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This article aims to outline a panoramic view of the paths taken by researchers, in the last 15 years, in the field of the religious history of the Modern Period in Portugal. Starting from the identification of the scientific production and activities that have achieved a more relevant place in the framework of the study of the religious history in early modern Portugal, since the 1950s, this article draws attention to a set of subjects that urgently need to be debated. It will be argued that research in the area in question continues to constitute a challenge. The focus of this article is the European space of Portugal, not considering productions and research about Portuguese imperial spaces, namely Asia and Brazil. [ABSTRACT FROM AUTHOR]

Abstract Some wastes are illegally dumped on public/private areas, causing several aesthetic, environmental, economic and social negative impacts and representing a public hazard. These sites need to be treated and managed and this task is often a responsibility of municipalities, representing high costs. However, there is a lack of strategies for the municipal management of these degraded areas that minimize costs, restore the ecological value of the area and eliminate the public hazard. This work proposes a conceptual model for the management of illegal dumping degraded areas by municipal services, based on a social life cycle assessment (SLCA). The model proposed is an open-participatory management tool which supplies the information needed for the waste management strategy for illegal waste deposit sites. Methods to evaluate and apply SLCA in this context are scarce. Therefore, SLCA is presented as a tool that can be applied to organisations in strategic analysis and structuring complex decision-making processes in order to identify optimisation potentials. It combines an environmental and a socio-economic assessment, contributing to the full assessment of products and services within the context of sustainable development. The framework intends to promote the improvement of social conditions and the socio-economic performance of a product throughout its life cycle for all the stakeholders involved within the context of sustainable development. Illegal deposits sites of Construction and Demolition Wastes (CDW) in municipalities are used as a case study for model implementation. The outputs of this model are: i) understanding the real situation of the illegally deposited wastes; ii) management practices comparing and integrating environmental, social, and economic objectives; iii) open-participatory management; iv) orientations to strategy definition; v) use of the life-cycle product principle contributing to a circular economy; and vi) assisting with municipalities performance. [ABSTRACT FROM AUTHOR]

Holistic management of water and energy resources is critical for municipalities facing increasing energy prices and stringent regulatory requirements. Management for energy efficiency in water supply and wastewater collection systems demands evaluation of how energy is consumed and how efficiently such energy is spent. The present work proposes a performance indicators matrix that allows the evaluation and monitoring of energy consumption, energy costs and CO 2 emissions, leading to the identification of opportunities for performance improvement for continuous and sustainable development in municipalities. The methodology for the development of the indicators performance matrix was based the application of the activities from integrated management systems – the integrated management energy (ISO 50001), quality (ISO 9001) and environment (ISO 14001) systems. A set of criteria and performance indicators adapted from international guidelines and literature indicators, which complement energy efficiency measure by municipalities, were chosen by consensus between experts and stakeholders. Indicators were classified according to their strategic objective in four categories: environmental (E), technical (T), social (S) and governance (G). The indicator matrix was tested in a case study, namely the municipality of Loulé in Portugal. Results showed that experts and stakeholders attribute more importance to indicators from the strategic objectives Environmental protection and Promote efficient use of water resource (34.3%), meaning that most of the chosen indicators are directly related with energy efficiency. Results of meta-evaluation of the tool showed optimal performance for most of the indicators. [ABSTRACT FROM AUTHOR]

Tin(IV)-based compounds (mono-n-butyltin hydroxide oxide ( a ), di- n -butyl-oxo-stannane ( b ), di-n-butyl tin dilaurate ( c ) and tin oxide ( d )) were used as catalysts in the hydrolysis of triacylglycerides (TGs). The effects of the nature and amount of the catalysts, the nature of the TGs, the temperature and reaction time were evaluated. Compared with the usual industrial processes, these systems showed excellent activities at mild temperatures and pressures, and low amounts of catalyst (ca. 0.3% w /w oil ). Fatty acid (FA) conversions of ca. 97% were obtained at 180 °C, 4 h at oil:water:catalyst a molar ratio of 1:24:0.01 and, using soybean oil. [ABSTRACT FROM AUTHOR]

