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The mechanism of carbamate activation promoted by different metal ions has been explored in this work. The reaction of the carbamate ligand H2L with chloride metal salts (M = Ni, Cu, Zn, Cd) leads to the coordination of the metal ions to the ligand, causing hydrolysis of the systems. This self-immolation process results in mononuclear dihydrazone complexes, carbon dioxide and the release of alcohol species from the pendant groups of the carbamate ligand. The conditions under which this process occurs have been studied in detail.

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In this work, four manganese(II) complexes derived from the ligands H2L1-H2L4, that incorporate dansyl or tosyl fluorescent dyes, have been investigated in term of their antioxidant properties. Two of the manganese(II) complexes have been newly prepared using the asymmetric half-salen ligand H2L2 and the thiosemicarbazone ligand H2L3. The four organic strands and the manganese complexes have been characterized by different analytical and spectroscopic techniques. The study of the antioxidant behaviour of these two new complexes and other two fluorophore-labelled analogues was tested in SH-SY5Y neuroblastoma cells. These four model complexes 1-4 were found to protect cells from oxidative damage in this human neuronal model, by reducing the release of reactive oxygen species. Complexes 1-4 significantly improved cell survival, with levels between 79.1 ± 0.8% and 130.9 ± 4.1%. Moreover, complexes 3 and 4 were able to restore the mitochondrial membrane potential at 1 µM, with 4 reaching levels higher than 85%, similar to the percentages obtained by the positive control agent cyclosporin A. The incorporation of the fluorescent label in the complexes allowed the study of their ability to enter the human neuroblastoma cells by confocal microscopy.

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A recent line of research concerns bedtime procrastination, its effects on sleep quality and duration, and the associated repercussions for health and wellbeing. The Bedtime Procrastination Scale is a brief, self-report instrument developed by Kroese et al. with the aim of evaluating this behavior and exploring its association with insufficient sleep, and hence with health. The aim was to develop and validate a Spanish version of the Bedtime Procrastination Scale (BPS-Sp) and to examine the relationship between bedtime procrastination and both general procrastination and self-control. The original BPS was translated from English into Spanish in accordance with international guidelines on the cross-cultural adaptation of measurement instruments. The sample for the validation study comprised 177 nursing students who completed a questionnaire requesting demographic data and which included the following instruments: the newly developed BPS-Sp, the Tuckman Procrastination Scale, and the Brief Self-Control Scale. Statistical analysis involved tests of normality (Kolmogorov-Smirnov), reliability (Cronbach's alpha, test-retest), construct validity, and confirmatory factor analysis. Scores on the BPS-Sp showed excellent internal consistency (α = .83) and temporal stability (test-retest r = .84), as well as significant correlations with general procrastination (r = .26; p < .01) and self-control (r = -.17; p < .05). Confirmatory factor analysis showed an adequate fit for the single-factor solution proposed by Kroese et al. The results suggest that the BPS-Sp is a valid and reliable instrument for assessing bedtime procrastination in the Spanish-speaking population.

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The benefits that technology can provide in terms of health and support for independent living are in many cases not enough to break the barriers that prevent older adults from accepting and embracing technology. This work proposes a hardware and software platform based on a smart mirror, which is equipped with a set of digital solutions whose main focus is to overcome older adults' reluctance to use technology at home and wearable devices on the move. The system has been developed in the context of two use cases: the support of independent living for older individuals with neurodegenerative diseases and the promotion of physical rehabilitation activities at home. Aspects such as reliability, usability, consumption of computational resources, performance and accuracy of the proposed platform and digital solutions have been evaluated in the initial stages of the pilots within the SHAPES project, an EU-funded innovation action. It can be concluded that the SHAPES smart mirror has the potential to contribute as a technological breakthrough to overcome the barriers that prevent older adults from engaging in the use of assistive technologies.

