Synthesis of b-substituted alanines via Michael addition of nucleophiles to dehydroalanine derivatives

Several b-substituted alanines are synthesised in high yields by a Michael addition of nucleophiles to N-acyl,N-tert-butyloxycarbonyl-dehydroalanine methyl ester, using mild reaction conditions and simple work-up procedures. The same method can be applied to dipeptides containing dehydroalanine

High yielding synthesis of dehydroamino acid and dehydropeptide derivatives

By using a dimethylaminopyridine (DMAP) catalysed reaction of b-hydroxyamino acid derivatives with tert-butylpyrocarbonate [(Boc)2O], dehydroamino acid derivatives are obtained in high yields. The same methodology applied to dipeptides with a b-hydroxyamino acid residue gives the corresponding dipeptides with a dehydroamino acid residue

Michael addition of thiols, carbon nucleophiles and amines to dehydroamino acid and dehydropeptide derivatives

Michael additions of nitrogen heterocycles, thiols, carbon nucleophiles and amines to dehydroalanine derivatives, including a glycyldehydroalanine peptide, were performed in fair to good yields. Dehydroaminobutyric acid derivatives reacted only with the stronger nucleophiles but in considerably lower yields and often no reaction was observed with the corresponding dehydrophenylalanine derivatives. When a tosyl group was bonded to the nitrogen atom of the dehydroamino acid, in some cases the addition product underwent elimination of this group and yielded the corresponding b-substituted derivative of the a,b-dehydroamino acid. Addition of some b- dicarbonyl compounds led to formation of products to which the structure of a,a-disubstituted cyclic amino acid derivatives was assigned

Clarifying changes in student empathy throughout medical school: a scoping review

Despite the increasing awareness of the relevance of empathy in patient care, some findings suggest that medical schools may be contributing to the deterioration of students' empathy. Therefore, it is important to clarify the magnitude and direction of changes in empathy during medical school. We employed a scoping review to elucidate trends in students' empathy changes/differences throughout medical school and examine potential bias associated with research design. The literature published in English, Spanish, Portuguese and French from 2009 to 2016 was searched. Two-hundred and nine potentially relevant citations were identified. Twenty articles met the inclusion criteria. Effect sizes of empathy scores variations were calculated to assess the practical significance of results. Our results demonstrate that scoped studies differed considerably in their design, measures used, sample sizes and results. Most studies (12 out of 20 studies) reported either positive or non-statistically significant changes/differences in empathy regardless of the measure used. The predominant trend in cross-sectional studies (ten out of 13 studies) was of significantly higher empathy scores in later years or of similar empathy scores across years, while most longitudinal studies presented either mixed-results or empathy declines. There was not a generalized international trend in changes in students' empathy throughout medical school. Although statistically significant changes/differences were detected in 13 out of 20 studies, the calculated effect sizes were small in all but two studies, suggesting little practical significance. At the present moment, the literature does not offer clear conclusions relative to changes in student empathy throughout medical school.info:eu-repo/semantics/publishedVersio

Long-term stability of a non-adapted aerobic granular sludge process treating fish canning wastewater associated to EPS producers in the core microbiome

The tolerance of aerobic granular sludge (AGS) to variable wastewater composition is perceived as one of its greatest advantages compared to other aerobic processes. However, research studies select optimal operational conditions for evaluating AGS performance, such as the use of pre-adapted biomass and the control of wastewater composition. In this study, non-adapted granular sludge was used to treat fish canning wastewater presenting highly variable organic, nutrient and salt levels over a period of ca. 8 months. Despite salt levels up to 14 g NaCl L−1, the organic loading rate (OLR) was found to be the main factor driving AGS performance. Throughout the first months of operation, the OLR was generally lower than 1.2 kg COD m−3 day−1, resulting in stable nitrification and low COD and phosphorous levels at the outlet. An increase in OLR up to 2.3 kg COD m−3 day−1 disturbed nitrification and COD and phosphate removal, but a decrease to average values between 1 and 1.6 kg COD m−3 day−1 led to resuming of those processes. Most of the bacteria present in the AGS core microbiome were associated to extracellular polymeric substances (EPS) production, such as Thauera and Paracoccus, which increased during the higher OLR period. Ammonium-oxidizing bacteria (AOB) and nitrite-oxidizing bacteria (NOB) species were detected in AGS biomass; while AOB were identified throughout the operation, NOB were no further identified after the period of increased OLR. Different polyphosphate-accumulating organisms (PAOs) were detected along the process: Candidatus Accumulibacter, Tetrasphaera and Gemmatimonas. A non-adapted granular sludge was able to treat the fish canning wastewater and to tolerate salinity fluctuations up to 14 g L−1. Overall, a high microbial diversity associated to EPS producers allowed to preserve bacterial groups responsible for nutrients removal, contributing to the adaptation and long-term stability of the AGS system.info:eu-repo/semantics/publishedVersio