Introduction: The -lipoic acid (ALA) has been used as a treatment to reduce oxidative damage in Systemic Arterial Hypertension (SAH), but there are no in vivo studies reporting the effect of its mechanism of action on iron metabolism.Objective: To evaluate the antioxidant effect of -lipoic acid on Blood cell count (CBC) and iron metabolism in hypertensive subjects with or without anemia.Method: Double-blind, randomized, placebo-controlled clinical trial. The sample consisted of 60 hypertensive patients that were randomly divided into treatment group (n = 32), receiving 600 mg / day of ALA for twelve weeks and control group (n = 28), receiving placebo for the same period. Blood cell count, serum iron, ferritin, Latent Iron-Binding Capacity (LIBC), Total Iron-Binding Capacity (TIBC), Transferrin Saturation Index (TSI) and transferrin were assessed before and after intervention. To assess changes between groups, the Student t-test and ANOVA were used, adopting a significance level of 5%.Results: After intervention, ALA supplementation showed a statistically significant (p < 0.05) association with the reduction of total leukocytes, increase in the number of neutrophils and reductions in the serum levels of iron and TSI.Conclusion: Oral administration of ALA as a therapeutic adjuvant changes the hematologic response of white blood cells and reduces the absorption of iron. It is observed that the mechanism of metals chelation by lipoic acid may be responsible for these changes and, consequently, could trigger a condition of iron deficiency anemia in hypertensive individuals. [ABSTRACT FROM AUTHOR]

Introduction: The α-lipoic acid (ALA) has been used as a treatment to reduce oxidative damage in Systemic Arterial Hypertension (SAH), but there are no in vivo studies reporting the effect of its mechanism of action on iron metabolism. Objective: To evaluate the antioxidant effect of α-lipoic acid on Blood cell count (CBC) and iron metabolism in hypertensive subjects with or without anemia. Method: Double-blind, randomized, placebo-controlled clinical trial. The sample consisted of 60 hypertensive patients that were randomly divided into treatment group (n = 32), receiving 600 mg / day of ALA for twelve weeks and control group (n = 28), receiving placebo for the same period. Blood cell count, serum iron, ferritin, Latent Iron-Binding Capacity (LIBC), Total Iron-Binding Capacity (TIBC), Transferrin Saturation Index (TSI) and transferrin were assessed before and after intervention. To assess changes between groups, the Student t-test and ANOVA were used, adopting a significance level of 5%.Results: After intervention, ALA supplementation showed a statistically significant (p < 0.05) association with the reduction of total leukocytes, increase in the number of neutrophils and reductions in the serum levels of iron and TSI. Conclusion: Oral administration of ALA as a therapeutic adjuvant changes the hematologic response of white blood cells and reduces the absorption of iron. It is observed that the mechanism of metals chelation by lipoic acid may be responsible for these changes and, consequently, could trigger a condition of iron deficiency anemia in hypertensive individuals. [ABSTRACT FROM AUTHOR]

Recently, there has been an outburst of research on engineered cell–material interfaces driven by nanotechnology and its tools and techniques. This tutorial review begins by providing a brief introduction to nanostructured materials, followed by an overview of the wealth of nanoscale fabrication and analysis tools available for their development. This background serves as the basis for a discussion of early breakthroughs and recent key developments in the endeavour to develop nanostructured materials as smart interfaces for fundamental cellular studies, tissue engineering and regenerative medicine. The review covers three major aspects of nanostructured interfaces – nanotopographical control, dynamic behaviour and intracellular manipulation and sensing – where efforts are continuously being made to further understand cell function and provide new ways to control cell behaviour. A critical reflection of the current status and future challenges are discussed as a conclusion to the review. [ABSTRACT FROM AUTHOR]

Objectives: cigarette smoking has been the modifiable risk factor most consistently associated with earlier menopause. This preliminary study based on cross-sectional data aimed to analyze the association between smoking status and age of onset of menopause in a Brazilian population. Methods: a cross-sectional study was carried out with 1,222 female employees of Rio de Janeiro university campuses aged over 35 years who were at risk of natural menopause. A Cox proportional hazards model was used to investigate the association between smoking status and age at the onset of menopause, adjusting for education, parity and alcohol consumption. Results: current smokers showed a 56% increase in the risk of menopause, being 1.8 years younger at menopause onset compared with women who had never smoked. However, no differences were observed between former smokers and women who had never smoked. The adjusted median age at menopause was 49.5 years for current smokers and 51.3 years for women who had never smoked (p<0.05). Conclusions: the results suggest a deleterious but potentially reversible effect of smoking on the age of onset of menopause, which should receive greater attention in tobacco control efforts. Longitudinal analyses of this association will be carried out in the future in a follow-up study of this population. [ABSTRACT FROM AUTHOR]

