Novel Ruthenium-Silver PTA-Based Polymers and Their Behavior in Water

New coordination polymers based on two metal-containing moieties Ru–Ag are synthesized: Na[RuCpX(PTA)-μ-(PTA)-1κP:2κ2N-AgX2]∞ (X = Cl (1), Br (2), I (3)). Characterization is performed by NMR, UV-visible and FT-IR spectroscopy, optical-electron microscopy, and elemental analyses (C, H, N, S). Light scattering is employed to characterize the colloidal particles growth by polymer self-assembling. These structures are stable over a broad range of pH and exhibit thermally-driven swelling, thus resembling a typical thermosensitive hydrogel

Liquid-gas separation in colloidal electrolytes

The liquid-gas transition of an electroneutral mixture of oppositely charged colloids, studied by Monte Carlo simulations, is found in the low-temperature–low-density region. The critical temperature shows a nonmonotonous behavior as a function of the interaction range, −1, with a maximum at 10, implying an island of coexistence in the - plane. The system is arranged in such a way that each particle is surrounded by shells of particles with alternating charge. In contrast with the electrolyte primitive model, both neutral and charged clusters are obtained in the vapor phase

Optimization of a Novel Method Based on Ultrasound-Assisted Extraction for the Quantification of Anthocyanins and Total Phenolic Compounds in Blueberry Samples (Vaccinium corymbosum L.)

In recent years, consumers' preference for fruits such as blueberry has increased noticeably. This fact is probably related to their bioactive components such as anthocyanins, phenolic compounds, vitamins, minerals, and tannins that have been found in blueberries by the latest research studies. Both total anthocyanins (TA) and total phenolic compounds (TPC) are known for their multiple beneficial effects on our health, due to their anti-inflammatory, anti-oxidant, and anti-cancer properties. This is the reason why the development of new methodologies for the quality control analysis of raw materials or derived products from blueberry has a great relevance. Two ultrasound-assisted extraction methods (UAE) have been optimized for the quantification of TA and TPC in blueberry samples. The six variables to be optimized were: solvent composition, temperature, amplitude, cycle, extraction solvent pH, and sample/solvent ratio using response surface methodology. The optimized methods have proven to be suitable for the extraction of the TPC and TA with good precision (repeatability and intermediate precision) (coefficient of variation (CV) < 5%) and potentially for application in commercial samples. This fact, together with the multiple advantages of UAE, makes these methods a good alternative to be used in quality control analysis by both industries and laboratories

Regioselective synthesis of neo-erlose by the beta-fructofuranosidase from Xanthophyllomyces dendrorhous

The beta-fructofuranosidase from the yeast Xanthophyllomyces dendrorhous (Xd-INV) catalyzes the synthesis of neo-fructooligosaccharides (neo-FOS of the 6G-series), which contain a beta(2-6) linkage between a fructose and the glucosyl moiety of sucrose. In this work we demonstrate that the enzyme is also able to fructosylate other carbohydrates that contain glucose, in particular disaccharides (maltose, isomaltulose, isomaltose, trehalose) and higher oligosaccharides (maltotriose, raffinose, maltotetraose), but not monosaccharides (glucose, fructose, galactose). With maltose as acceptor, the reaction in the presence of Xd-INV proceeded with high regioselectivity; the product was purified and chemically characterized, and turned out to be 6’-O--fructosylmaltose (neo-erlose). Using 100 g/L sucrose as fructosyl donor and 300 g/L maltose as acceptor, the maximum concentration of neo-erlose was 38.3 g/L. Thus, novel hetero-fructooligosaccharides with potential applications in the functional food and pharmaceutical industries can be obtained with Xd-INV.Projects BIO2010-20508-C04-01 and BIO2010-20508-C04-04 from Spanish Ministry of Science and Innovation supported this research. We thank Fundación Ramon Areces for an institutional grant to the Centro de Biología Molecular Severo Ochoa.Peer reviewe

First exfoliated Ru–Ru–Au organometallic polymer with layered structure.

