Dynamic TG studies on the thermal decomposition of PVC plastisols

The kinetics involved in the thermal decomposition of PVC plastisols and unmixed PVC-plasticizer systems were compared using dynamic thermogravimetric (TG) analysis. Three kinetic models were tested. In all cases thermograms obtained at different heating rates were simultaneously correlated with the same constants. Significant differences indicative of PVC-plasticizer (DOP) interactions were found between the plastisol systems and the unmixed PVC-plasticizer systems. When the plasticizer is in the paste, its evolution suffers a delay with respect to the case when PVC and plasticizer were separated. The activation energy for DOP evolution takes the value 109.2 in the first case and 81.6 KJ/mol in the second case. PVC decomposition takes place at lower temperatures when it is in the paste, and its activation energy is 177.4 and 206.7 KJ/mol for PVC in plastisol and unmixed PVC, respectively.     

The Era of Digital Health: A Review of Portable and Wearable Affinity Biosensors

Digital health facilitated by wearable/portable electronics and big data analytics holds great potential in empowering patients with real‐time diagnostics tools and information. The detection of a majority of biomarkers at trace levels in body fluids using mobile health (mHealth) devices requires bioaffinity sensors that rely on “bioreceptors” for specific recognition. Portable point‐of‐care testing (POCT) bioaffinity sensors have demonstrated their broad utility for diverse applications ranging from health monitoring to disease diagnosis and management. In addition, flexible and stretchable electronics‐enabled wearable platforms have emerged in the past decade as an interesting approach in the ambulatory collection of real‐time data. Herein, the technological advancements of mHealth bioaffinity sensors evolved from laboratory assays to portable POCT devices, and to wearable electronics, are synthesized. The involved recognition events in the mHealth affinity biosensors enabled by bioreceptors (e.g., antibodies, DNAs, aptamers, and molecularly imprinted polymers) are discussed along with their transduction mechanisms (e.g., electrochemical and optical) and system‐level integration technologies. Finally, an outlook of the field is provided and key technological bottlenecks to overcome identified, in order to achieve a new sensing paradigm in wearable bioaffinity platforms.     

Incentivized provision of metadata, semantic reasoning and time-driven filtering: Making a puzzle of personalized e-commerce

e-Commerce recommender systems select potentially interesting products for users by looking at their purchase histories and preferences. In order to compare the available products against those included in the user’s profile, semantics-based recommendation strategies consider metadata annotations that describe their main attributes. Besides, to ensure successful suggestions of products, these strategies adapt the recommendations as the user’s preferences evolve over time. Traditional approaches face two limitations related to the aforementioned features. First, product providers are not typically willing to take on the tedious task of annotating accurately a huge diversity of commercial items, thus leading to a substantial impoverishment of the personalization quality. Second, the adaptation process of the recommendations misses the time elapsed since the user has bought an item, which is an essential parameter that affects differently to each purchased product. This results in some pointless recommendations, e.g. including regularly items that the users are only willing to buy sporadically. In order to fight both limitations, we propose a personalized e-commerce system with two main features. On the one hand, we incentivize the users to provide high-quality metadata for commercial products; on the other, we explore a strategy that offers time-aware recommendations by combining semantic reasoning about these annotations with item-specific time functions. The synergetic effects derived from this combination lead to suggestions adapted to the particular needs of the users at any time. This approach has been experimentally validated with a set of users who accessed our personalized e-commerce system through a range of fixed and handheld consumer devices.     

Endocrine alteration and other biochemical responses in juvenile turbot exposed to the Prestige fuel oil

Juvenile turbot (Scophthalmus maximus) were exposed to different concentrations of the Prestige fuel oil through the diet. The effects on hepatic biotransformation enzymes, namely, 7-ethoxyresorufin O-deethylase (EROD), catalase, and phase II activities - UDP-glucuronosyltransferases (UGT) and cytosolic sulfotransferases (SULT) -, were monitored after 42-day exposure. Additionally, potential alterations on the endocrine system of juvenile turbot were assessed by measuring circulating levels of testosterone and 17beta-estradiol in plasma, together with gonadal P450 aromatase activity and the glucuronidation of testosterone by liver microsomal fractions. Fluorescent aromatic compounds (FACs) in bile were determined as an indicator of exposure to polycyclic aromatic hydrocarbons (PAHs). EROD activity increased in a dose dependent manner, and a positive correlation between levels of FACs in bile and EROD activity was observed. A significant increase in UGT activity was observed in fish exposed to medium and high fuel doses, whereas SULT cytosolic activity was not responsive to exposure. Exposure to the Prestige fuel oil sharply reduced circulating levels of testosterone in plasma. The obtained results suggest the ability of the Prestige fuel oil to alter hepatic biotransformation enzymes and to disrupt endogenous hormone levels in juvenile turbot, with unknown consequences in terms of sexual differentiation and reproduction.     

Poly(vinyl alcohol)-poly(acrylic acid) interpenetrating networks. Study on phase separation and molecular motions

We report on the preparation and characterization of interpenetrating polymer networks (IPNs) composed of poly(vinyl alcohol) (PVA) and poly(acrylic acid) (PAAc) formed by a sequential method. Interpolymer interactions were examined using ¹³C CP/MAS NMR and DSC methods. Evidence on the formation of a PVA-PAAc complex through hydrogen bonds between the hydroxyl groups of the PVA chains and the carbonyl group of the PAAc chains was obtained. The existence of polymer interactions between PVA and PAAc and its effect on the molecular motion of polymer chains, was further investigated by means of the analysis of the ¹³C spin-lattice relaxation times in the rotating frame, . To elucidate the scale of the mixing in the PVA/PAAc IPNs, proton spin-lattice relaxation times in the rotating frame, , were also investigated. The analysis of the results reveals the compatibility between the PVA and the PAAc polymer networks at low PVA concentrations and the occurrence of phase separation at relatively high PVA concentrations.     

Unexpected effect of the vehicle (grain ethanol) of homeopathic FSH on the in vitro survival and development of isolated ovine preantral follicles

The aims of this study were to investigate the effects of medium replacement system (experiment I) and of FSH presentations (homeopathic – FSH 6cH and allopathic FSH – rFSH; experiment II) on the in vitro development, hormone production and gene expression of isolated ovine preantral follicles cultured for 6 days. In experiment I, secondary follicles were cultured in the α‐MEM⁺ supplemented with FSH 6cH (0.05 fg/ml) or recombinant bovine FSH (100 ng/ml) without/with daily medium addition. The homeopathic FSH treatments with/without medium addition improved (p < .05) follicular development compared to rFSH100 treatment without addition. FSH 6cH with addition showed the highest (p < .05) estradiol production. To verify whether the effects of homeopathic FSH were not due to its vehicle, experiment II was performed. The α‐MEM⁺ was supplemented or not with alcohol (0.2% grain ethanol, v/v), FSH 6cH or rFSH100 with daily medium addition. Surprisingly, we found that all treatments improved follicular development compared to the α‐MEM⁺ (p < .05). Moreover, homeopathic FSH was similar to the other treatments including its vehicle. In conclusion, its vehicle (ethanol) causes the effect of homeopathic FSH on in vitro development of isolated ovine preantral follicles.