The Biomodified Lignin Platform: A Review.

A reliance on fossil fuel has led to the increased emission of greenhouse gases (GHGs). The excessive consumption of raw materials today makes the search for sustainable resources more pressing than ever. Technical lignins are mainly used in low-value applications such as heat and electricity generation. Green enzyme-based modifications of technical lignin have generated a number of functional lignin-based polymers, fillers, coatings, and many other applications and materials. These bio-modified technical lignins often display similar properties in terms of their durability and elasticity as fossil-based materials while also being biodegradable. Therefore, it is possible to replace a wide range of environmentally damaging materials with lignin-based ones. By researching publications from the last 20 years focusing on the latest findings utilizing databases, a comprehensive collection on this topic was crafted. This review summarizes the recent progress made in enzymatically modifying technical lignins utilizing laccases, peroxidases, and lipases. The underlying enzymatic reaction mechanisms and processes are being elucidated and the application possibilities discussed. In addition, the environmental assessment of novel technical lignin-based products as well as the developments, opportunities, and challenges are highlighted.

The hidden microbial ecosystem in the perennial ice from a Pyrenean ice cave.

Over the last years, perennial ice deposits located within caves have awakened interest as places to study microbial communities since they represent unique cryospheric archives of climate change. Since the beginning of the twentieth century, the temperature has gradually increased, and it is estimated that by the end of this century the increase in average temperature could be around 4.0°C. In this context of global warming the ice deposits of the Pyrenean caves are undergoing a significant regression. Among this type of caves, that on the Cotiella Massif in the Southern Pyrenees is one of the southernmost studied in Europe. These types of caves house microbial communities which have so far been barely explored, and therefore their study is necessary. In this work, the microbial communities of the Pyrenean ice cave A294 were identified using metabarcoding techniques. In addition, research work was carried out to analyze how the age and composition of the ice affect the composition of the bacterial and microeukaryotic populations. Finally, the in vivo effect of climate change on the cellular machinery that allow microorganisms to live with increasing temperatures has been studied using proteomic techniques.

Improving Properties of Starch-Based Adhesives with Carboxylic Acids and Enzymatically Polymerized Lignosulfonates.

A novel strategy for improving wet resistance and bonding properties of starch-based adhesives using enzymatically polymerized lignosulfonates and carboxylic acids as additives was developed. Therefore, lignosulfonates were polymerized by laccase to a molecular weight of 750 kDa. Incorporation of low concentrations (up to 1% of the starch weight) of 1,2,3,4-butanetetracarboxylic acid (BTCA) led to further improvement on the properties of the adhesives, while addition of greater amounts of BTCA led to a decrease in the properties measured due to large viscosity increases. Great improvements in wet-resistance from 22 to 60 min and bonding times (from 30 to 20 s) were observed for an adhesive containing 8% enzymatically polymerized lignin and 1% BTCA. On the other hand, the addition of citric acid (CA) deteriorated the properties of the adhesives, especially when lignosulfonate was present. In conclusion, this study shows that the addition of the appropriate amount of enzymatically polymerized lignosulfonates together with carboxylic acids (namely BTCA) to starch-based adhesives is a robust strategy for improving their wet resistance and bonding times.

A Photochemoenzymatic Hunsdiecker-Borodin-Type Halodecarboxylation of Ferulic Acid.

A photochemoenzymatic halodecarboxylation of ferulic acid was achieved using vanadate-dependent chloroperoxidase as (bio)catalyst and oxygen and organic solvent as sole stoichiometric reagents in a biphasic system. Performance and selectivity were improved through a phase transfer catalyst, reaching a turnover number of 660.000 for the enzyme.

Role of Surface Enhancement in the Enzymatic Cross-Linking of Lignosulfonate Using Alternative Downstream Techniques.

Lignosulfonate (LS), one of the byproducts of the paper and pulp industry, was mainly used as an energy source in the last decade until the valorization of lignin through different functionalization methods grew in importance. Polymerization using multicopper oxidase laccase (from the Myceliophthora thermophila fungus) is one of such methods, which not only enhances properties such as hydrophobicity, flame retardancy, and bonding properties but can also be used for food and possesses pharmaceutical-like antimicrobial properties and aesthetic features of materials. Appropriate downstream processing methods are needed to produce solids that allow the preservation of particle morphology, a vital factor for the valorization process. In this work, an optimization of the enzymatic polymerization via spray-drying of LS was investigated. The response surface methodology was used to optimize the drying process, reduce the polymerization time, and maximize the dried mass yield. Particles formed showed a concave morphology and enhanced solubility while the temperature sensitivity of spray-drying protected the phenol functionalities beneficial for polymerization. Using the optimized parameters, a yield of 65% in a polymerization time of only 13 min was obtained. The experimental values were found to be in agreement with the predicted values of the factors (R 2: 95.2% and p-value: 0.0001), indicating the suitability of the model in predicting polymerization time and yield of the spray-drying process.