A new water soluble heterometallic polymeric complex [{(PTA)2 CpRu-l-CN-1jC:2j2N-RuCp(PTA)2}-l-{Au(CN)4}4]n 2H2O (1) is synthesized and characterized by single crystal X-ray diffraction. This complex self-assembles forming 3D polymeric structures with large scale hexagonal conformation. They also organize as 3D stacks of polymer sandwiches that can be exfoliated providing mono heterometallic-3D layers, as shown by electron microscopy. Regarding the polymer dynamics, quasi-elastic neutron scattering shows a transition from vibrational Debye–Waller behaviour to a more dynamically active state as a result of the loss of structural water molecules

Sistema de b-learning en Farmacología (I): pilotando

Siguiendo el espíritu renovador derivado de la implementación del Espacio Europeo de Educación Superior y utilizando el entorno del Campus Virtual de la UCM (WebCT), se han desarrollado las bases para la implantación de un sistema de b-learning. Los estudiantes de “Farmacología, Farmacia y Terapéutica” de la Licenciatura de Veterinaria podrán consultar, organizado por módulos temáticos, material didáctico para aprender de forma activa los contenidos de esta asignatura troncal. Las herramientas que conforman este sistema presentan diversas finalidades y formatos: formativas (guiones, presentaciones, vídeos, problemas); comunicativas (foro de intercambio de ideas, dudas e iniciativas y avisos); y evaluadoras (autoevaluaciones para los alumnos y encuestas sobre la utilidad de la propia herramienta). La idea es que los estudiantes sean los gestores de su propio aprendizaje. Para ello, cuentan con el apoyo de una herramienta virtual (Aula Virtual de Farmacología), con actividades docentes presenciales (seminarios y tutorías) y con herramientas de evaluación de los conocimientos adquiridos.Following the innovative spirit derived from implementation of the European Higher Education Area and using an online learning environment (Campus Virtual-UCM), the bases for the implantation of a b-learning system have been developed. The students of "Pharmacology, Pharmacy and Therapeutic" of the Veterinary Medicine degree will be able to consult, organized by thematic modules, educational material to learn in an active way the contents of this core subject. The tools that shape this system present diverse purposes and formats: formatives (scripts, presentations, videos, problems); communicatives (forum to exchanging of ideas, doubts or initiatives and notices); assessments (autoevaluations for the pupils and surveys on the usefulness of the own tool). The idea is that students are the managers of their own learning. For it, they have the support of a virtual tool (Virtual Classroom of Pharmacology), face-to-face educational activities (seminars, tutorials) and tools of evaluation of the acquired knowledge

Selective Synthesis of Galactooligosaccharides Containing β(1→3) Linkages with β-Galactosidase from Bifidobacterium bifidum (Saphera)

[EN] The transglycosylation activity of a novel commercial β-galactosidase from Bifidobacterium bifidum (Saphera) was evaluated. The optimal conditions for the operation of this enzyme, measured with o-nitrophenyl-β-d-galactopyranoside, were 40 °C and pH around 6.0. Although at low lactose concentrations the property of this enzyme was basically hydrolytic, an increase of lactose concentration to 400 g/L resulted in a significant formation (107.2 g/L, 27% yield) of prebiotic galactooligosaccharides (GOS). The maximum amount of GOS was obtained at a lactose conversion of approximately 90%, which contrasts with other β-galactosidases, for which the highest GOS yield is achieved at 40-50% lactose conversion. Using high-performance anion-exchange chromatography with pulsed amperometric detection, semipreparative high-performance liquid chromatography-hydrophilic interaction liquid chromatography, mass spectrometry, and 1D and 2D NMR, we determined the structure of most of the GOS synthesized by this enzyme. The main identified products were Gal-β(1→3)-Gal-β(1→4)-Glc (3′-O-β-galactosyl-lactose), Gal-β(1→6)-Glc (allolactose), Gal-β(1→3)-Glc (3-galactosyl-glucose), Gal-β(1→3)-Gal (3-galactobiose), and the tetrasaccharide Gal-β(1→3)-Gal-β(1→3)-Gal-β(1→4)-Glc. In general, B. bifidum β-galactosidase showed a tendency to form β(1→3) linkages followed by β(1→6) and more scarcely β(1→4).This work was supported by a grant from the Spanish Ministry of Economy and Competitiveness (BIO2016-76601-C3-1). The group at CIC bioGUNE thanks Agencia Estatal de Investigación (Spain) for the Severo Ochoa Excellence Accreditation (SEV-2016-0644)

