Electrochemical Conversion of the Lignin Model Veratryl Alcohol to Veratryl Aldehyde Using Manganese(III)-Schiff Base Homogeneous Catalysts

Lignin and other colored structures need to be bleached after the Kraft process in the pulp industry. Development of environmentally-safe bleaching catalysts or electrocatalysts constitutes an attractive strategy for selective removal of lignin. Seven manganese(III)-complexes with Schiff base ligands 1–7 were synthetized and characterized by different analytical and spectroscopic techniques. The tetragonally elongated octahedral geometry for the manganese coordination sphere and the global µ-aquo dimeric structure were revealed by X-ray diffraction (XRD) studies for 1, Mn2L12(H2O)2(N(CN)2)2 (N(CN)2 = dicyanamide). Complexes 1–4 behave as more efficient peroxidase mimics as compared to 5–7. Electrochemical oxidation of the lignin model veratrylalcohol (VA) to veratrylaldehyde (VAH) is efficiently catalyzed by a type of dimanganese(III) complexes in a chlorine-free medium. The electrocatalytic reaction proceeds through the oxidation of chloride into hypochlorite at alkaline pH along with the formation of hydrogen from water as a subproductThis research was funded by Xunta de Galicia (GRC GI-1584-ED431C2018/13 Suprabioin Research Group, and MetalBIO Network ED431D 2017/01)S

Possession in Football: More Than a Quantitative Aspect – A Mixed Method Study

The aim of the present study was to identify and differentiate the factors that determine the possession times of successful and unsuccessful elite football teams, with the purpose of identifying a more effective possession model. For this, match corresponding to the round of eighth-finals, quarter-finals, semi-finals and final of the 2016 UEFA Euro France in which 2,636 offensive sequences occurred, were analyzed. Video recordings of matches were analyzed and coded post-event using systematic observation. The performance indicators recorded and analyzed were: phase; match period; type of start-up; interaction context; intention; field zone; possession time, passes, attack outcome; match status and final outcome. An ANOVA was performed to analyze data in order to study the influence of a set of variables. A Box–Cox transformation was applied on the variable explained to achieve normal conditions. A study of the main effects and significant interactions was also carried out, complemented with a set of predictions with the variables that were more significant. It is hypothesized that possession analysis from a mixed methods perspective will identify a more effective offensive playstyle. Results show how, in successful teams, possession time is influenced by: Type of start-up, intention and field zone. On the other hand, in unsuccessful teams, possession time is determined fundamentally by intention and match status. In terms of the results of the predictive models, in the case of successful teams, they will have longer possessions in the offensive zone with the score in favor and, in the defensive zone with a draw score, in both situations, initiated with the intention of progressing by means of a transition. For unsuccessful teams, possessions will be of longer duration in the defensive zone with a draw score, regardless of the type of start-up and, in the offensive zone, losing and initiating the play by means of a set ball action and winning by means of a transition. Results obtained in this work identify key factors that determine possession time in teams and allow to differentiate the possessions of successful and unsuccessful teams, identifying a more effective ball possession model. This information can be used to design a possession model with greater probabilities of success and increase the offensive performance of teams

Nutritional status and physical condition in active vs. sedentary elderly people

El objetivo del estudio fue conocer la relación entre el estado nutricional, la adherencia a la dieta mediterránea y el nivel de condición física de personas mayores. Participaron 168 personas mayores de 65 años (grupo control=84 personas activas y grupo experimental=84 personas sedentarias). La adherencia a la dieta mediterránea fue medida con el cuestionario MEDIS-FFQ, el nivel de práctica de actividad física mediante una pregunta creada a tal efecto, y las diferentes pruebas físicas con los instrumentos específicos. Los resultados revelaron que el 63.1% manifestó baja adherencia a la dieta mediterránea y el 34.5% alta, teniendo los sujetos sedentarios mayor adherencia que los activos (p≤0.05; 46.4% vs. 22.6%). Los sujetos activos tienen mejor condición física que los sedentarios (p≤0.001). Por tanto, la mayor parte de las personas mayores deben incrementar su adherencia a la dieta mediterránea y la práctica de actividad física como mecanismo de mejora de su saludThe objective of the study was to know the relationship between nutritional status, adherence to the Mediterranean diet and the level of physical displacement of older people. 168 people older than 65 years participated (control group = 84 active people and experimental group = 84 sedentary people). Adherence to the Mediterranean diet was measured with the MEDIS-FFQ questionnaire, the level of physical activity practice through a question created for that purpose, and the different physical tests with the specific instruments. The results revealed that 63.1% showed low adherence to the Mediterranean diet and 34.5% high, according to the sedentary subject’s greater adherence than the active ones (p≤0.05, 46.4% versus 22.6%). Active subjects have better physical income than sedentary people (p≤0.001). Therefore, most elderly people want to increase their adherence to the Mediterranean diet and the practice of physical activity as a mechanism to reduce their healt

Dark Triad Traits and Risky Behaviours: Identifying Risk Profiles from a Person-Centred Approach

Education and Child Studie

Rapporto tecnico sulla valutazione della biomassa ittioplanctonica mediante l'utilizzo del Multi Plankton Sampler (MPS)