Abstract: The evaluation of municipal solid waste (MSW) services using management systems (ISO 9001, ISO 14001, and OHSAS 18001) is important for improving the quality of such services. In this study, we prioritize and select performance indicators (PIs) for MSW service evaluation and organize them in a Balanced Scorecard (BSC) tool. The tool is applied for the period 2008–2011 to the public administration organization responsible for waste management in Loulé Municipality, Portugal, a region characterized by strong tourist seasonality. MSW management priorities are well established through EU directives and the application of PIs should allow service objectives to be quantified, including reducing the production of waste, increasing the quantity of recyclables, improving clients’ satisfaction with the service, improving workers’ motivation, decreasing the quantities of waste in landfills, and reducing service costs. The results indicate that the use of indicators and BSC tool can assess the strategic objectives of the organization and monitor its performance over time. The overall BSC assessment ratings were 51.7%, 66.1%, and 70.1% for 2009, 2010, and 2011, respectively, indicating an improvement in overall service performance over time. The results demonstrate that monitoring seasonal variations of PIs in tourist regions is important since these variations can help to explain annual changes in the factors affecting waste services management, their impacts on overall service quality, and the best time for measures to be applied. Based on this case study, the BSC can effectively contribute to improvements in the quality and cost of MSW services in areas characterized by strong seasonal variations in population and waste. [Copyright &y& Elsevier]

Abstract: Municipal solid waste management is an area where improvements are needed, in accordance with European Union regulations, in order to ensure sustainable development principles and best management practices. In this context, Portugal implemented a strategy in 2003 under the title “New Public Management”, the main objective of which is to create value for citizens, with a particular focus on improving performance in the public management of wastes and allocating resources. This strategy is based on the introduction of market mechanisms, thus adopting management tools common in the private sector. The objective of this paper is to propose and implement a management tool − the Balanced Scorecard (BSC) − suited for the needs of the Public Administration (PA) service in the waste sector. The BSC was applied to the Urban Hygiene and Solid Waste Division of the Loulé Municipality in the south of Portugal. Four perspectives were used, namely, clients, internal processes, learning and growth and finances. Results indicate an overall management performance of 52.45%, which was considered a good result since it was the first implementation approach. Out of the four BSC perspectives, the learning and growth perspective (15% weighting of overall management performance) and the financial perspective (10% weighting) had the smaller achievement performances, of just 4% and 1.75% of the indicators achieved, respectively. The internal process perspective (50% weighting) and the client perspective (25% weighting) had higher achievement performances at 34.2% and 12.5%, respectively. Overall, in the Portuguese PA service, the BSC is able to: i) contribute to the precepts of modern public waste management; ii) focus on the strategic management of the client–customer relationship; iii) guarantee the best combination of improvement in service, through monitoring and a follow-up process; and iv) achieve management objectives. [Copyright &y& Elsevier]

Abstract: A Pt/C electrocatalyst was prepared from colloidal Pt nanoparticles stabilised by Nafion. This electrocatalyst was found to exhibit negligible degradation under a potential cycling regime conducted on a model thin-film catalyst layer in a 3-electrode cell set-up, in which an E-Tek Pt/C commercial catalyst showed a 23% loss of specific electrochemical surface area (SECSA). The enhanced durability of the Nafion-derived is thought to arise from the protection of Pt particles against dissolution and sintering by the surrounding Nafion layer. The use of the ionomer phase as a protective agent in the catalyst layer presents a novel strategy for the production of more durable Pt/C catalysts for the Proton Exchange Membrane Fuel Cell (PEMFC), which currently presents a significant challenge for the commercialisation of this technology. [Copyright &y& Elsevier]

Acid-base switchable supramolecular dendronized polyacetylenes (DPAs) with increasing steric bulk on going from generation one [G1] to three [G3], were constructed using multiple self-assembly processes between Fréchet-type [G1]–[G3]-dendritic dialkylammonium salts and a dibenzo[24]crown-8-containing polymer. The formation of the supramolecular systems is acid-base switchable to either an ON (rodlike dendronized polymers) or an OFF (flexible polymers) state. Thus, by controlling the superstructures of the supramolecular polymers with the [G1]–[G3] dendrons, it is possible to induce conformational changes within the polymer backbones. The supramolecular dendronized polymers, as well as their threading-dethreading properties, were characterized by 1H NMR and UV absorption spectroscopies, gel permeation chromatography (GPC) and light scattering (LS). Independent measures of molecular weight (GPC, LS) indicate that DPAs behave as increasingly rigid macromolecules with each generation in solution. Molecular dynamics simulations of each DPA suggest that the lengths of the polymer backbones increase accordingly. Atomic force microscopy of the [G3]-dendronized polystyrene (DPS), as well as the DPAs, reveal surface morphologies indicative of aggregated superstructures. [ABSTRACT FROM AUTHOR]

Precise control over functional three-dimensional nanoarchitectures and how to integrate them across different length scales is a significant challenge in nanoscience and nanoengineering. In recent years, hybrid top-down/bottom-up processes, which combines the precision of lithographic techniques and the parallelism of self-assembly—what might be termed precision chemical engineering, have been actively pursued for realising such a major task. Lithographic radiative techniques, including ultraviolet (UV) light, X-rays and electron-beam (e-beam), have been used for creating nanostructured surfaces on self-assembled monolayers (SAMs), which offer unprecedented range of surface chemical functionalities. Generation of three-dimensional nanostructures by self-organisation of self-assembled nanoscale components onto nanopatterned SAM surface templates has also been demonstrated. Nevertheless, these methodologies are in their early stages offering ample opportunity for further research and process development. [Copyright &y& Elsevier]

