Cu(111) single crystal electrodes: Modifying interfacial properties to tailor electrocatalysis

Tailoring electrocatalyst materials to the specific requirements of a certain reaction and to optimize activity or enhance selectivity is a key tactic for the development of low-temperature fuel and electrolyzer cells for clean energy production. Here, we demonstrate the modification of Cu(111) electrodes with different sub-monolayer coverages of foreign metals (Cd) and metal hydroxides (Co(OH)2 and Ni(OH)2) for application in the hydrogen evolution reaction (HER) in alkaline media. In situ electrochemical scanning tunneling microscopy (EC-STM) reveals that these modifications have a significant influence on the morphology and structure of the Cu(111) surface with its characteristics depending on both the nature and the amount of the adsorbed metal(hydroxide). Ni(OH)2 and Co(OH)2 on Cu(111) lead to a significant enhancement of the electrocatalytic activity towards the HER in alkaline electrolyte, whereas a decrease in activity is found for Cd modified Cu(111). These trends can be rationalized by considering the strength of the interfacial electric field and its influence on the specific interactions of the electrode with the water ad-layer close to the surface, as determined by laser-induced temperature jump measurements. This comparative study therefore provides valuable information on the structure-activity relation as well as insights on the interfacial characteristics of different bimetallic Cu electrocatalysts.A.A. is a recipient of a doctorate (DOC) Fellowship of the Austrian Academy of Sciences at the Institute of Physical Chemistry. C.G. thanks the Austrian Research Promotion Agency (FFG) for funding by the project number 870523. J.K-L. acknowledges funding by the Austrian Science Fund (FWF) via grant I-4114-N37. J.M.F and V.C. acknowledge financial support from Ministerio de Ciencia e Innovación (project PID2019-105653GB-100) and Generalitat Valenciana (project PROMETEO/2020/063)

A thermostable GH45 endoglucanase from yeast: impact of its atypical multimodularity on activity

BACKGROUND: The gene encoding an atypical multi-modular glycoside hydrolase family 45 endoglucanase bearing five different family 1 carbohydrate binding modules (CBM1), designated PpCel45A, was identified in the Pichia pastoris GS115 genome. RESULTS: PpCel45A (full-length open reading frame), and three derived constructs comprising (i) the catalytic module with its proximal CBM1, (ii) the catalytic module only, and (iii) the five CBM1 modules without catalytic module, were successfully expressed to high yields (up to 2 grams per litre of culture) in P. pastoris X33. Although the constructs containing the catalytic module displayed similar activities towards a range of glucans, comparison of their biochemical characteristics revealed striking differences. We observed a high thermostability of PpCel45A (Half life time of 6 h at 80°C), which decreased with the removal of CBMs and glycosylated linkers. However, both binding to crystalline cellulose and hydrolysis of crystalline cellulose and cellohexaose were substantially boosted by the presence of one CBM rather than five. CONCLUSIONS: The present study has revealed the specific features of the first characterized endo β-1,4 glucanase from yeast, whose thermostability is promising for biotechnological applications related to the saccharification of lignocellulosic biomass such as consolidated bioprocessing

Interfacial Water Structure as a Descriptor for Its Electro-Reduction on Ni(OH)2-Modified Cu(111)

