Janus electrochemistry: asymmetric functionalization in one step

Janus structures represent an overwhelming member of materials with adaptable chemical and physical properties. Development of new synthesis routes has allowed the fabrication of Janus architectures with specific characteristics depending on the final applications. In the case of the membranes, the improvement of wet routes has been limited to the capillary effect, in which the solution can gradually penetrate through the membrane, avoiding a double modification different at each face of the membrane. In this work, we propose a new electrochemical methodology to circumvent the capillary limitation and obtain a double electrochemical functionalization in only one step in a controlled way. This innovative methodology has been validated using a tridirectional spectroelectrochemistry setup. Moreover, the information provided by this optical arrangement should be especially useful for the study of the different processes (ion transfer, assisted ion transfer, and electron transfer) that can take place at liquid/liquid interfaces. Janus electrochemistry allows us to modify the two faces of a free-standing single-walled carbon nanotube electrode in a single experiment. As proof of concept, the free-standing films have been functionalized with two different conducting polymers, polyaniline and poly(3-hexylthiophene), in one electrochemical experiment. According to the obtained results, this new electrochemical methodology will open new gates for the design and functionalization of Janus materials.Ministerio de Economía y Competitividad (Grants CTQ2014-61914-EXP, CTQ2014-55583-R, TEC2014-51940-C2-2R, and CTQ2015-71955-REDT) and Junta de Castilla y León (Grant BU033-U16

Spectroelectrochemical monitoring of contaminants during the electrochemical filtration process using free-standing carbon nanotube filters

Ministerio de Economía y Competitividad (CTQ2014-61914-EXP, CTQ2014-55583-R, TEC2017-85059-C3-2-R, CTQ2015-71955-REDT) and Junta de Castilla y León (BU033-U16

Silver nanoparticles/free-standing carbon nanotube Janus membranes

Janus materials are attracting intense interest due to their exceptional possibilities in the design of structures with specific properties. In this work, Janus structures were constructed by the functionalization of free-standing single-walled carbon nanotube (FS-SWCNT) membranes with silver nanoparticles (AgNPs) electrodeposited on one face of the free-standing structure. The modification of the FS-SWCNT films with AgNPs was carried out from an ionic liquid solution, a green and environmentally friendly procedure. Before the functionalization of the free-standing membranes, the optimal electrodeposition conditions of AgNPs from an ionic liquid in different carbon substrates were studied. We demonstrate by UV–vis spectroelectrochemistry that the functionalization of the FS-SWCNT membranes on only one face is achieved, remaining unmodified the other face, as SEM images confirm. Moreover, the morphology of AgNPs, and, consequently, the properties of the Janus structures strongly depend on the specific electrodeposition conditions selected, determining their future applicability.Ministerio de Economía y Competitividad (CTQ2014-61914-EXP, CTQ2014-55583-R, TEC2014-51940-C2-2R, CTQ2015-71955-REDT) and Junta de Castilla y León (BU033-U16)Ministerio de Economía y Competitividad (CTQ2014-61914-EXP, CTQ2014-55583-R, TEC2014-51940-C2-2R, CTQ2015-71955-REDT) and Junta de Castilla y León (BU033-U16

Effects of regularly consuming dietary fibre rich soluble cocoa products on bowel habits in healthy subjects: a free-living, two-stage, randomized, crossover, single-blind intervention

Abstract Background Dietary fibre is both preventive and therapeutic for bowel functional diseases. Soluble cocoa products are good sources of dietary fibre that may be supplemented with this dietary component. This study assessed the effects of regularly consuming two soluble cocoa products (A and B) with different non-starch polysaccharides levels (NSP, 15.1 and 22.0% w/w, respectively) on bowel habits using subjective intestinal function and symptom questionnaires, a daily diary and a faecal marker in healthy individuals. Methods A free-living, two-stage, randomized, crossover, single-blind intervention was carried out in 44 healthy men and women, between 18-55 y old, who had not taken dietary supplements, laxatives, or antibiotics six months before the start of the study. In the four-week-long intervention stages, separated by a three-week-wash-out stage, two servings of A and B, that provided 2.26 vs. 6.60 g/day of NSP respectively, were taken. In each stage, volunteers' diet was recorded using a 72-h food intake report. Results Regularly consuming cocoa A and B increased fibre intake, although only cocoa B significantly increased fibre intake (p < 0.001) with respect to the non-cocoa stage. No changes in body weight were observed in either of the 4 week interventions. With cocoa product B, the number of daily bowel movements increased (p = 0.002), the frequency of having a bowel movement once a day increased (p = 0.009), the time to have a bowel movement was lower (p = 0.016) as well as the feeling of constipation (p = 0.046) without inducing adverse gastrointestinal symptoms, only flatulence increased (p = 0.019). Conclusions Regular consumption of the cocoa products increases dietary fibre intake to recommended levels and product B improves bowel habits. The use of both objective and subjective assessments to evaluate the effects of food on bowel habits is recommended.Projects AGL2007-64042 and Consolider-Ingenio (CSD2007-00063) from the Spanish Ministry of Science and Innovation also acknowledged. S.M.-L. is a JAE-Predoc fellow of CSIC Programme "Junta para la Ampliación de Estudios" co-funded by the European Social Fund (ESF). M.G.-J. is a predoctoral fellow of the Spanish Ministry of Science and Innovation. A.F.-E. was a FINNOVA fellow also cofinanced by CSIC and the ESF.Peer Reviewe