Enzymatic synthesis of wet-resistant lignosulfonate-starch adhesives.

This work describes a new method for improving the properties, mainly the wet-resistance, of starch-based adhesives using enzymatically polymerized lignosulfonates. A correlation of viscosity with molecular weight was found, allowing simple control of enzymatic polymerization of lignosulfonates. Incorporation of lignosulfonates polymerized from 29 kDa to > 4500 kDa using laccase led to a considerable increase in wet-resistance (from 15 to 20 min for the laminating glue and from 150 to 1200 min for the bag glue) while not affecting (for the laminating glue) or even improving the bonding time (from 80 to 60 s for the bag glue). Finally, the effect of active laccase in the final adhesive was investigated by enzymatic inactivation using NaN3 before formulation of the glue, as well as by extra laccase addition. In conclusion, this study shows that enzymatically polymerized lignosulfonate is a robust strategy for improving wet resistance of starch-based adhesives.

Glacial Ice Age Shapes Microbiome Composition in a Receding Southern European Glacier.

Glaciers and their microbiomes are exceptional witnesses of the environmental conditions from remote times. Climate change is threatening mountain glaciers, and especially those found in southern Europe, such as the Monte Perdido Glacier (northern Spain, Central Pyrenees). This study focuses on the reconstruction of the history of microbial communities over time. The microorganisms that inhabit the Monte Perdido Glacier were identified using high-throughput sequencing, and the microbial communities were compared along an altitudinal transect covering most of the preserved ice sequence in the glacier. The results showed that the glacial ice age gradient did shape the diversity of microbial populations, which presented large differences throughout the last 2000 years. Variations in microbial community diversity were influenced by glacial conditions over time (nutrient concentration, chemical composition, and ice age). Some groups were exclusively identified in the oldest samples as the bacterial phyla Fusobacteria and Calditrichaeota, or the eukaryotic class Rhodophyceae. Among groups only found in modern samples, the green sulfur bacteria (phylum Chlorobi) stood out, as well as the bacterial phylum Gemmatimonadetes and the eukaryotic class Tubulinea. A patent impact of human contamination was also observed on the glacier microbiome. The oldest samples, corresponding to the Roman Empire times, were influenced by the beginning of mining exploitation in the Pyrenean area, with the presence of metal-tolerant microorganisms. The most recent samples comprise 600-year-old ancient ice in which current communities are living.

Timing and structure of the Younger Dryas event and its underlying climate dynamics.

The Younger Dryas (YD), arguably the most widely studied millennial-scale extreme climate event, was characterized by diverse hydroclimate shifts globally and severe cooling at high northern latitudes that abruptly punctuated the warming trend from the last glacial to the present interglacial. To date, a precise understanding of its trigger, propagation, and termination remains elusive. Here, we present speleothem oxygen-isotope data that, in concert with other proxy records, allow us to quantify the timing of the YD onset and termination at an unprecedented subcentennial temporal precision across the North Atlantic, Asian Monsoon-Westerlies, and South American Monsoon regions. Our analysis suggests that the onsets of YD in the North Atlantic (12,870 ± 30 B.P.) and the Asian Monsoon-Westerlies region are essentially synchronous within a few decades and lead the onset in Antarctica, implying a north-to-south climate signal propagation via both atmospheric (decadal-time scale) and oceanic (centennial-time scale) processes, similar to the Dansgaard-Oeschger events during the last glacial period. In contrast, the YD termination may have started first in Antarctica at ∼11,900 B.P., or perhaps even earlier in the western tropical Pacific, followed by the North Atlantic between ∼11,700 ± 40 and 11,610 ± 40 B.P. These observations suggest that the initial YD termination might have originated in the Southern Hemisphere and/or the tropical Pacific, indicating a Southern Hemisphere/tropics to North Atlantic-Asian Monsoon-Westerlies directionality of climatic recovery.