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BACKGROUND: Immunomodulatory drugs have been used in patients with severe COVID-19. The objective of this study was to evaluate the effects of two different strategies, based either on an interleukin-1 inhibitor, anakinra, or on a JAK inhibitor, such as baricitinib, on the survival of patients hospitalized with COVID-19 pneumonia. METHODS: Individuals admitted to two hospitals because of COVID-19 were included if they fulfilled the clinical, radiological, and laboratory criteria for moderate-to-severe disease. Patients were classified according to the first immunomodulatory drug prescribed: anakinra or baricitinib. All subjects were concomitantly treated with corticosteroids, in addition to standard care. The main outcomes were the need for invasive mechanical ventilation (IMV) and in-hospital death. Statistical analysis included propensity score matching and Cox regression model. RESULTS: The study subjects included 125 and 217 individuals in the anakinra and baricitinib groups, respectively. IMV was required in 13 (10.4%) and 10 (4.6%) patients, respectively (p = 0.039). During this period, 22 (17.6%) and 36 (16.6%) individuals died in both groups (p = 0.811). Older age, low functional status, high comorbidity, need for IMV, elevated lactate dehydrogenase, and use of a high flow of oxygen at initially were found to be associated with worse clinical outcomes. No differences according to the immunomodulatory therapy used were observed. For most of the deceased individuals, early interruption of anakinra or baricitinib had occurred at the time of their admission to the intensive care unit. CONCLUSIONS: Similar mortality is observed in patients treated with anakinra or baricitinib plus corticosteroids.

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Purpose: To examine the temporal trends of accelerometer-based total daily sedentary time (ST) and self-reported domain-specific sedentary behavior (SB) on weekdays and weekends in Spanish children. Method: A total of 560 (50.53% girls) children (4th graders) in 2011/12 from 23 Spanish schools and 462 (48.70% girls) children (4th graders) in 2017/18 from 19 schools across Cadiz participated. Hip-worn accelerometers and questionnaires were used to assess total daily ST and self-reported time in SB modalities, respectively. Results: The objectively measured total daily ST tended to increase in boys on weekdays and weekends. Time spent watching television (TV) decreased during the week and weekend days, while time surfing on the internet increased on weekdays and weekends. Playing video-games increased in boys during the weekends. The trend to increase the time spent on educational activities with a computer during the weekdays and weekends was accompanied by a reduction of the same activities without using a computer. There was a trend to increase reading for fun, talking on the phone and total time in other SB, on weekdays and weekends in boys and girls. Conclusion(s): Spanish boys tended to increase objectively measured total daily ST. Moreover, SB modalities have changed in recent years in children, replacing TV viewing by computer use for both educational and non-educational purposes, as well as by the use of smartphones or other sedentary activities that does not imply the presence of a screen. These findings highlight the need to promote interventions to decrease total daily ST and reduce SB activities.

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The effect of the ligand and/or metal-related factors on the formation of tristhiosemicarbazone metallosupramolecular complexes has been studied in this work. The crystal structures of zinc(II) and lead(II) tristhiosemicarbazone mesocates and a hydrolyzed cadmium(II) helicate let us better rationalize some factors involved in the selective formation of helicates or mesocates.

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The lectin DLasiL was isolated from seeds of the Dioclea lasiocarpa collected from the northeast coast of Brazil and characterized for the first time by mass spectrometry, DNA sequencing, inductively coupled plasma-mass spectrometry, electron paramagnetic resonance, and fluorescence spectroscopy. The structure of DLasiL lectin obtained by homology modelling suggested strong conservation of the dinuclear Ca/Mn and sugar-binding sites, and dependence of the solvent accessibility of tryptophan-88 on the oligomerisation state of the protein. DLasiL showed highly potent (low nanomolar) antiproliferative activity against several human carcinoma cell lines including A2780 (ovarian), A549 (lung), MCF-7 (breast) and PC3 (prostate), and was as, or more, potent than the lectins ConBr (Canavalia brasiliensis), ConM (Canavalia maritima) and DSclerL (Dioclea sclerocarpa) against A2780 and PC3 cells. Interestingly, DLasiL lectin caused a G2/M arrest in A2780 cells after 24h exposure, activating caspase 9 and delaying the on-set of apoptosis. Confocal microscopy showed that fluorescently-labelled DLasiL localized around the nuclei of A2780 cells at lectin doses of 0.5-2× IC50 and gave rise to enlarged nuclei and spreading of the cells at high doses. These data reveal the interesting antiproliferative activity of DLasiL lectin, and suggest that further investigations to explore the potential of DLasiL as a new anticancer agent are warranted.