Polymer materials derived from the SEAr reaction for gas separation applications

Producción CientíficaA set of linear polymers were synthesized utilizing an electrophilic aromatic substitution reaction (SEAr) between biphenyl and ketone containing electron-withdrawing groups (isatin, IS; N-methylisatin, MeIS; and 4,5-diazafluoren-9-one, DF). Optimization of the polycondensation reaction was made to obtain high molecular weight products when using DF, which has not previously been used for linear polymer synthesis. Due to the absence of chemically labile units, these polymers exhibited excellent chemical and thermal stability. Linear SEAr polymers were blended with porous polymer networks derived from IS and MeIS, and both neat/mixed materials were tested as membranes for gas separation. The gas separation properties of both pristine polymers and mixed matrix membranes were good, showing some polymer membrane CO2 permeability values higher than 200 barrer

Modelling the mid-late Holocene evolution of the Huelva Estuary and its human colonization, South-Western Spain

The major changes that occurred in the southwestern estuaries of the Spanish Atlantic coast during the last 6500 yr BP were simultaneous to human settlement and therefore the understanding of their coastal evolution will help interpreting human patterns in these areas. The study of the morpho-sedimentary features of new outcrops appearing in the middle sector of Saltés Island (Huelva Estuary, Spain) has been used to develop a model to understand the complex evolution of sand barriers than can be applied to similar inlets along the Atlantic Iberian coast. The first human settlements (6000–4000 yr BP) in the early Huelva Estuary (Tinto and Odiel rivers) were located in the ancient coastal banks or in the nearby hills. From 4000 yr BP onwards, the estuarine sediments started to emerge as sand barriers and chenier plains, prograding towards the mouth. As the littoral strands stabilized morphologically, they were colonized by human settlements in successive periods, the oldest inland (Almendral) and more recent outward (Cascajera). The study of the upper sedimentary layers of La Cascajera barrier display a tempestitic sequence of landward progradational washover-fans. The calibrated and modelled AMS dates in marine shells provide a storminess time range between the second half of first century BCE and the entire first century CE. Sedimentary records are useful to evaluate environmental changes, either from natural or anthropogenic causes, such as global and climate change. The interrelationship between the archaeological findings (mainly salting fish factories and old ports) and the morpho sedimentary evolution at the mouth of the Tinto and Odiel rivers allows us to highlight not only the Huelva Estuary's dynamics evolution, but also the possible regional patterns of human habitation from the beginning of the present sea-level highstand (middle Holocene).Ministerio de Economía y Competitividad CGL2010-15810/BTEEuropean Union (UE) EU Excellence Project of the Andalusia Board SEJ-477

Multidimensional Scale of Perceived Social Support (MSPSS) in cancer patients: psychometric properties and measurement invariance

Background: The aim of this study was to evaluate the psychometric properties, convergent validity, and factorial invariance of the Multidimensional Scale of Perceived Social Support (MSPSS) in cancer patients. Method: Confi rmatory factor analysis (CFA) was conducted to explore the scale's dimensionality and test for strong measurement invariance across sex and age in a cross-sectional, multicenter, prospective study. Patients completed the MSPSS and Satisfaction with Life Scale (SWLS). Results: A total of 925 consecutive patients were recruited in 13 hospitals between July 2015 and December 2018. The CFA indicated that the original three factor model was replicated in patients with cancer. The results of the multi-group CFA revealed a strong invariance according to sex and age. The Spanish version of the MSPSS had high estimated reliability with values exceeding .90. The simple sum of the items of each scale was a good indicator of oncology patients' perceived social support. The three MSPSS subscales correlated signifi cantly with the SWLS. Women scored higher on social support by friends than men. Conclusion: The Spanish version of the MSPSS proved to be a valid, reliable instrument to assess perceived social support in cancer patients

The Ancient Neolithic in Sierra Morena. Geoarchaeological analysis of an occupation deposit in cueva del Ocho (Cazalla de la Sierra, Seville, SW of Spain)