We analyzed the results of treating patients who had chronic daily headaches that were refractory to standard medications with repetitive low-dose boluses of intravenous propofol (2,6-diisopropylphenol). Patients were treated over a 1-year period at Thomas Jefferson University Hospital. A total of 18 patients were treated a total of 21 times. Over 90% of patients had at least some headache relief after treatment. The headache cycle was broken in eight patients. There were no complications. Intravenous propofol is safe and effective when used under monitored conditions and should be considered for patients who have refractory chronic daily headache and have failed other interventions. [ABSTRACT FROM AUTHOR]

Recognition of oligosaccharides is associated with very limited specificity due to their strong solvation in water and the high degree of subtle structural variations between them. Here, oligosaccharide recognition sites are created on material surfaces with unmatched, binary on–off binding behavior, sharply discriminating a target oligosaccharide over closely related carbohydrate structures. The basis for the superselective binding behavior relies on the highly efficient generation of a pure, high order complex of the oligosaccharide target with synthetic carbohydrate receptor sites, in which the spatial arrangement of the multiple receptors in the complex is preserved upon material surface incorporation. The synthetic binding scaffolds can easily be tailored to recognize different oligosaccharides and glycoconjugates, opening up a realm of possibilities for their use in a wide field of applications, ranging from life sciences to diagnostics. [ABSTRACT FROM AUTHOR]

The commercialisation of polymer electrolyte fuel cells (PEFCs) has been hampered by the high cost of platinum metal. Due to its high durability and catalytic activity, platinum is widely used to catalyse the oxygen reduction and hydrogen oxidation reactions essential to the operation of these cells. Core@shell nanoparticles with thin layers of platinum deposited on cores composed of cheaper materials have offered an attractive route towards the reduction of overall loading of platinum, with the retention of active catalyst surface area. This review surveys approaches taken to prepare idealised active and durable core@shell nanocatalysts by tweaking core compositions. A critical reflection on the current status of the field, as well as predictions as to likely directions for future developments, are discussed as a conclusion to the review. [ABSTRACT FROM AUTHOR]

Review: 59 refs. [ABSTRACT FROM AUTHOR]

Chlortalidone (CTD) is a diuretic drug largely used as part of antihypertensive therapies. It is marketed as an equimolar mixture of its enantiomers in the racemic crystal phase named Form I, despite of the higher aqueous solubility of another crystal form. The latter, named Form II, was thought to contain both enantiomers as a racemic conglomerate, i . e ., in the form of a mixture of crystals, half of which consists solely of the (R)-enantiomer, the other half the (S)-enantiomer. The occurrence of both enantiomers in individual crystals of CTD Form II was demonstrated in this study. Spontaneous resolution does really occur upon crystallization, as presumed previously even without physical evidence of the (S)-enantiomer. Both (R) and (S)-enantiomers were successfully identified as two domains of a twinned by inversion single crystal of CTD Form II. A reliable Flack parameter of 0.14(4) allowed to determine the proportion of the enantiomers in the crystal, which is formed with 86% of the (R)-enantiomer and 14% of the (S)-enantiomer. [ABSTRACT FROM AUTHOR]

The kynurenine metabolite is associated with many diseases and disorders, ranging from diabetes and sepsis to more recently COVID-19. Here we report a fluorescence-based assay for the detection of kynurenine in urine using a specific chemosensor, 3-formyl-4-(ethylthio)-7-(diethylamino)-coumarin. The assay produces a linear response at clinically relevant ranges (1–20 μM), with a limit of detection of 0.7 μM. The average standard addition recoveries of kynurenine in synthetic urine samples are near to 100%, and the relative standard deviation values are less than 8%. The established fluorescence assay for quantitative analysis of kynurenine in urine is facile, sensitive and accurate and holds great potential for low-cost and high-throughput analysis of kynurenine in clinical laboratory settings. [ABSTRACT FROM AUTHOR]

Reported herein is a switchable surface that relies on electrically-induced conformational changes within surface-grafted arginine-glycine- aspartate (RGD) oligopeptides as the means of modulating cell adhesion. [ABSTRACT FROM AUTHOR]