The hydrogen evolution reaction (HER) has been crucial for the development of fundamental knowledge on electrocatalysis and electrochemistry, in general. In alkaline media, many key questions concerning pH-dependent structure–activity relations and the underlying activity descriptors remain unclear. While the presence of Ni(OH)2 deposited on Pt(111) has been shown to highly improve the rate of the HER through the electrode’s bifunctionality, no studies exist on how low coverages of Ni(OH)2 influence the electrocatalytic behavior of Cu surfaces, which is a low-cost alternative to Pt. Here, we demonstrate that Cu(111) modified with 0.1 and 0.2 monolayers (ML) of Ni(OH)2 exhibits an unusual non-linear activity trend with increasing coverage. By combining in situ structural investigations with studies on the interfacial water orientation using electrochemical scanning tunneling microscopy and laser-induced temperature jump experiments, we find a correlation between a particular threshold of surface roughness and the decrease in the ordering of the water network at the interface. The highly disordered water ad-layer close to the onset of the HER, which is only present for 0.2 ML of Ni(OH)2, facilitates the reorganization of the interfacial water molecules to accommodate for charge transfer, thus enhancing the rate of the reaction. These findings strongly suggest a general validity of the interfacial water reorganization as an activity descriptor for the HER in alkaline media.A.A. is a recipient of a doctorate (DOC) Fellowship of the Austrian Academy of Sciences at the Institute of Physical Chemistry. C.G. thanks the Austrian Research Promotion Agency (FFG) for funding via the project number 870523. J.K.-L. acknowledges funding by the Austrian Science Fund (FWF) via grant I-4114-N37. J.M.F. and V.C. acknowledge financial support from Ministerio de Ciencia e Innovación (project PID2019-105653GB-100) and Generalitat Valenciana (project PROMETEO/2020/063)

Clinical nutrition as part of the treatment pathway of pancreatic cancer patients: an expert consensus

Consensus; Nutritional screening; Pancreatic cancerConsenso; Cribado nutricional; Cáncer de páncreasConsens; Cribratge nutricional; Càncer de pàncreesPurpose Malnutrition is a common problem among pancreatic cancer (PC) patients that negatively impacts on their quality of life (QoL) and clinical outcomes. The main objective of this consensus is to address the role of Medical Nutrition Therapy (MNT) into the comprehensive therapeutic management of PC patients. Methods A Spanish multidisciplinary group of specialists from the areas of Medical Oncology; Radiation Oncology; Endocrinology and Nutrition; and General Surgery agreed to assess the role of MNT as part of the best therapeutic management of PC patients. Results The panel established different recommendations focused on nutritional screening and nutritional screening tools, MNT strategies according to PC status, and MNT in palliative treatment. Conclusions There is an unmet need to integrate nutritional therapy as a crucial part of the multimodal care process in PC patients. Health authorities, health care professionals, cancer patients, and their families should be aware of the relevance of nutritional status and MNT on clinical outcomes and QoL of PC patients.Open Access funding provided thanks to the CRUE-CSIC agreement with Springer Nature.

Endothelin-1 as a Mediator of Heme Oxygenase-1-Induced Stemness in Colorectal Cancer: Influence of p53

Heme oxygenase-1 (HO-1) is an antioxidant protein implicated in tumor progression, metastasis, and resistance to therapy. Elevated HO-1 expression is associated with stemness in several types of cancer, although this aspect has not yet been studied in colorectal cancer (CRC). Using an in vitro model, we demonstrated that HO-1 overexpression regulates stemness and resistance to 5-FU treatment, regardless of p53. In samples from CRC patients, HO-1 and endothelin converting enzyme-1 (ECE-1) expression correlated significantly, and p53 had no influence on this result. Carbon monoxide (CO) activated the ECE-1/endothelin-1 (ET-1) pathway, which could account for the protumoral effects of HO-1 in p53 wild-type cells, as demonstrated after treatment with bosentan (an antagonist of both ETRA and ETRB endothelin-1 receptors). Surprisingly, in cells with a non-active p53 or a mutated p53 with gain-of-function, ECE-1-produced ET-1 acted as a protective molecule, since treatment with bosentan led to increased efficiency for spheres formation and percentage of cancer stem cells (CSCs) markers. In these cells, HO-1 could activate or inactivate certain unknown routes that could induce these contrary responses after treatment with bosentan in our cell model. However more research is warranted to confirm these results. Patients carrying tumors with a high expression of both HO-1 and ECE-1 and a non-wild-type p53 should be considered for HO-1 based-therapies instead of ET-1 antagonists-based ones.Instituto de Salud Carlos IIIFEDER (PI18/01947)MINECO grant (DPI2017-84439-R)Nicolás Monardes Program from the Andalusian Health Service (C-0033-2015)FPU2019 fellowship (FPU19/02269) from the Ministerio de Ciencia, Innovación y Universidades (Spain