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The effect of the metal ion and ligand design on the enantioselectivity and linkage isomerization of neutral cobalt and zinc bisthiosemicarbazone metallohelicates has been investigated in this work. The electrochemical synthesis has afforded the enantioselective formation of chirally pure cobalt helicates, and the ΛΛ isomer of a single enantiomer has been crystallized as only product for the cobalt methyl-substituted thiosemicarbazone helicate. Interestingly linkage isomers have been formed from zinc ethyl-substituted thiosemicarbazone helicate enantiomers for the first time. The co-existence of these isomers has been evaluated from the point of view of both experimental results and computational calculations.

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A dinuclear Pb(ii) mesocate has been prepared with an unprecedented four-coordinated kernel in which the Pb(ii) lone pair is stereochemically active. This is the first time that this effect has been observed in a supramolecular Pb(ii) helicate or meso-helicate.

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Gold compounds to be obtained by the direct electrochemical oxidation of a noble metal are reported. This achievement provides an alternative procedure to obtaining neutral gold compounds with potential medical or catalytic applications.

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Dinuclear trihydroxido-bridged osmium-arene complexes are inert and biologically inactive, but we show here that linking dihydroxido-bridged Os(II) -arene fragments by a bridging di-imine to form a metallacycle framework results in strong antiproliferative activity towards cancer cells and distinctive knotting of DNA. The shortened spacer length reduces biological activity and stability in solution towards decomposition to biologically inactive dimers. Significant differences in behavior toward plasmid DNA condensation are correlated with biological activity.

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This study aimed to quantify the adsorption affinity of neutralized 10-methacryloyloxydecyl dihydrogen phosphate (10-MDP-N) toward hydroxyapatite (HA) and dicalcium phosphate dihydrate (DCPD) at pH 7.0 by employing the Langmuir isotherm model. Furthermore, the effects of inorganic phosphate (Pi) and fluoride (F(-) ) ions on the adsorption of 10-MDP-N onto HA and DCPD were examined. Fixed amounts of HA and DCPD powders were suspended in different concentrations of 10-MDP-N solutions and were incubated for 18 h. Equilibrated concentrations of 10-MDP-N were measured by spectrophotometry and the adsorption affinity was estimated using the Langmuir model. Moreover, the adsorption was examined by zeta-potential analysis. The results indicated that significant Langmuir correlation was noted in both substrates, along with an increasing negative zeta-potential; however, in DCPD the correlation was less strong. The addition of 1.0 mM Pi slightly delayed the adsorption of 10-MDP-N onto both substrates, whereas 3.0 mM Pi drastically delayed adsorption onto HA but completely inhibited adsorption onto DCPD. Up to 50 ppm, F(-) enhanced the adsorption onto HA, and the adsorption plateaued at higher concentrations of F(-) , whereas no obvious influence of F(-) on the adsorption onto DCPD was noted.