Charge interactions play a critical role in the activation of the innate immune system by damage- and pathogen-associated molecular pattern receptors. The ability of these receptors to recognize a wide spectrum of ligands through a common mechanism is critical in host defense. In this article, we argue that platelet glycoprotein receptors that signal through conserved tyrosine-based motifs function as pattern recognition receptors (PRRs) for charged endogenous and exogenous ligands, including sulfated polysaccharides, charged proteins and nanoparticles. This is exemplified by GPVI, CLEC-2 and PEAR1 which are activated by a wide spectrum of endogenous and exogenous ligands, including diesel exhaust particles, sulfated polysaccharides and charged surfaces. We propose that this mechanism has evolved to drive rapid activation of platelets at sites of injury, but that under some conditions it can drive occlusive thrombosis, for example, when blood comes into contact with infectious agents or toxins. In this Opinion Article, we discuss mechanisms behind charge-mediated platelet activation and opportunities for designing nanoparticles and related agents such as dendrimers as novel antithrombotics. [ABSTRACT FROM AUTHOR]

In the biomedical field, many innovative materials to improve diagnosis and treatment of diseases are currently being developed. The ability to respond to different stimuli is one of the more interesting properties of such materials. Light, as one of the nature's elementary stimuli, offers an attractive and flexible stimulus for controlling the properties and functions of biomedical‐related materials. As such, photoresponsive systems have been increasingly pursued and finding applications in various biomedical settings, ranging from tissue engineering for the fabrication of bespoke tissue scaffolds to drug delivery, aims at manipulating treatment distribution inside the human body. Efforts have also been devoted to the development of highly efficient methods to control biological activity and bring us closer to mimicking impressive biological actuators. In this progress report, an overview of recent developments in the field is provided and current challenges discussed. Key strategies tailored to address specific issues are examined, offering useful perspectives for future designs. [ABSTRACT FROM AUTHOR]

Glycans – simple or complex carbohydrates – play key roles as recognition determinants and modulators of numerous physiological and pathological processes. Thus, many biotechnological, diagnostic and therapeutic opportunities abound for molecular recognition entities that can bind glycans with high selectivity and affinity. This review begins with an overview of the current biologically and synthetically derived glycan-binding scaffolds that include antibodies, lectins, aptamers and boronic acid-based entities. It is followed by a more detailed discussion on various aspects of their generation, structure and recognition properties. It serves as the basis for highlighting recent key developments and technical challenges that must be overcome in order to fully deal with the specific recognition of a highly diverse and complex range of glycan structures. [ABSTRACT FROM AUTHOR]

Our ability to tailor the electronic properties of surfaces by nanomodification is paramount for various applications, including development of sensing, fuel cell, and solar technologies. Moreover, in order to improve the rational design of conducting surfaces, an improved understanding of structure/function relationships of nanomodifications and effect they have on the underlying electronic properties is required. Herein, we report on the tuning and optimization of the electrochemical properties of indium tin oxide (ITO) functionalized with single-walled carbon nanotubes (SWCNTs). This was achieved by controlling in situ grafting of aryl amine diazonium films on the nanoscale which were used to covalently tether SWCNTs. The structure/function relationship of these nanomodifications on the electronic properties of ITO was elucidated via time-of-flight secondary ion mass spectrometry and electrochemical and physical characterization techniques which has led to new mechanistic insights into the in situ grafting of diazonium. We discovered that the connecting bond is a nitro group which is covalently linked to a carbon on the aryl amine. The increased understanding of the surface chemistry gained through these studies enabled us to fabricate surfaces with optimized electron transfer kinetics. The knowledge gained from these studies allows for the rational design and tuning of the electronic properties of ITO-based conducting surfaces important for development of various electronic applications. [ABSTRACT FROM AUTHOR]

The important role of vesicles in many aspects of cell function is well-recognized, but only recently have sophisticated imaging techniques begun to reveal their ubiquity in nature. While we further our understanding of the biological properties of vesicles and their physiological functions, increasingly elegant artificial vesicles are being developed for a wide range of technological applications and basic research. Herein, we examine the state of the art of biological and synthetic vesicles and place their biological features in the context of recent synthetic developments, thus providing a unique overview of these complex and rapidly developing fields. The challenges and opportunities associated with future biological and synthetic studies of vesicles are also presented. [ABSTRACT FROM AUTHOR]

