Medical Cyber-Physical Systems (MCPS) hold the promise of reducing human errors and optimizing healthcare by delivering new ways to monitor, diagnose and treat patients through integrated clinical ...environments (ICE). Despite the benefits provided by MCPS, many of the ICE medical devices have not been designed to satisfy cybersecurity requirements and, consequently, are vulnerable to recent attacks. Nowadays, ransomware attacks account for 85% of all malware in healthcare, and more than 70% of attacks confirmed data disclosure. With the goal of improving this situation, the main contribution of this paper is an automatic, intelligent and real-time system to detect, classify, and mitigate ransomware in ICE. The proposed solution is fully integrated with the ICE++ architecture, our previous work, and makes use of Machine Learning (ML) techniques to detect and classify the spreading phase of ransomware attacks affecting ICE. Additionally, Network Function Virtualization (NFV) and Software Defined Networking (SDN)paradigms are considered to mitigate the ransomware spreading by isolating and replacing infected devices. Different experiments returned a precision/recall of 92.32%/99.97% in anomaly detection, an accuracy of 99.99% in ransomware classification, and promising detection and mitigation times. Finally, different labelled ransomware datasets in ICE have been created and made publicly available.
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IZUM, KILJ, NUK, PILJ, PNG, SAZU, UL, UM, UPUK
In this work, the sequential Electrocoagulation + Electro-oxidation + Activated carbon adsorption (EC + EO + AC) process was studied as an alternative for the treatment of an industrial textile ...wastewater (TWW) issuing from a manufacturing company located in Medellín (Colombia). The EC's and EO's operational conditions were optimized using a Box-Behnken experimental design, the Response Surface Methodology and a constrained nonlinear optimization algorithm in terms of organic matter degradation efficiency. The best performance for EC (i. e., dye removal = 94%, COD and TOC degradation of 45 and 40%, respectively) was obtained using Fe anode and Boron Doped Diamond (BDD) cathode, with current density, jEC, equals to 5 mA/cm2, pH = 9.3, 60 RPM and 10 min of electrolysis. After EC treatment, the effluent biodegradability (evaluated as the BOD5/COD ratio) increases from 0.14 to 0.23. Regrettably, EC was not effective for the removal of acute toxicity to Artemia salina since the treated effluent remained very toxic (100%). The treatment of EC's effluent by EO enhanced organic pollutant removal. For EC + EO sequential process, EO optimal operational conditions (jEO = 10 mA/cm2, pH = 3, 240 RPM, BDD as anode and Fe as cathode) allowed reduction of 100% of color, 88% of COD and 79% of TOC after 30 min of electrolysis. Moreover, the BOD5/COD ratio increased from 0.23 to 0.58; however, the treated effluent remained very toxic to the Artemia salina. Consequently, an activated carbon adsorption step was included to complete the treatment process. Thus, by coupling the EC + EO + AC process, effluent's acute toxicity decreased completely. From molecular weight distribution analysis, it was concluded that EC + EO was efficient in eliminating low molecular weight (< 5 kDa) compounds. Finally, the operation cost, which includes chemical reagents, electrodes, energy consumption, and sludge disposal, for the EC + EO + AC sequential process was estimated in 3.83 USD /m3.
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GEOZS, IJS, IMTLJ, KILJ, KISLJ, NLZOH, NUK, OILJ, PNG, SAZU, SBCE, SBJE, UILJ, UL, UM, UPCLJ, UPUK, ZAGLJ, ZRSKP
Here, we report the development of cobalt(I)‐catalyzed regioselective allylic alkylation reactions of tertiary allyl carbonates with 1,3‐dicarbonyl compounds. A family of well‐defined tetrahedral ...cobalt(I) complexes bearing commercially available bidentate bis(phosphine) ligands (P,P)Co(PPh3)Cl are synthesized and explored as catalysts in allylic alkylation reactions. The catalyst (dppp)Co(PPh3)Cl (dppp=1,3‐Bis(diphenylphosphino)propane) enables the alkylation of a large variety of tertiary allyl carbonates with high yields and excellent regioselectivity for the branched product. Remarkably, this methodology is selective for the activation of tertiary allyl carbonates even in the presence of secondary allyl carbonates. This contrasts with the selectivity observed in cobalt‐catalyzed allylic alkylations enabled by visible light photocatalysis. Mechanistic insights by means of experimental and computational investigations support a Co(I)/Co(III) catalytic cycle.
A cobalt(I)‐catalyzed regioselective allylic alkylation of tertiary allylic carbonates with 1,3‐dicarbonyl compounds is described. The alkylated products are obtained in high yields and with excellent selectivity towards the kinetic branched regioisomer. Mechanistic insights by combining experimental and computational investigations support a Co(I)/Co(III) catalytic cycle.