Se lleva a cabo el estudio geoarqueológico del Perfil A de la sala del Lago de la cueva del Ocho (complejo kárstico de las cuevas de Santiago, Cazalla de la Sierra, Sevilla, SO de España), con el objetivo de caracterizar la secuencia de ocupación antrópica de este sector de la cavidad, a partir del análisis de un depósito mediante técnicas de análisis arqueológicas, edafo-sedimentarias y geocronológicas. Los resultados obtenidos han permitido identificar una serie de unidades geoarqueológicas a partir de las cuales se ha establecido la secuencia de la ocupación antrópica de este sector de la cavidad. Se trata de una ocupación Neolítico antiguo, corta pero intensa, de cronología ca. 5300 cal. BC, que se conforma en el plazo de apenas 500 años y que queda sellada y amortizada en torno al cambio de era por una colada estalagmítica. Diferentes usos antrópicos caracterizan la conformación del depósito, desde una actividad ocupacional (hábitat) y redil inicial, que se transforma posteriormente en un ámbito de vertedero, reconociéndose depósitos con características sedimentológicas similares a los de tipo fumier, aunque desplazados de su lugar original. Los altos niveles de materia orgánica presente en los sedimentos, así como, de otras variables asociadas a la presencia humana (fósforo y susceptibilidad magnética) refuerzan la idea de la génesis antrópica del depósito. En este sentido, el estudio de la cerámica muestra que no se ha registrado ningún cambio tipológico ni tecnológico a lo largo de toda secuencia, siendo su tipo y características compatibles con las cronologías radiocarbónicas aportadas en el presente trabajo. A su vez, el estudio de arqueofauna muestra unos resultados, en cuanto a la presencia y manejo de fauna doméstica, propios de yacimientos correspondientes a las cronologías y el uso ofrecidos por la cueva del Ocho.The Geoarchaeological study of Profile A of the Sala del Lago of cueva del Ocho (karstic complex of cuevas de Santiago, Cazalla de la Sierra, Seville, SW of Spain) is carried out. The aim of characterizing sequence of anthropic occupation of this sector of the cave, from the analysis of a deposit by means of archaeological, pedo-sedimentary and geo-chronological analysis techniques has been characterized. The results obtained have allowed to identify a geo-archaeological series units from which the sequence of the anthropic occupation of this sector of the cavity. It is an Ancient Neolithic occupation, short but intense, of chronology ca.5300 cal. BC, which is formed in a period of just 500 years and which it is sealed and amortized around the change of Era by a stalagmite deposit. Different anthropic uses characterize the conformation of this deposit, from an occupational activity (habitat) and initial fold, which is later transformed into a landfill area, recognizing fumier type deposits, although displaced from their original place. The high levels of organic matter present in the sediments, as well as other parameters associated like phosphorus and magnetic susceptibility reinforce the idea of the anthropic genesis for this deposit. In this sense, the study of ceramics shows that no typological or technological change has been recorded in throughout any sequence, its type and characteristics being compatible with radiocarbon chronologies contributed in the present work. At the same time the archaeofauna study shows some results the presence and management of domestic fauna, typical of deposits corresponding to the chronologies and use offered through the cueva del Ocho

Cumulative exposure to tacrolimus and incidence of cancer after liver transplantation

Cancer is the leading cause of death after liver transplantation (LT). This multicenter case–control nested study aimed to evaluate the effect of maintenance immunosuppression on post-LT malignancy. The eligible cohort included 2495 LT patients who received tacrolimus-based immunosuppression. After 13 922 person/years follow-up, 425 patients (19.7%) developed malignancy (cases) and were matched with 425 controls by propensity score based on age, gender, smoking habit, etiology of liver disease, and hepatocellular carcinoma (HCC) before LT. The independent predictors of post-LT malignancy were older age (HR = 1.06 [95% CI 1.05–1.07]; p < .001), male sex (HR = 1.50 [95% CI 1.14–1.99]), smoking habit (HR = 1.96 [95% CI 1.42–2.66]), and alcoholic liver disease (HR = 1.53 [95% CI 1.19–1.97]). In selected cases and controls (n = 850), the immunosuppression protocol was similar (p = .51). An increased cumulative exposure to tacrolimus (CET), calculated by the area under curve of trough concentrations, was the only immunosuppression-related predictor of post-LT malignancy after controlling for clinical features and baseline HCC (CET at 3 months p = .001 and CET at 12 months p = .004). This effect was consistent for de novo malignancy (after excluding HCC recurrence) and for internal neoplasms (after excluding non-melanoma skin cancer). Therefore, tacrolimus minimization, as monitored by CET, is the key to modulate immunosuppression in order to prevent cancer after LT