Co-precipitation of grape residue extract using sub- and supercritical CO2 technology

a micronización y secado de extractos líquidos crudos por procesos verdes no térmicos es muy interesante cuando se desea reducir el espacio de almacenamiento, los costos de transporte y concentrar y encapsular compuestos de interés. En este trabajo, se estudió la co-precipitación de extracto de etanol a partir de residuos de uva con un polímero biodegradable y biocompatible, polivinilpirrolidona (PVP), utilizando tecnología de CO2 subcrítica y supercrítica, es decir, en el presente trabajo mediante un antisolutorio presurizado (PAS). Se utilizó un diseño factorial completo (3 x 3) para evaluar el efecto de la presión (90, 130 y 170 bar) y la temperatura (20, 32 y 45 ºC) sobre el proceso PAS y las características de las partículas formadas por él. Presiones más altas (170 bar) y temperaturas (45 ºC) resultaron significativamente en condiciones operativas con con mejores rendimientos de precipitación global y en la producción de partículas con un diámetro medio más bajo y un contenido residual de etanol. Las partículas tenían una forma casi esférica con tamaños de 1,3 a 4,1 µm. La interacción de baja temperatura (20 ºC) con alta presión (170 bar) llevó a la producción de polvos secos más concentrados en antocianinas y compuestos fenólicos totales, y en procesos con mayores rendimientos de co-precipitación de estos bioactivos. Aunque los factores en estudio no tienen un efecto significativo sobre la capacidad antioxidante (CA) de las partículas, se observó que la CA se correlacionó fuertemente con el contenido de antocianinas y fenoles totales, demostrando así que el poder antioxidante del PAS co-precipitados del residuo de uva que era debido a la presencia de fenólico, principalmente antocianinas. Trece antocianinas fueron identificadas y cuantificadas en el extracto original y micropartículas co-precipitadas por UHPLC, siendo trans-malvidina-3-O-(6"-cumaril)-glucósido, malvidina-3-O-glucósido y malvidina-3-(6"-acetil)-glucósido las principales antocianinas. A partir de los estudios de liberación in vitro, se observó que las micropartículas, producidas en las mejores condiciones experimentales, liberaban compuestos fenólicos más lentamente en fluidos gastrointestinales simulados que el extracto precipitado sin polímero. Las antocianinas totales se detectaron parcialmente en el líquido intestinal, mientras que en el líquido gástrico se liberaron al 100% en un corto período. Al final, se puede concluir que la técnica del PAS, cuando se realiza principalmente en condiciones supercríticas, es un proceso muy prometedor para co-precipitación, concentración y fraccionamiento simultáneo de compuestos polares sensibles, como antocianinas, presentes en extractos de plantas crudas. Además, conduce a la producción de sistemas de administración bioactivos con mejores tasas de disolución en fluidos gastrointestinales simuladosThe micronization and drying of crude liquid extracts by green non-thermal processes is very interesting when it is desired to reduce storage space, transport costs, and to concentrate and encapsulate compounds of interest. In this work, the co-precipitation of ethanol extract from grape residue with a biodegradable and biocompatible polymer, polyvinylpyrrolidone (PVP), was studied using sub- and supercritical CO2 technology, namely in the present work by pressurized anti-solvent (PAS). A full factorial design (3 x 3) was used to evaluate the effect of pressure (90, 130 and 170 bar) and temperature (20, 32 and 45 ºC) on the PAS process and the characteristics of the particles formed by it. Higher pressures (170 bar) and temperatures (45 ºC) significantly resulted in operational conditions with better global precipitation yields and in the production of particles with a lower average diameter and residual ethanol content. The particles had a quasi-spherical shape with sizes from 1.3 to 4.1 µm. The interaction of low temperature (20 ºC) with high pressure (170 bar) led to the production of dry powders more concentrated in anthocyanins and total phenolic compounds, and in processes with higher co-precipitation yields of these bioactives. Although the factors under study do not have a significant effect on the antioxidant capacity (AC) of the particles, it was noted that AC correlated strongly with the content of anthocyanins and total phenolics, thus demonstrating that the antioxidant power of the PAS co-precipitates of the grape residue it was due to the presence of phenolic compounds, mainly anthocyanins. Thirteen anthocyanins were identified and quantified in the original extract and co-precipitated microparticles by UHPLC, being trans-malvidin-3-O-(6"-cumaryl)-glucoside, malvidin-3-O-glucoside and malvidin-3-(6"-acetyl)-glucoside the major anthocyanins. From the in vitro release studies, it was observed that the microparticles, produced from the best experimental conditions, released more slowly phenolic compounds in simulated gastrointestinal fluids than the precipitated extract without polymer. Total anthocyanins were partially detected in the intestinal fluid, while in the gastric fluid were 100% released in a short period. In the end, it can be concluded that the PAS technique, when performed mainly in supercritical conditions, is a very promising process for co-precipitating, concentrating and simultaneously fractionating sensitive polar compounds, such as anthocyanins, present in crude plant extracts. Furthermore, it leads to the production bioactive delivery systems with better dissolution rates in simulated gastrointestinal fluids