Controlled enzymatic hydrolysis and synthesis of lignin cross-linked chitosan functional hydrogels.

This study presents a novel fully enzymatic process for the controlled depolymerisation of fungal and shrimp chitosan, and their subsequent use in the synthesis of lignin cross-linked chitosan (CTS) hydrogels. Cellobiosehydrolase (CBH) was used to depolymerize CTS resulting in decrease in average molecular weight (Mw) of shrimp CTS from 140 kDa and degree of deacetylation (DD %) from 91.3% to an average MW of 15 kDa and 16% DD. Similarly, fungal chitosan average molecular weight decreased from 92 kDa and the degree of deacetylation (DD) of 48.3% to 12 kDa and a DD of 13%. The depolymerized CTS were completely soluble in water and miscible with lignosulfonates without encountering the usual problem of formation of flocs. Introduction of laccase into a lignosulfonate-chitosan mixture resulted in the oxidation and generation of lignin reactive phenoxyl radicals that cross-linked with CTS-NH2 reactive groups resulting in the increase of Mw from 20 kDa to >500 kDa and viscosity from 20 mPa to >500 mPa. This resulted in the formation of stable lignin-cross-linked hydrogels with elongation at break of 111% and tensile strength of 7 mPa. The produced functional hydrogels have potential application in food and biomedical industries as e.g. as oxygen barriers in packaging or as functional wound dressing or tissue engineering platforms.

Narcea-an unknown, ancient cultivated rose variety from northern Spain.

The present work reports the discovery and the complete characterisation of an ancient cultivated rose variety found growing in a private garden in the southwest of the Principality of Asturias (northern Spain). The variety is here given the name Narcea. The majority of roses currently cultivated belong to the so-called group of 'Modern Roses', all of which were obtained after 1867 via artificial crosses and improvement programmes. All are destined for ornamental use. Until the 19th century, the great majority of the many ancient cultivated roses in Europe were used in perfumery and cosmetics, or had medicinal uses. Rosa damascena and Rosa centifollia are still grown and used by the French and Bulgarian perfume industries. The Asturian Massif of the Cantabrian Mountain Range provides a natural habitat for some 75% of the wild members of the genus Rosa, but until now there was no evidence that this area was home to ancient cultivated roses. A complete botanical description is here provided for a discovered ancient rose. It is also characterised according to a series of sequence tagged microsatellite sites, and its agronomic features are reported. In addition, a histological description (optical and scanning electronic microscope studies) of the petals is offered, along with an analysis of the volatile compounds present in these organs as determined by solid phase microextraction and gas chromatography-mass spectroscopy. The results reveal the uniqueness of this ancient type of rose and suggest it may be of interest to the perfume industry.

Global analysis reveals climatic controls on the oxygen isotope composition of cave drip water.

The oxygen isotope composition of speleothems is a widely used proxy for past climate change. Robust use of this proxy depends on understanding the relationship between precipitation and cave drip water δ18O. Here, we present the first global analysis, based on data from 163 drip sites, from 39 caves on five continents, showing that drip water δ18O is most similar to the amount-weighted precipitation δ18O where mean annual temperature (MAT) is < 10 °C. By contrast, for seasonal climates with MAT > 10 °C and < 16 °C, drip water δ18O records the recharge-weighted δ18O. This implies that the δ18O of speleothems (formed in near isotopic equilibrium) are most likely to directly reflect meteoric precipitation in cool climates only. In warmer and drier environments, speleothems will have a seasonal bias toward the precipitation δ18O of recharge periods and, in some cases, the extent of evaporative fractionation of stored karst water.

Lack of a Synergistic Effect on Cardiometabolic and Redox Markers in a Dietary Supplementation with Anthocyanins and Xanthophylls in Postmenopausal Women.