High carbon load in food processing industrial wastewater is a driver for metabolic competition in aerobic granular sludge

The Supplementary Material for this article can be found online at: https://www.frontiersin.org/articles/10.3389/fenvs.2021.735607/ full#supplementary-materialAerobic granular sludge (AGS) processes are among the most robust wastewater treatments. One of their greatest advantages is related to the granules multi-layered structure, which creates a protective barrier against organic shock loads and variable wastewater composition, particularly attractive for the treatment of industrial wastewater. However, when treating a wastewater with variable and complex composition, the difficulty in identifying factors that most affect a specific biological process increases. In this study, the effect of organic loading rate (OLR), namely carbon content, on nitrification in an AGS process treating fish canning wastewater was investigated. Besides process performance, also biomass structural changes, and microbial community composition were analysed. Reactor operation lasted for 107 days and was divided in three phases during which different OLR and C/N ratios were applied. A higher OLR was applied during the first two phases (ca. 1.1 and 1.5 kg COD m3 day1, respectively) compared to the third phase (between 0.12 and 0.78 kg COD m3 day1) and the C/N ratios also varied (ca. 4.4, 7.8, and 2.9, respectively). Throughout the operation, COD concentration in the outlet was lower than 100 mg O2 L1. Nitrification was inhibited during the second phase and recovered afterwards. Principal component analysis (PCA) of quantitative image analysis (QIA) and performance data allowed to distinguish process changes over the three operational phases. During the first two phases, the decrease in the biomass robustness occurred, but recovered during the last phase, indicating that the high content of organic matter had possibly an effect on the aerobic granules structural characteristics. The composition of the AGS microbiome did not change substantially after the end of the higher OLR periods. The main microbial diversity shifts were mostly associated to adaptation to higher or lower carbon availability. Bacteria and inferred enzymes associated to nitrogen and phosphorous removal were identified. Chryseobacterium, a bacterium with high metabolic versatility, was able to adapt to the organic shock load, becoming dominant over operation. Despite the variable composition of the fish canning wastewater, carbon was identified as the main driver for nitrification inhibition, while promoting changes in the physical characteristics and on the microbial community of granules.This work was supported by National Funds from FCT—Fundação para a Ciência e a Tecnologia, through the project GReAT-PTDC/BTA-BTA/29970/2017 (POCI-01-0145-FEDER-029970).We would like to thank the scientific collaboration of CBQF under the FCT project UIDB/50016/2020 and of CEB under the FCT project UIDB/04469/2020. We would like also to thank “A Poveira S.A.” (Póvoa de Varzim, Portugal) for providing the fish canning wastewater.info:eu-repo/semantics/publishedVersio

Towards customized footwear with improved comfort

A methodology enabling the customization of shoes for comfort improvement is proposed and assessed. For this aim, 3D printed graded density inserts were placed in one of the critical plantar pressure zones of conventional insoles, the heel. A semi-automated routine was developed to design the 3D inserts ready for printing, which comprises three main stages: (i) the definition of the number of areas with different mesh density, (ii) the generation of 2D components with continuous graded mesh density, and (iii) the generation of a 3D component having the same 2D base mesh. The adequacy of the mesh densities used in the inserts was previously assessed through compression tests, using uniform mesh density samples. Slippers with different pairs of inserts embedded in their insoles were mechanically characterized, and their comfort was qualitatively assessed by a panel of users. All users found a particular pair, or a set, of prototype slippers more comfortable than the original ones, taken as reference, but their preferences were not consensual. This emphasizes the need for shoe customization, and the usefulness of the proposed methodology to achieve such a goal.This work was funded by National Funds through FCT—Portuguese Foundation for Science and Technology, Reference UID/CTM/50025/2019 and UIDB/04436/2020, and Project FAMEST, Reference POCI-01-0247-FEDER-024529, co-financed by COMPETE2020 through PT2020 and FEDER