Current Advances Research in Nutraceutical Compounds of Legumes, Pseudocereals and Cereals

The increase of the Western-type diet and life-style, with high content of highly processed fats, salt and sugar, as well as sedentary life, is directly linked to an increasing incidence of chronic diseases such as diabetes and obesity, cancer, cardiovascular diseases or stroke, and inflammatory-related diseases, which are a great challenge in global health and are usually associated with negative effects of globalization: rapid urbanization, diet and increased sedentary life worldwide. This has brought new interest and increased research into plant-based diets. In this context, the implementation in the diet of legumes, cereals and pseudo-cereals, due to their nutraceutical properties, which is interesting as well as advisable. These foods, in addition of having a high nutritional value themselves, have synergistic properties as part of a balanced diet. For example, most legumes are rich in lysine which is scarce in cereals, and these are rich in sulphur amino acids, such as methionine, while these amino acids are scarce in legumes and are of great importance for the central nervous system development. These foods or part of a food, due to their qualities, and that they provide health benefits can be classified as nutraceuticals. In addition, due to their health benefits beyond nutritional properties, can be classified as functional foods, promoting prevention and treatment for the above mentioned diseases, among others. This double function is due mainly to the proteins and the presence of various secondary metabolites and bioactive compounds in these foods of plant (grain and seed) origin. Last discovered knowledge and research features will be described in the present book chapter

A randomized, phase III trial of capecitabine plus bevacizumab (Cape-Bev) versus capecitabine plus irinotecan plus bevacizumab (CAPIRI-Bev) in first-line treatment of metastatic colorectal cancer: The AIO KRK 0110 Trial/ML22011 Trial

<p>Abstract</p> <p>Background</p> <p>Several randomized trials have indicated that combination chemotherapy applied in metastatic colorectal cancer (mCRC) does not significantly improve overall survival when compared to the sequential use of cytotoxic agents (CAIRO, MRC Focus, FFCD 2000-05). The present study investigates the question whether this statement holds true also for bevacizumab-based first-line treatment including escalation- and de-escalation strategies.</p> <p>Methods/Design</p> <p>The AIO KRK 0110/ML22011 trial is a two-arm, multicenter, open-label randomized phase III trial comparing the efficacy and safety of capecitabine plus bevacizumab (Cape-Bev) versus capecitabine plus irinotecan plus bevacizumab (CAPIRI-Bev) in the first-line treatment of metastatic colorectal cancer. Patients with unresectable metastatic colorectal cancer, Eastern Cooperative Oncology Group (ECOG) performance status 0-1, will be assigned in a 1:1 ratio to receive either capecitabine 1250 mg/m²bid for 14d (d1-14) plus bevacizumab 7.5 mg/kg (d1) q3w (Arm A) or capecitabine 800 mg/m²BID for 14d (d1-14), irinotecan 200 mg/m²(d1) and bevacizumab 7.5 mg/kg (d1) q3w (Arm B). Patients included into this trial are required to consent to the analysis of tumour tissue and blood for translational investigations. In Arm A, treatment escalation from Cape-Bev to CAPIRI-Bev is recommended in case of progressive disease (PD). In Arm B, de-escalation from CAPIRI-Bev to Cape-Bev is possible after 6 months of treatment or in case of irinotecan-associated toxicity. Re-escalation to CAPIRI-Bev after PD is possible. The primary endpoint is time to failure of strategy (TFS). Secondary endpoints are overall response rate (ORR), overall survival, progression-free survival, safety and quality of life.</p> <p>Conclusion</p> <p>The AIO KRK 0110 trial is designed for patients with disseminated, but asymptomatic mCRC who are not potential candidates for surgical resection of metastasis. Two bevacizumab-based strategies are compared: one starting as single-agent chemotherapy (Cape-Bev) allowing escalation to CAPIRI-Bev and another starting with combination chemotherapy (CAPIRI-Bev) and allowing de-escalation to Cape-Bev and subsequent re-escalation if necessary.</p> <p>Trial Registration</p> <p>ClinicalTrials.gov Identifier <a href="http://www.clinicaltrials.gov/ct2/show/NCT01249638">NCT01249638</a></p> <p>EudraCT-No.: 2009-013099-38</p