Die wichtige Rolle von Vesikeln in vielen Bereichen der Zellfunktion ist gut bekannt, aber erst seit kurzem offenbart sich mithilfe neuer, komplexerer Bildgebungsverfahren ihre Allgegenwart in der Natur. Während die biologischen Eigenschaften von Vesikeln und ihre physiologischen Funktionen immer besser verstanden werden, werden auch vermehrt sehr elegante, künstliche Vesikel für eine Reihe technischer Anwendungen und die Grundlagenforschung entwickelt. Hier wollen wir den Stand der Technik von biologischen und synthetischen Vesikeln darstellen und ihre biologischen Eigenschaften in Zusammenhang mit aktuellen Syntheseentwicklungen bringen, um so einen Überblick über diese komplexen, rasch aufstrebenden Fachgebiete zu geben. Darüber hinaus werden die Herausforderungen und Möglichkeiten für die zukünftige biologische und präparative Entwicklung von Vesikeln präsentiert. Natürliche und künstliche Vesikel: Parallel zur Aufklärung der biologischen Eigenschaften und physiologischen Funktion von Vesikeln werden immer elegantere künstliche Vesikel beschrieben. In diesem Aufsatz soll ein Überblick über biologische und präparative Fortschritte gegeben und gezeigt werden, wie beide Forschungsgebiete voneinander profitieren können. [ABSTRACT FROM AUTHOR]

Conspectus Stimuli-responsive surfaces have sparked considerable interest in recent years, especially in view of their biomimetic nature and widespread biomedical applications. Significant efforts are continuously being directed at developing functional surfaces exhibiting specific property changes triggered by variations in electrical potential, temperature, pH and concentration, irradiation with light, or exposure to a magnetic field. In this respect, electrical stimulus offers several attractive features, including a high level of spatial and temporal controllability, rapid and reverse inducement, and noninvasiveness. In this Account, we discuss how surfaces can be designed and methodologies developed to produce electrically switchable systems, based on research by our groups. We aim to provide fundamental mechanistic and structural features of these dynamic systems, while highlighting their capabilities and potential applications. We begin by briefly describing the current state-of-the-art in integrating electroactive species on surfaces to control the immobilization of diverse biological entities. This premise leads us to portray our electrically switchable surfaces, capable of controlling nonspecific and specific biological interactions by exploiting molecular motions of surface-bound electroswitchable molecules. We demonstrate that our self-assembled monolayer-based electrically switchable surfaces can modulate the interactions of surfaces with proteins, mammalian and bacterial cells. We emphasize how these systems are ubiquitous in both switching biomolecular interactions in highly complex biological conditions while still offering antifouling properties. We also introduce how novel characterization techniques, such as surface sensitive vibrational sum-frequency generation (SFG) spectroscopy, can be used for probing the electrically switchable molecular surfaces in situ. SFG spectroscopy is a technique that not only allowed determining the structural orientation of the surface-tethered molecules under electroinduced switching, but also provided an in-depth characterization of the system reversibility. Furthermore, the unique support from molecular dynamics (MD) simulations is highlighted. MD simulations with polarizable force fields (FFs), which could give proper description of the charge polarization caused by electrical stimulus, have helped not only back many of the experimental observations, but also to rationalize the mechanism of switching behavior. More importantly, this polarizable FF-based approach can efficiently be extended to light or pH stimulated surfaces when integrated with reactive FF methods. The interplay between experimental and theoretical studies has led to a higher level of understanding of the switchable surfaces, and to a more precise interpretation and rationalization of the observed data. The perspectives on the challenges and opportunities for future progress on stimuli-responsive surfaces are also presented. [ABSTRACT FROM AUTHOR]

The fabrication of a molecularly tailored surface functionalised with a saccharide binding motif, a phenyl boronic acid derivative is reported. The functionalised surface facilitated the transfer of electrons, via unique electronic interactions mediated by the presence of the boronic acid, from a macrophage cell line. This is the first example of eukaryotic cellular-electrical communication mediated by the binding of cells via their cell–surface saccharide units. [ABSTRACT FROM AUTHOR]

Sn(IV) complexes (dimethyltin dineodecanoate ( 1 ), dibutyltin dineodecanoate ( 2 ), dioctyltin dineodecanoate ( 3 ), dimethyltin diundec-10-enoate ( 4 ), dibutyltin diundec-10-enoate ( 5 ), tributyltin undec-10-enoate ( 6 ) and tributyltin undecanoate ( 7 )) were tested as catalysts for transesterification or esterification in the presence of methanol, in order to investigate the effect of the substituents coordinated to the metal center. All complexes were active at relative high reaction temperatures, and their reactivity can be associated with the steric effects induced by the substituents (alkyls and carboxylates) at the metal center. [ABSTRACT FROM AUTHOR]

Herein, electrically switchable mixed self-assembled monolayers based on oligopeptides have been developed and investigated for their suitability in achieving control over biomolecular interactions in the presence of complex biological conditions. Our model system, a biotinylated oligopeptide tethered to gold within a background of tri(ethylene glycol) undecanethiol, is ubiquitous in both switching specific protein interactions in highly fouling media while still offering the non-specific protein-resistance to the surface. Furthermore, the work demonstrated that the performance of the switching on the electro-switchable oligopeptide is sensitive to the characteristics of the media, and in particular, its protein concentration and buffer composition, and thus such aspects should be considered and addressed to assure maximum switching performance. This study lays the foundation for developing more realistic dynamic extracellular matrix models and is certainly applicable in a wide variety of biological and medical applications. [ABSTRACT FROM AUTHOR]