Enzymatic Synthesis of a Novel Pterostilbene α-Glucoside by the Combination of Cyclodextrin Glucanotransferase and Amyloglucosidase

The synthesis of a novel α-glucosylated derivative of pterostilbene was performed by a transglycosylation reaction using starch as glucosyl donor, catalyzed by cyclodextrin glucanotransferase (CGTase) from Thermoanaerobacter sp. The reaction was carried out in a buffer containing 20% (v/v) DMSO to enhance the solubility of pterostilbene. Due to the formation of several polyglucosylated products with CGTase, the yield of monoglucoside was increased by the treatment with a recombinant amyloglucosidase (STA1) from Saccharomyces cerevisiae (var. diastaticus). This enzyme was not able to hydrolyze the linkage between the glucose and pterostilbene. The monoglucoside was isolated and characterized by combining ESI-MS and 2D-NMR methods. Pterostilbene α-d-glucopyranoside is a novel compound. The α-glucosylation of pterostilbene enhanced its solubility in water to approximately 0.1 g/L. The α-glucosylation caused a slight loss of antioxidant activity towards ABTS˙+ radicals. Pterostilbene α-d-glucopyranoside was less toxic than pterostilbene for human SH-S5Y5 neurons, MRC5 fibroblasts and HT-29 colon cancer cells, and similar for RAW 264.7 macrophages.This research was funded by the Spanish Ministry of Economy and Competitiveness (Grants BIO2016-76601-C3-1-R and BIO2016-76601-C3-3-R).Peer reviewe

Heart failure in COVID-19 patients: prevalence, incidence and prognostic implications

Aims: Data on the impact of COVID-19 in chronic heart failure (CHF) patients and its potential to trigger acute heart failure (AHF) are lacking. The aim of this work was to study characteristics, cardiovascular outcomes and mortality in patients with confirmed COVID-19 infection and a prior diagnosis of heart failure (HF). Further aims included the identification of predictors and prognostic implications for AHF decompensation during hospital admission and the determination of a potential correlation between the withdrawal of HF guideline-directed medical therapy (GDMT) and worse outcomes during hospitalization. Methods and results: Data for a total of 3080 consecutive patients with confirmed COVID-19 infection and follow-up of at least 30 days were analysed. Patients with a previous history of CHF (n = 152, 4.9%) were more prone to the development of AHF (11.2% vs. 2.1%; P < 0.001) and had higher levels of N-terminal pro brain natriuretic peptide. In addition, patients with previous CHF had higher mortality rates (48.7% vs. 19.0%; P < 0.001). In contrast, 77 patients (2.5%) were diagnosed with AHF, which in the vast majority of cases (77.9%) developed in patients without a history of HF. Arrhythmias during hospital admission and CHF were the main predictors of AHF. Patients developing AHF had significantly higher mortality (46.8% vs. 19.7%; P < 0.001). Finally, the withdrawal of beta-blockers, mineralocorticoid receptor antagonists and angiotensin-converting enzyme inhibitors or angiotensin receptor blockers was associated with a significant increase in in-hospital mortality. Conclusions: Patients with COVID-19 have a significant incidence of AHF, which is associated with very high mortality rates. Moreover, patients with a history of CHF are prone to developing acute decompensation after a COVID-19 diagnosis. The withdrawal of GDMT was associated with higher mortalit