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BFBNIB, FZAB, GIS, IJS, KILJ, NLZOH, NUK, OILJ, SAZU, SBCE, SBMB, UL, UM, UPUK
To further target product development with low environmental impact, an integral green electrospinning (G‐ES) approach has been adopted through the simultaneous application of various strategies, ...such as the use of biopolymers, reduction of energy use to avoid melting temperatures, and selection of non‐toxic solvents and surfactants. Green solubility spinnability maps for cellulose acetate (CA), poly ε‐caprolactone (PCL), and polyvinyl alcohol (PVA) are presented. Green electrospinning (G‐ES) allows the production of new morphologies for CA and PCL nanofiber membranes. In this work, CA exhibits a ribbon‐like morphology, PCL shows a honeycomb‐like morphology and PVA cylindrical fibers. Membrane morphologies are compared with filtration efficiency (FE) for particle size of 1.0 μm and quality factor (QF) at a volumetric flux of 27.63 cm−1. For CA is between 83% and 96% and high QF = 0.31–0.38 Pa−1, PCL is 92% and 99% and high QF = 0.28–0.21 Pa−1 and for PVA between 96% and 99% and high QF = 0.14–0.08 Pa−1. These results suggest that the hierarchical nanofiber structure improves filtration performance because of the reduction in pressure drop and increase in PM interception. CA ribbon‐like fibers favored air filtration performance, followed by PCL honeycomb‐like fibers.
Nanofibers produced by green electrospinning for filtration applications.
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BFBNIB, FZAB, GIS, IJS, KILJ, NLZOH, NUK, OILJ, SAZU, SBCE, SBMB, UL, UM, UPUK
In contrast to transition-metal-catalyzed difunctionalization of activated alkenes, selective alkylarylation of vinyl azaarenes is underdeveloped. Consequently, the lack of modular and rapid ...syntheses of 1,1-bis(hetero)arylalkanes limits their exploration in medicinal chemistry. Herein we report a protocol using commercially available iron salts, bisphosphine ligands, fluoroalkyl halides, and Grignard reagents that enables the selective 1,2-fluoroalkyl(hetero)arylation of vinyl azaarenes. We demonstrate the versatility and robustness of the method through the selective synthesis of a range of unsymmetrical 1,1-bis(hetero)arylalkenes, including pyridine N-oxides, triazoles, pyrazines, carbazoles, indazoles, and 1,2-azaborines. Mechanistic insights from experimental and computational investigations support a radical pathway and provide insights into the role of non-covalent interactions in iron catalysis.
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IJS, KILJ, NUK, PNG, UL, UM
It is well established in mammals that the gastrointestinal tract (GIT) senses the luminal presence of nutrients and responds to such information by releasing signaling molecules that ultimately ...regulate feeding. However, gut nutrient sensing mechanisms are poorly known in fish. This research characterized fatty acid (FA) sensing mechanisms in the GIT of a fish species with great interest in aquaculture: the rainbow trout (
). Main results showed that: (i) the trout GIT has mRNAs encoding numerous key FA transporters characterized in mammals (FA transporter CD36 -FAT/CD36-, FA transport protein 4 -FATP4-, and monocarboxylate transporter isoform-1 -MCT-1-) and receptors (several free FA receptor -Ffar- isoforms, and G protein-coupled receptors 84 and 119 -Gpr84 and Gpr119-), and (ii) intragastrically-administered FAs differing in their length and degree of unsaturation (i.e., medium-chain (octanoate), long-chain (oleate), long-chain polyunsaturated (α-linolenate), and short-chain (butyrate) FAs) exert a differential modulation of the gastrointestinal abundance of mRNAs encoding the identified transporters and receptors and intracellular signaling elements, as well as gastrointestinal appetite-regulatory hormone mRNAs and proteins. Together, results from this study offer the first set of evidence supporting the existence of FA sensing mechanisms n the fish GIT. Additionally, we detected several differences in FA sensing mechanisms of rainbow trout vs. mammals, which may suggest evolutionary divergence between fish and mammals.
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IZUM, KILJ, NUK, PILJ, PNG, SAZU, UL, UM, UPUK
Scope
Some very‐low density lipoprotein (VLDL) properties may render them more pro‐atherogenic. We aimed to assess whether a Mediterranean diet (MedDiet) or an energy‐reduced MedDiet with increased ...physical activity improves them.