Abstract: In the present work we develop a real-time electrochemical mediator assay to enable the assessment of cell numbers and chemical toxicity. This allowed us to monitor metabolism down to a single cell in a low cost easy to use rapid assay which is not possible with current technology. The developed assay was based on the determination of oxygen. This was made possible via the use of electrochemical mediator ferrocene carboxylic acid (FcA). The FcA showed distinctive catalytic properties in interacting with reactive oxygen species generated from oxygen when compared to ferrocene methanol (FcMeOH). A deeper insight into the chemistry controlling this behaviour is provided. The behaviour is then taken advantage of to develop a cellular aerobic respiration assay. We describe the properties of the FcA system to detect, in real-time, the oxygen consumption of Escherichia coli DH5-α (E. coli). We demonstrated that the FcA-based oxygen assay is highly sensitive, and using a population of cells, oxygen consumption rates could be calculated down to a single cell level. More importantly, the results can be accomplished in minutes, considerably outperforming current commercially available biooxygen demand assays. The developed assay is expected to have a significant impact in diverse fields and industries, ranging from environmental toxicology through to pharmaceutical and agrochemical industries. [Copyright &y& Elsevier]

Saccharides – a versatile class of biologically important molecules – are involved in a variety of physiological and pathological processes, but their detection and quantification is challenging. Herein, surface plasmon resonance and self-assembled monolayers on gold generated from bis-boronic acid bearing a thioctic acid moiety, whose intramolecular distance between the boronic acid moieties is well defined, are shown to detect d-glucose with high selectivity, demonstrating a higher affinity than other saccharides probed, namely d-galactose, d-fructose and d-mannose. [ABSTRACT FROM AUTHOR]

A bis-boronic acid modified electrode for the sensitive and selective determination of glucose concentrations has been developed. The electrochemical characteristics of the sensor with added saccharides were investigated using cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS). The bis-boronic acid modified electrode was both sensitive and selective for glucose. [ABSTRACT FROM AUTHOR]

Abstract: Three Sn(IV) complexes, named butyl stannoic acid (BTA), di-n-butyl-oxo-stannane (DBTO) and dibutyltin dilaurate (DBTDL), were initially tested as catalysts for esterification reaction of fatty acids in the presence of methanol as alcoholysis agent. Parameters like reaction time, temperature, and catalyst amount were systematically evaluated in this work. All complexes were active at relative high reaction temperatures, but BTA displayed the highest activity. Former studies have already demonstrated that these same complexes display good catalytic activity in methanolysis of triacylglycerides (TAGs). These results prompted us to test BTA catalyst also in simultaneous esterification/transesterification reactions from a mixture of free fatty acids (FFAs) and TAGs in the presence of methanol. BTA was able to convert the mixtures in to fatty acid methyl esters (FAMEs) with good yields, with simple isolation processes. The results obtained and discussed in this work can help the development of new catalytic systems to biodiesel production from oils with very high acid content. [Copyright &y& Elsevier]

The article presents a study that examines the solitary bone fragments from the uterine cavity by using deoxyribonucleic acid (DNA) genotyping to determine its origin. It states that DNA was extracted from the blood and bone fragments of 14 patients and was genotyped through polymerase chain reactions for DNA loci. Furthermore, it shows that the blood and tissue samples produced similar pair of alleles for all loci suggesting that the bone formation was due to osseous metaplasia.

Kidney and anemia in familial amyloidosis type I.Background.Familial amyloid polyneuropathy (FAP) type I is caused by a mutated transthyretin (TTR V30M) and characterized by a sensorimotor and autonomic neuropathy. Renal, cardiac, and ocular abnormalities can also occur. Anemia has been described in previous reports, but its prevalence in Portuguese FAP patients is not precisely known. The aim of this study was to estimate the prevalence of anemia in FAP type I Portuguese patients and to evaluate the contribution of erythropoietin (Epo) to its genesis.Methods.A retrospective cross-sectional study was undertaken to determinate the prevalence and characteristics of anemia in 165 FAP patients. For comparison analysis, 3 control groups were also evaluated, 1 group of 46 apparently healthy subjects, 1 group of 17 asymptomatic carriers of FAP-trait, and a group of 14 non-FAP patients with chronic renal insufficiency. Serum Epo levels were analyzed in all groups.Results.Anemia was present in 24.8% of symptomatic FAP patients. Iron stores, B12 vitamin, and serum folate levels were normal. FAP patients presented significantly lower serum Epo levels than healthy controls (P= 0.003). Epo levels were found lower than expected for the degree of anemia and in 17.5% were undetectable. Low Epo values were observed independently of the presence of renal failure or anemia, and sometimes preceded clinical disease.Conclusion.Anemia in FAP type I is a common manifestation. The results clearly suggest a defective endogenous Epo production in the genesis of the anemia. [ABSTRACT FROM AUTHOR]

