-20. [19617]. https://doi.org/10.1038/s41598-021-98975-wSuccessive generalisations of the basic SEIR model have been proposed to accommodate the different needs of the organisations handling the SARS-CoV-2 epidemic. These generalisations have not been able until today to represent the potential of the epidemic to overwhelm hospital capacity until today. This work builds on previous generalisations, including a new compartment for hospital occupancy that allows accounting for the infected patients that need specialised medical attention. Consequently, a deeper understanding of the hospitalisations rate and probability as well as of the recovery rates for hospitalised and non-hospitalised individuals is achieved, offering new information and predictions of crucial importance for the planning of the health systems and global epidemic response. Additionally, a new methodology to calibrate epidemic flows between compartments is proposed. We conclude that the two-step calibration procedure is able to recalibrate non-error-free data and showed crucial to reconstruct the series in a specific situation characterised by significant errors over the official recovery cases. The performed modelling also allowed us to understand how effective the several interventions (lockdown or other mobility restriction measures) were, offering insight for helping public authorities to set the timing and intensity of the measures in order to avoid the implosion of the health systems.publishersversionpublishe

Physiological roles of regulated Ire1 dependent decay

Inositol-requiring enzyme 1 (Ire1) is an important transducer of the unfolded protein response (UPR) that is activated by the accumulation of misfolded proteins in the endoplamic reticulum (ER stress). Activated Ire1 mediates the splicing of an intron from the mRNA of Xbp1, causing a frame-shift during translation and introducing a new carboxyl domain in the Xbp1 protein, which only then becomes a fully functional transcription factor. Studies using cell culture systems demonstrated that Ire1 also promotes the degradation of mRNAs encoding mostly ER-targeted proteins, to reduce the load of incoming ER "client" proteins during ER stress. This process was called RIDD (regulated Ire1-dependent decay), but its physiological significance remained poorly characterized beyond cell culture systems. Here we review several recent studies that have highlighted the physiological roles of RIDD in specific biological paradigms, such as photoreceptor differentiation in Drosophila or mammalian liver and endocrine pancreas function. These studies demonstrate the importance of RIDD in tissues undergoing intense secretory function and highlight the physiologic role of RIDD during UPR activation in cells and organisms.publishersversionpublishe

A heterogeneous age-related generalisation of the SEIR model

Mendes, J. M., & Coelho, P. S. (2023). The effect of non-pharmaceutical interventions on COVID-19 outcomes: A heterogeneous age-related generalisation of the SEIR model. Infectious Disease Modelling, 8(3), 742-768. https://doi.org/10.1016/j.idm.2023.05.009. Funding Information: This work was supported by national funds through FCT (Fundação para a Ciência e a Tecnologia) under the project UIDB/04152/2020 - Centro de Investigação em Gestão de Informação (MagIC)Successive generalisations of the basic SEIR model have been proposed to accommodate the different needs of the organisations handling the SARS-CoV-2 epidemic and the assessment of the public health measures adopted and named under the common umbrella of Non-Pharmaceutical Interventions (NPIs). So far, these generalisations have not been able to assess the ability of these measures to avoid infection by the SARS-CoV-2 and thus their contribution to contain the spread of the disease. This work proposes a new generalisation of SEIR model and includes a heterogeneous and age-related generation of infections that depends both on a probability that a contact generates the transmission of the disease and a contact rate. The results show (1) thanks to the universal wearing of facial coverings, the probability that a contact provokes the transmission of the disease was reduced by at least 50% and (2) the impact of the other NPI is so significant that otherwise Portugal would have gone into a non-sustainable situation of having 80% of its population infected in the first 300 days of the pandemic. This situation would have led to a number of deaths almost twenty times higher than the number that was actually recorded by December 26th, 2020. Moreover, the results suggest that even if the requirement of universal wearing of facial coverings was adopted sooner jointly with closing workplaces and resorting to teleworking would have postponed the peak of the incidence, altought the epidemic path would have result in a number of infections hardly managed by the National Health System. Complementary, results confirm that (3) the health authorities adopted a conservative approach on the criteria to consider an infected individual not infective any longer; and (4) the most effective NPIs and stringency levels either impacting on self-protection against infection or reducing the contacts that would eventually result in infection are, in decreasing order of importance, the use of Facial coverings, Workplace closing and Stay at home requirements.publishersversionpublishe

Educação e literacia sexual: representações de professores (estudo de caso)

A Lei n.º 60/2009 generalizou a Educação Sexual (ES) nas escolas do ensino básico e secundário. Os modelos de ES caracterizam diferentes posições perante a sexualidade, sejam socioeconómicas, profissionais ou religiosas. Hoje, a ES tem como desafio a promoção de competências, baseadas na responsabilidade e na autonomia, para usar o conhecimento e estimular o desenvolvimento pessoal. A capacidade de aplicar o conhecimento e as aptidões, para analisar, raciocinar e comunicar eficazmente, interpretar e resolver problemas em situações variadas é hoje indispensável. A ES deve seguir uma orientação baseada na literacia sexual ou ser um receituário de prevenção e saúde pública? Num estudo de caso, verificou-se que para os professores inquiridos a educação da sexualidade de crianças até aos 11/12 anos deve valorizar conhecimentos (gerais básicos) sob supervisão dos pais, complementada pela escola, em contexto estruturado, o que corresponde ao previsto no nível 1 do QEQ (EU, 2008). A partir dos 12 anos os professores inquiridos continuam a valorizar o papel educativo dos pais em relação à sexualidade, considerando, no entanto, que deve haver um certo grau de autonomia e responsabilidade por parte dos alunos, o que corresponde ao previsto no nível 2 do QEQ. Globalmente os professores inquiridos apontam para uma educação sexual baseada no modelo de formação pessoal e social, reforçando-se progressivamente a autonomia e a responsabilidade dos alunos para a literacia sexual

The Value of Design Thinking for PhD Students: A Retrospective Longitudinal Study

Doctoral studies are changing worldwide, with growing concerns about doctoral graduates' employability and ability to develop relevant links with industrial challenges. The present study aims examine the impact of Design Thinking skills on PhD students on their future academic and professional performance. Drawing on 7 years of pedagogical experimentation, we conducted a mixed methods longitudinal study to investigate the perceptions of students who attended a two-day Design Thinking workshop. Two questionnaires, with a total of 40 items measuring the quality and course impact dimensions, were given to 415 and 41 students, respectively. Finally, 12 students were chosen for in-depth interviews to learn more about how they applied their newly acquired design thinking skills in their research and work. Our findings show that developing Design Thinking skills impacts the professional lives of students of all fields of knowledge, ages, and stages of their PhD. The primary outcomes mentioned are associated with increased creative confidence and collaboration abilities. This study focuses on relevant dimensions for designing and delivering Design Thinking skills within doctoral programmes, as well as the impact of design thinking on the quality of PhD education and student employability opportunities. Doi: 10.28991/ESJ-2023-SIED2-02 Full Text: PD