Methods and results
In a sample of the PREvención con DIeta MEDiterránea (PREDIMED) study, a 1‐year intervention with MedDiet with extra‐virgin olive oil (n = 89) or nuts (MedDiet‐Nuts; n = 79) is compared with a low‐fat diet (n = 90). In the PREDIMED‐Plus study, a 1‐year intervention with energy‐reduced MedDiet and physical activity (n = 103) is compared with an ad libitum MedDiet (n = 101). VLDL levels of apolipoprotein C‐I, C‐III, triglycerides, and cholesterol; the apolipoprotein E‐/C‐I ratio; and VLDL ex‐vivo triglyceride transfer are measured. In PREDIMED participants in both MedDiet groups combined, VLDL apolipoprotein C‐III levels are nominally reduced (−0.023 SD units, 95% CI −0.44 to −0.014, p = 0.037). VLDL triglyceride transfer is nominally increased in the MedDiet‐Nuts group (+0.39 SD units, 95% CI 0.012–0.78, p = 0.045). In PREDIMED‐Plus, no inter‐group differences are detected.
Conclusions
In older adults at high cardiovascular risk, MedDiet is associated with lower VLDL atherogenicity versus a low‐fat diet. No differences are seen after an energy‐reduced MedDiet with physical activity.
According to two randomized controlled trials in older adults at high cardiovascular risk, a traditional Mediterranean diet decreases VLDL atherogenicity relative to a low‐fat control diet (it reduces VLDL levels of apolipoprotein C‐III and boosts the lipoprotein capacity to transfer triglycerides). An energy reduces Mediterranean diet with increased physical activity does not further improve these characteristics.
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BFBNIB, FZAB, GIS, IJS, KILJ, NLZOH, NUK, OILJ, SAZU, SBCE, SBMB, UL, UM, UPUK
A detailed mechanistic study of the Z-selective allylic functionalization via thianthrenium salts is presented. Kinetic analyses, deuterium labeling experiments, and computational methods are used to ...rationalize the observed reactivity and selectivity. We find that the reaction proceeds via a rate-determining and stereodetermining allylic deprotonation of an alkenylthianthrenium species. The Z-configuration of the resultant allylic ylide is translated into the Z-allylic amine product through a sequence of subsequent fast and irreversible steps: protonation to form a Z-allylic thianthrenium electrophile and then regioselective substitution by the nucleophile. In the stereodetermining deprotonation step, computational studies identified a series of stabilizing nonbonding interactions in the Z-alkene-forming transition state that contribute to the stereoselectivity.
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IJS, KILJ, NUK, PNG, UL, UM
The aim of the study was to (i) analyze the match performance of professional female tennis players in different Grand Slams; (ii) model the relationships between match performance variables and ...relative quality; and (iii) build typical performance profiles for those players in Grand Slams.
Data of a total of 1369 matches were collected within 2014-2017 four Grand Slams (Australian Open: n = 499; Roland Garros: n = 249; Wimbledon: n = 249 and US Open, n = 372). Correlations between 37 performance variables and relative quality (difference of expected rounds between two competing players of given ranking) were determined and automatically classified into two groups of magnitudes via two-step cluster analysis. Higher-correlated variables were used to build players' typical performance profiles via regression-based technique to give percentage evaluation scores (%ES), which means the percentage of matches where a performance variable value would be expected to be lower than the observed value considering the RQ of two competing players.
Players had more service winners, double faults, return winners and return unforced errors in the Australian Open and US Open, implying a "fast-fast" serve strategy, and higher dominance ratio and better serving performance in Wimbledon. While receiving players had better chances to break opponents' service game in Roland Garros. Distance covered became similar in all Grand Slams. All studied variables showed obvious correlation with RQ expect for those of physical performance.
The findings (i) indicate that female game in Grand Slams remained to be a contest over baseline, although players had good efficiency at net; (ii) demonstrate the influence of relative quality on serve and return, break point, net point and efficiency performance; and (iii) evidence the usefulness of applying %ES to evaluate performance of individual player.
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DOBA, IZUM, KILJ, NUK, PILJ, PNG, SAZU, SIK, UILJ, UKNU, UL, UM, UPUK
This study aimed to determine whether the role of technical, physical performance indicators and situational variables in determining match outcome has varied from a long-term analysis (seasons 2012 ...to 2017) of the Chinese Soccer Super League (CSL). The sample included 1,429 matches where 17 technical performance-related indicators, 11 physical performance-related indicators and two situational variables (match location and quality of opposition) were analysed. Three binary logistic regression models (inclusion of different variables) were used to measure the level of association between factors and match outcome over the six seasons studied. Results of models 1 and 2 revealed that shots on target, possession, total distance in ball possession, total distance out of ball possession, and match location exerted a decreased influence on winning the matches from 2012 to 2014 seasons. However, these indicators play a more important role in winning matches from 2014 to 2017 seasons. Additionally, the quality of opposition has a continuously increased negative effect on the match outcome. In model 3, more variables, such as high-speed distance, high-speed out of ball possession, had a meaningful influence on winning the match. These results provide valuable information about performance indicators and situational variables on winning the matches from a long-term approach.
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BFBNIB, FSPLJ, GIS, IJS, KISLJ, NUK, PNG, UL, UM, UPUK
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