Type III-B first generation [3]rotaxane and second generation [4]rotaxane dendrimers have been synthesized via (1) a modified copper-catalyzed alkyne–azide cycloaddition (CuAAC), (2) Glaser–Hay's acetylenic oxidative homo-coupling, and (3) amide formation. The dendron does not reveal obvious cytotoxicities in L929 fibroblast cells. The rotaxane dendrimers can capture ammonia and are switchable both in solution and on surfaces. [ABSTRACT FROM AUTHOR]

Correction for 'The challenges of glycan recognition with natural and artificial receptors' by Stefano Tommasone et al., Chem. Soc. Rev., 2019, 48, 5488–5505. [ABSTRACT FROM AUTHOR]

Background: Postoperative pulmonary complications (PPCs) contribute significantly to overall postoperative morbidity and mortality. In abdominal surgery, PPCs remain frequent. The study aimed to analyze the profile and outcomes of PPCs in patients submitted to abdominal surgery and admitted in a Portuguese polyvalent intensive care unit. Methods: From January to December 2017 in the polyvalent intensive care unit of Hospital Garcia de Orta, Almada, Portugal, we conducted a retrospective, observational study of inpatients submitted to urgent or elective abdominal surgery who had severe PPCs. We evaluated the perioperative risk factors and associated mortality. Logistic regression was performed to find which perioperative risk factors were most important in the occurrence of PPCs. Results: Sixty patients (75% male) with a median age of 64.5 [47–81] years who were submitted to urgent or elective abdominal surgery were included in the analysis. Thirty-six patients (60%) developed PPCs within 48 h and twenty-four developed PPCs after 48 h. Pneumonia was the most frequent PPC in this sample. In this cohort, 48 patients developed acute respiratory failure and needed mechanical ventilation. In the emergency setting, peritonitis had the highest rate of PPCs. Electively operated patients who developed PPCs were mostly carriers of digestive malignancies. Thirty-day mortality was 21.7%. The risk of PPCs development in the first 48 h was related to the need for neuromuscular blocking drugs several times during surgery and preoperative abnormal arterial blood gases. Median abdominal surgical incision, long surgery duration, and high body mass index were associated with PPCs that occurred more than 48 h after surgery. The American Society of Anesthesiologists physical status score 4 and COPD/Asthma determined less mechanical ventilation needs since they were preoperatively optimized. Malnutrition (low albumin) before surgery was associated with 30-day mortality. Conclusion: PPCs after abdominal surgery are still a major problem since they have profound effects on outcomes. Our results suggest that programs before surgery, involve preoperative lifestyle changes, such as nutritional supplementation, exercise, stress reduction, and smoking cessation, were an effective strategy in mitigating postoperative complications by decreasing mortality. [ABSTRACT FROM AUTHOR]

Herein, a concise and novel method is developed to directly generate Mn‐doped ZnS QDs/alginate nanocomposite beads. In this method, the ionic gelation of alginate is employed to produce alginate gel beads in a solution of Zn2+ and Mn2+ ions. Subsequently, the gel beads serve as the reaction support for in situ synthesis of Mn‐doped ZnS QDs in the beads through the reaction of sodium sulfide with Zn2+ and Mn2+ ions. The method has many benefits such as the simple preparation, the environmentally friendly process, the mild conditions, and the easy post‐treatment for the beads. The resulting QDs/alginate beads are homogeneous and stable gel spheres which show clear fluorescence. TEM images demonstrate that Mn‐doped ZnS QDs are homogeneously distributed within the QDs/alginate nanocomposite, and their average size is 2.4 ± 0.3 nm. Potentially, the QDs/alginate beads can be utilized for fluorescence bioimaging, as well as fluorescence detection toward metal ions. In this work, a novel, concise, and convenient method, based on the ionic gelation of alginate and in situ synthesis of QDs, is developed to directly fabricate Mn‐doped ZnS QDs/alginate nanocomposite beads. The method offers benefits such as the simple operation, the environmentally friendly process, the mild conditions, and the easy separation and post‐treatment for the nanocomposite beads. [ABSTRACT FROM AUTHOR]

Novel type III-B dendrimers are synthesized via a modified copper-catalyzed alkyne-azide cycloaddition, a Glaser-Hay′s acetylenic oxidative homocoupling, and an amide formation. [ABSTRACT FROM AUTHOR]