Fruits and vegetables are pivotal for a healthy diet due partly to their content in bioactive compounds. It is for this reason that we conducted a parallel study to unravel the possible effect on cardiometabolic parameters of the ingestion of anthocyanins, xanthophylls, or both groups of bioactives together in postmenopausal women. Seventy-two postmenopausal women were randomized into an 8-month parallel study: a group consuming 60 mg/day anthocyanins (Group A), a group consuming 6 mg lutein and 2 mg zeaxanthin per day (Group X), and a third group consuming a combination of anthocyanins and xanthophylls in the same amounts (Group A+X). Non-targeted metabolomic analysis was done in plasma samples at baseline and after the 8-month intervention by HPLC-QTOF-MS. Inflammatory, antioxidant, and cardiometabolic parameters were measured at the beginning of the study and after 4 and 8-months intervention. Compared with baseline values, none of the 8-month treatments significantly (p < 0.05) changed systolic or diastolic blood pressure (BP), plasma C-reactive protein, interleukin 6, vascular cell adhesion molecule-1, intercellular adhesion molecule-1, monocyte chemoattractant protein-1 or matrix metalloproteinases 2 and 9. Only plasma glucose levels were significantly decreased by treatment A+X after 8 months, and the plasma metabolomic profile was clearly affected by all three dietary supplementations after 8 months. In parallel, there was an increase, also for the three groups, in the plasma ferric reducing antioxidant power value that did not show any synergistic effect between the two groups of bioactives. Postmenopausal women could benefit from an increase in anthocyanins and xanthophylls intake, through the consumption of fruits and vegetables rich in these two types of compounds. Accordingly, plasma glucose and, above all, the reducing power in plasma, could be improved.

The effect of the combined use of high pressure treatment and antimicrobial edible film on the quality of salmon carpaccio.

Fish carpaccio is a ready-to-eat product with a very limited shelf life. In the present work, the use of high pressure treatment (HP) and/or antimicrobial edible film was studied in order to improve quality and stability of salmon carpaccio. In a preliminary part of the work, a film composed of gelatin plus chitosan incorporating clove essential oil was selected, based on its physicochemical and antimicrobial properties. Eugenol and ß-caryophyllene, the main volatile components of the film, migrated to salmon muscle, the release being favored by HP and storage time. Concurrently, reducing power of the muscle increased, resulting in prevention of lipid oxidation derived from either HP or refrigerated storage. HP treatment reduced total microbial counts by 1.5 log cycles from the onset of storage, whereas the film reduced it by 2 log cycles after 3 days. The combination of HP and edible film exerted the most intense antimicrobial effect, total bacterial counts, luminescent bacteria, H2S-producing organisms, pseudomonads, enterobacteria, and lactic acid bacteria remaining constant or under detection limit over the whole storage period (11 days). The combined use of HP treatment and gelatin-chitosan-clove essential oil film is an effective way of improving quality and stability of salmon carpaccio.

AAL Platform with a "De Facto" Standard Communication Interface (TICO): Training in Home Control in Special Education.

Framed within a long-term cooperation between university and special education teachers, training in alternative communication skills and home control was realized using the "TICO" interface, a communication panel editor extensively used in special education schools. From a technological view we follow AAL technology trends by integrating a successful interface in a heterogeneous services AAL platform, focusing on a functional view. Educationally, a very flexible interface in line with communication training allows dynamic adjustment of complexity, enhanced by an accessible mindset and virtual elements significance already in use, offers specific interaction feedback, adapts to the evolving needs and capacities and improves the personal autonomy and self-confidence of children at school and home. TICO-home-control was installed during the last school year in the library of a special education school to study adaptations and training strategies to enhance the autonomy opportunities of its pupils. The methodology involved a case study and structured and semi-structured observations. Five children, considered unable to use commercial home control systems were trained obtaining good results in enabling them to use an open home control system. Moreover this AAL platform has proved efficient in training children in previous cognitive steps like virtual representation and cause-effect interaction.

Abrupt climate changes during Termination III in Southern Europe.

The Late Quaternary glacial-interglacial transitions represent the highest amplitude climate changes over the last million years. Unraveling the sequence of events and feedbacks at Termination III (T-III), including potential abrupt climate reversals similar to those of the last Termination, has been particularly challenging due to the scarcity of well-dated records worldwide. Here, we present speleothem data from southern Europe covering the interval from 262.7 to 217.9 kyBP, including the transition from marine isotope stage (MIS) 8 to MIS 7e. High-resolution δ13C, δ18O, and Mg/Ca profiles reveal major millennial-scale changes in aridity manifested in changing water availability and vegetation productivity. uranium-thorium dates provide a solid chronology for two millennial-scale events (S8.1 and S8.2) which, compared with the last two terminations, has some common features with Heinrich 1 and Heinrich 2 in Termination I (T-I).

Metástasis hepáticas secundarias a cáncer adenoide quístico de mama: una evolución poco frecuente / Hepatic metastasis due to adenoid cystic breast cancer: an uncommon progression

No disponible

Hydrological change in Southern Europe responding to increasing North Atlantic overturning during Greenland Stadial 1.