Il piano di campionamento della campagna oceanografica BANSIC'14, condotta a bordo della N/O "URANIA" dal 22 Luglio al 9 Agosto 2014, lungo transetti sotto costa e a largo delle coste meridionali della Sicilia, ha avuto l’obiettivo generale dello studio delle relazioni tra le strutture oceanografiche a mesoscala (vortici verticali ed orizzontali, upwelling, etc.) e le strutture spaziali dei fenomeni biologici relativi ai primi anelli della catena trofica (zooplancton, distribuzione e abbondanza di larve di piccoli pelagici e grandi pelagici) (vedi Rapporto finale BANSIC 2014) per la stima dell’abbondanza dello stock riproduttore. E' una campagna di ricerca nell'ambito del WP3 del progetto SSD-Pesca, finanziato dal MIUR su fondi MISE, a supporto della pesca italiana nelle Regioni Obiettivo 1 e del progetto RITMARE (SP2_WP4_AZ2_UO04). Il campionamento ittioplanctonico è inserito anche nel piano di lavoro del progetto regionale MIPAF-FAO “MedSudMed” (“Assessment and Monitoring of the Fishery Resources and the Ecosystems in the Straits of Sicily”). Il campionamento dell’ittioplancton, durante questa campagna, oltre ai metodi tradizionali quali le reti di tipo Bongo, ha visto l'utilizzo del Multi Plankton Sampler (MPS) MultiNet. I campionatori ittioplanctonici hanno lo scopo di prelevare porzioni di mesozooplancton da un massimo di 100 m fino alla superficie, in quanto le uova di pesci pelagici possiedono una galleggiabilità tale che nonostante le turbolenze superficiali dell’acqua, un campionamento entro i primi metri restituisce un dato affidabile della distribuzione anche se alcune uova possono trovarsi a maggiore profondità (Ahlstrom, 1959). Il campionatore MPS consente, a differenza di altri strumenti, di prelevare la frazione di zooplancton d'interesse con diverse modalità di campionamento: orizzontale, verticale e obliquo e, allo stesso tempo, permette di campionare a differenti quote di profondità. Le informazioni così ottenute sono state utilizzate per valutare la variazione della biomassa ittioplanctonica, l'abbondanza e la composizione delle specie lungo gli strati della colonna d'acqua anche in relazione alle componenti oceanografiche. Grazie all'utilizzo di questo strumento è possibile validare e verificare alcune informazioni e acquisirne delle nuove sull’ecologia delle specie larvali e sul mesozooplancton, sul modo in cui queste si distribuiscono lungo la colonna d'acqua e sulle interazioni intra ed interspecifiche legate anche a fattori oceanografici. Ciò consente di ottenere maggiori informazioni e contribuire al miglioramento della comprensione della biologia e dell'ecologia delle specie rinvenute e, nel contempo, approfondire e migliorare le conoscenze sugli stadi di sviluppo di uova di specie ittiche che allo stadio embrionale sono ancora poco conosciuti

Salen-manganese complexes for controlling ROS damage: Neuroprotective effects, antioxidant activity and kinetic studies

A new manganese(III) complex [MnL1(DCA)(H2O)](H2O), 1, has been prepared using the chelating ligand N,N’-bis(2-hydroxy-3-methoxybenzylidene)-1,2-diaminopropane (H2L1), and characterized by different analytical and spectroscopic techniques. The tetragonally elongated octahedral geometry for the manganese coordination sphere was revealed by X-ray diffraction studies for 1. The antioxidant behavior of this complex and other manganese(III)-salen type complexes was tested through SOD and catalase probes, and through the study of their neuroprotective effects in SH-SY5Y neuroblastoma cells. In this human neuronal model, these model complexes were found to improve cell survival in an oxidative stress model. During studies aimed to getting a better understanding of the kinetics of the processes involved in this antioxidant behavior, an important effect on the solvent in the kinetics of reaction of the complexes with H2O2 was revealed that suggests a change in the mechanism of reaction of the complexes. The kinetic data in methanol and buffered aqueous solutions correlate well with the results of the test of catalase activity, thus showing that the rate determining step in the catalytic cycle corresponds to the initial reaction of the complexes with H2O2

Antibody–PROTAC conjugates enable HER2-dependent targeted protein degradation of BRD4

Targeting protein degradation with Proteolysis-Targeting Chimeras (PROTACs) is an area of great current interest in drug discovery. Nevertheless, although the high effectiveness of PROTACs against a wide variety of targets has been established, most degraders reported to date display limited intrinsic tissue selectivity and do not discriminate between cells of different types. Here, we describe a strategy for selective protein degradation in a specific cell type. We report the design and synthesis of a trastuzumab-PROTAC conjugate (Ab-PROTAC 3) in which E3 ligase-directed degrader activity is caged with an antibody linker which can be hydrolyzed following antibody–PROTAC internalization, releasing the active PROTAC and inducing catalytic protein degradation. We show that 3 selectively targets bromodomain-containing protein 4 (BRD4) for degradation only in HER2 positive breast cancer cell lines, while sparing HER2 negative cells. Using live cell confocal microscopy, we show internalization and lysosomal trafficking of the conjugate specifically in HER2 positive cells, leading to the release of active PROTAC in quantities sufficient to induce potent BRD4 degradation. These studies demonstrate proof-of-concept for tissue-specific BRD4 degradation, overcoming limitations of PROTAC selectivity, with significant potential for application to novel targets