Trabajo de coordinación para la implementación del cuarto curso del Grado en Química

En el curso 2013-14 se implantará el cuarto y último curso del Grado en Química. La experiencia adquirida durante la implementación de los tres primeros cursos ha puesto de manifiesto la conveniencia de realizar un proceso de coordinación entre los profesores de las diferentes asignaturas que garantice la consecución de las competencias previstas en la memoria del título. Por ello, se ha creado en la Facultad de Ciencias de la Universidad de Alicante una red de investigación en docencia universitaria que ha estado trabajando desde el inicio del presente curso académico en este tema. Dicha red está constituida por el Vicedecano de Ordenación Académica de la Facultad de Ciencias, la Coordinadora Académica de Química y los profesores coordinadores de todas las asignaturas del 4º curso del grado (excepto Prácticas Externas y Trabajo Fin de Grado). En esta comunicación se presentarán los resultados del trabajo de investigación realizado por estos profesores que ha permitido elaborar las guías docentes de las asignaturas, planificar y coordinar las actividades a realizar para que los alumnos adquieran las competencias transversales, realizar un cronograma de actividades de evaluación y otro de prácticas de laboratorio que asegure la distribución homogénea del trabajo del alumno durante el curso académico

Jardins per a la salut

Facultat de Farmàcia, Universitat de Barcelona. Ensenyament: Grau de Farmàcia. Assignatura: Botànica farmacèutica. Curs: 2014-2015. Coordinadors: Joan Simon, Cèsar Blanché i Maria Bosch.Els materials que aquí es presenten són el recull de les fitxes botàniques de 128 espècies presents en el Jardí Ferran Soldevila de l’Edifici Històric de la UB. Els treballs han estat realitzats manera individual per part dels estudiants dels grups M-3 i T-1 de l’assignatura Botànica Farmacèutica durant els mesos de febrer a maig del curs 2014-15 com a resultat final del Projecte d’Innovació Docent «Jardins per a la salut: aprenentatge servei a Botànica farmacèutica» (codi 2014PID-UB/054). Tots els treballs s’han dut a terme a través de la plataforma de GoogleDocs i han estat tutoritzats pels professors de l’assignatura. L’objectiu principal de l’activitat ha estat fomentar l’aprenentatge autònom i col·laboratiu en Botànica farmacèutica. També s’ha pretès motivar els estudiants a través del retorn de part del seu esforç a la societat a través d’una experiència d’Aprenentatge-Servei, deixant disponible finalment el treball dels estudiants per a poder ser consultable a través d’una Web pública amb la possibilitat de poder-ho fer in-situ en el propi jardí mitjançant codis QR amb un smartphone

Atomic spectrometry update: Review of advances in the analysis of metals, chemicals and materials

There has been a large increase in the number of papers published that are relevant to this review over this review period. The growth in popularity of LIBS is rapid, with applications being published for most sample types. This is undoubtedly because of its capability to analyse in situ on a production line (hence saving time and money) and its minimally destructive nature meaning that both forensic and cultural heritage samples may be analysed. It also has a standoff analysis capability meaning that hazardous materials, e.g. explosives or nuclear materials, may be analysed from a safe distance. The use of mathematical algorithms in conjunction with LIBS to enable improved accuracy has proved a popular area of research. This is especially true for ferrous and non-ferrous samples. Similarly, chemometric techniques have been used with LIBS to aid in the sorting of polymers and other materials. An increase in the number of papers in the subject area of alternative fuels was noted. This was at the expense of papers describing methods for the analysis of crude oils. For nanomaterials, previous years have seen a huge number of single particle and field flow fractionation characterisations. Although several such papers are still being published, the focus seems to be switching to applications of the nanoparticles and the mechanistic aspects of how they retain or bind with other analytes. This is the latest review covering the topic of advances in the analysis of metals, chemicals and materials. It follows on from last year's review1-6 and is part of the Atomic Spectrometry Updates series