Greenland Stadial 1 (GS-1) was the last of a long series of severe cooling episodes in the Northern Hemisphere during the last glacial period. Numerous North Atlantic and European records reveal the intense environmental impact of that stadial, whose origin is attributed to an intense weakening of the Atlantic Meridional Overturning Circulation in response to freshening of the North Atlantic. Recent high-resolution studies of European lakes revealed a mid-GS-1 transition in the climatic regimes. The geographical extension of such atmospheric changes and their potential coupling with ocean dynamics still remains unclear. Here we use a subdecadally resolved stalagmite record from the Northern Iberian Peninsula to further investigate the timing and forcing of this transition. A solid interpretation of the environmental changes detected in this new, accurately dated, stalagmite record is based on a parallel cave monitoring exercise. This record reveals a gradual transition from dry to wet conditions starting at 12,500 y before 2000 A.D. in parallel to a progressive warming of the subtropical Atlantic Ocean. The observed atmospheric changes are proposed to be led by a progressive resumption of the North Atlantic convection and highlight the complex regional signature of GS-1, very distinctive from previous stadial events.

Regular consumption of an antioxidant-rich juice improves oxidative status and causes metabolome changes in healthy adults.

An improvement in oxidative status is associated with a reduction in the incidence of several chronic diseases. However, daily intake of antioxidants in Western diets is decreasing. This study evaluates the effect of daily consumption of an antioxidant-rich juice (ARJ) on oxidative status, cardiovascular disease risk parameters, and untargeted plasma and urine metabolomes. Twenty-eight healthy young adults participated in an 8-week clinical trial by drinking 200 mL of ARJ (pomegranate and grape) daily. At the end of the study, the subjects showed a significant decrease (-29%) in plasma lipid oxidation (malondialdehyde concentration), and a significant increase (+115%) in plasma antioxidant capacity. Plasma and urine metabolomes were also significantly modified and some ions modified in urine were identified, including metabolites of polyphenols, ascorbic acid and biliary acids. No significant changes were observed in lipid profile, inflammation, blood pressure or glycaemia. These results show that incorporating antioxidant-rich beverages into common diets may improve oxidative status in healthy subjects.

Endometriosis como causa de obstrucción intestinal tratada por vía laparoscópica / Endometriosis as a cause of bowel obstruction treated with laparoscopy

La endometriosis intestinal es una causa poco frecuente de abdomen agudo que debe incluirse en el diagnóstico diferencial de la obstrucción intestinal en mujeres fértiles con antecedentes de episodios repetidos de dolor abdominal. Presentamos un caso clínico de dicha patología, diagnosticada mediante laparoscopia exploradora ante un cuadro de obstrucción intestinal sin respuesta al tratamiento conservador (AU)

Intestinal endometriosis is a very uncommon cause of acute abdomen that must be included in the differential diagnosis of small bowel obstruction in young fertile women with a history of recurrent abdominal pain. We present a case of this disease diagnosed by exploratory laparoscopy in a patient with bowel obstruction and no response to conservative treatment (AU)

Cost-effectiveness of translocation options for a threatened waterbird.

Reintroduction of captive-reared animals has become increasingly popular in recent decades as a conservation technique, but little is known of how demographic factors affect the success of reintroductions. We believe whether the increase in population persistence associated with reintroduction is sufficient to warrant the cost of rearing and relocating individuals should be considered as well. We examined the trade-off between population persistence and financial cost of a reintroduction program for Crested Coots (Fulica cristata). This species was nearly extirpated from southern Europe due to unsustainable levels of hunting and reduction in amount and quality of habitat. We used a stochastic, stage-based, single-sex, metapopulation model with site-specific parameters to examine the demographic effects of releasing juveniles or adults in each population for a range of durations. We parameterized the model with data from an unsuccessful reintroduction program in which juvenile captive-bred Crested Coots were released between 2000 and 2009. Using economic data from the captive-breeding program, we also determined whether the strategy that maximized abundance coincided with the least expensive strategy. Releasing adults resulted in slightly larger final abundance than the release of nonreproductive juveniles. Both strategies were equally poor in achieving a viable metapopulation, but releasing adults was 2-4 times more expensive than releasing juveniles. To obtain a metapopulation that would be viable for 30 years, fecundity in the wild would need to increase to the values observed in captivity and juvenile survival would need to increase to almost unity. We suggest that the most likely way to increase these vital rates is by increasing habitat quality at release sites.