Anticipated adaptation difficulties to higher education: a study with first-year students

A qualidade da adaptação e sucesso no Ensino Superior está relacionada com características prévias dos estudantes, sendo que a literatura sugere diferenças de género, de tipos de estudos e de background familiar nos resultados dos estudantes. Além de variáveis socioculturais nesta determinação, variáveis mais sociocognitivas como as expetativas de resultado e a autoeficácia parecem influenciar as experiências adaptativas dos estudantes. Este estudo caracteriza as dificuldades antecipadas de adaptação de um grupo de 931 estudantes de uma universidade pública portuguesa, que acedem ao primeiro ano do Ensino Superior, uma semana antes do início das suas aulas. A análise das dificuldades antecipadas, avaliadas em três domínios – adaptação académica, integração social e autonomia -, é feita em função da área do curso frequentado, do sexo e do agrupamento em estudantes de primeira geração (pais sem frequência do Ensino Superior) ou estudantes de famílias com formação superior. Os resultados sugerem o impacto destas variáveis, sobretudo em termos da antecipação de dificuldades de integração social e autonomia, apontando para maiores dificuldades antecipadas nas mulheres, estudantes de primeira geração e estudantes de cursos de ciências sociais e humanas. Discutem-se implicações para a investigação e intervenção e contexto de Ensino Superior.The quality of adaptation and success in Higher Education is related to students’ entry characteristics, as literature suggests the impact of gender, the field of studies, and family background on students’ results. In addition to sociocultural factors, social-cognitive variables such as outcome expectations and self-efficacy also influence students’ adaptation experiences. This study characterizes the anticipated difficulties presented by a group of 931 first-year students matriculating at a Portuguese public university, one week before the beginning of classes. The analysis of anticipated difficulties, assessed in three major domains – academic adjustment, social integration, and autonomy -, is conducted concerning the field of studies, sex, and grouping in firstgeneration (students’ whose parents do not have a college education) or students from families with higher education backgrounds. Findings suggest the impact of these variables, namely regarding anticipated social integration and autonomy difficulties, suggesting higher anticipated difficulties by women, first-generation students, and students in social sciences and humanities courses. The results are discussed regarding implications for research and intervention in Higher Education

Probable Person-to-Person Transmission of Legionnaires’ Disease

Correspondence to the Editor.Legionnaires’ disease is an often severe form of pneumonia that is typically acquired by susceptible persons (e.g., elderly persons and smokers) through inhalation of aerosols that contain legionella species.1-4 A cluster of cases of this disease occurred in Vila Franca de Xira, Portugal, in 2014

Proof-of-Concept Study of Multifunctional Hybrid Nanoparticle System Combined with NIR Laser Irradiation for the Treatment of Melanoma

Supplementary Materials - available online at https://www.mdpi.com/article/10.3390/biom11040511/s1The global impact of cancer emphasizes the importance of developing innovative, effective and minimally invasive therapies. In the context of superficial cancers, the development of a multifunctional nanoparticle-based system and its in vitro and in vivo safety and efficacy characterization are, herein, proposed as a proof-of-concept. This multifunctional system consists of gold nanoparticles coated with hyaluronic and oleic acids, and functionalized with epidermal growth factor for greater specificity towards cutaneous melanoma cells. This nanoparticle system is activated by a near-infrared laser. The characterization of this nanoparticle system included several phases, with in vitro assays being firstly performed to assess the safety of gold nanoparticles without laser irradiation. Then, hairless immunocompromised mice were selected for a xenograft model upon inoculation of A375 human melanoma cells. Treatment with near-infrared laser irradiation for five minutes combined with in situ administration of the nanoparticles showed a tumor volume reduction of approximately 80% and, in some cases, led to the formation of several necrotic foci, observed histologically. No significant skin erythema at the irradiation zone was verified, nor other harmful effects on the excised organs. In conclusion, these assays suggest that this system is safe and shows promising results for the treatment of superficial melanoma.The authors would like to thank to Fundação para a Ciência e Tecnologia (FCT) for the essential financial support under the project’s references PTDC/BBB-BMC/0611/2012, UIDB/00645/2020, UIDB/04138/2020 and UIDP/04138/2020 as well as for the PhD fellowships SFRH/BD/148044/2019 and SFRH/BD/147306/2019.info:eu-repo/semantics/publishedVersio