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Despite the suggestion that impulsivity plays a central role in the transfer from a recreational drug use to a substance use disorder, very few studies focused on neurobiological markers for addiction. This study aimed to identify volumetric alterations in a sample of patients with mild alcohol use disorder with a short history of alcohol use, compared with a control group, and also focused on its association with impulsivity levels. Most magnetic resonance imaging studies have focused on severe alcohol use disorder, formerly called alcohol-dependent patients, showing alcohol-related structural alterations and their association with alcohol use history variables but not with personality parameters like impulsivity. Our hypothesis is that our group of alcohol users may already display structural alterations especially in brain regions related to inhibitory control like medial-prefrontal regions, and that those structural alterations could be more associated to personality traits like impulsivity than to drug use variables. Our results clearly demonstrate that our population showed lower regional grey and white matter volumes in the medial-prefrontal and orbitofrontal cortices, as well as higher regional white matter volume in the ventral striatum and the internal capsule. Volumetric alterations were associated to the Barratt's impulsivity score: the more impulsive the subjects, the lower the medial-prefrontal cortex grey matter volume.

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Salivary phosphoproteins are essential in tooth mineral regulation but are often overlooked in vitro. This study aimed to evaluate the effect of casein, as a salivary phosphoprotein homologue, on the deposition and growth of hydroxyapatite (HA) on tooth surfaces. Hydroxyapatite growth was quantified using seeded crystal systems. Artificial saliva (AS) containing HA powder and 0, 10, 20, 50, or 100 µg ml(-1) of casein, or 100 µg ml(-1) of dephosphorylated casein (Dcasein), was incubated for 0-8 h at 37°C, pH 7.2. Calcium concentrations were measured using atomic absorption spectroscopy (AAS). Surface precipitation of HA on bovine enamel and dentine blocks, incubated in similar conditions for 7 d, was examined using field emission scanning electron microscopy (FE-SEM) and transmission electron microscopy (TEM) with selected area electron diffraction (SAED). Casein adsorption was assessed using modified Lowry assays and zeta-potential measurements. The AAS results revealed a concentration-dependent inhibition of calcium consumption. Hydroxyapatite precipitation occurred when no casein was present, whereas precipitation of HA was apparently completely inhibited in casein-containing groups. Adsorption data demonstrated increasingly negative zeta-potential with increased casein concentration and an affinity constant similar to proline-rich proteins with Langmuir modelling. Casein inhibited the deposition and growth of HA primarily through the binding of esterized phosphate to HA active sites, indicating its potential as a mineral-regulating salivary phosphoprotein homologue in vitro.

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Four chiral Os(II) arene anticancer complexes have been isolated by fractional crystallization. The two iodido complexes, (S(Os),S(C))-[Os(η(6)-p-cym)(ImpyMe)I]PF6 (complex 2, (S)-ImpyMe: N-(2-pyridylmethylene)-(S)-1-phenylethylamine) and (R(Os),R(C))-[Os(η(6)-p-cym)(ImpyMe)I]PF6 (complex 4, (R)-ImpyMe: N-(2-pyridylmethylene)-(R)-1-phenylethylamine), showed higher anticancer activity (lower IC50 values) towards A2780 human ovarian cancer cells than cisplatin and were more active than the two chlorido derivatives, (S(Os),S(C))-[Os(η(6)-p-cym)(ImpyMe)Cl]PF6, 1, and (R(Os),R(C))-[Os(η(6)-p-cym)(ImpyMe)Cl]PF6, 3. The two iodido complexes were evaluated in the National Cancer Institute 60-cell-line screen, by using the COMPARE algorithm. This showed that the two potent iodido complexes, 2 (NSC: D-758116/1) and 4 (NSC: D-758118/1), share surprisingly similar cancer cell selectivity patterns with the anti-microtubule drug, vinblastine sulfate. However, no direct effect on tubulin polymerization was found for 2 and 4, an observation that appears to indicate a novel mechanism of action. In addition, complexes 2 and 4 demonstrated potential as transfer-hydrogenation catalysts for imine reduction.

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A series of highly ordered mesoporous Cr(2)O(3) were prepared through the nanocasting pathway from decomposition of chromium(VI) oxide using KIT-6 as a hard template. The effects of the calcination temperature on the crystal structure, textural parameters and magnetic properties of the material were investigated. It was found that with increasing calcination temperature, surface area and pore volume of the mesoporous Cr(2)O(3) decreased slightly. Unpredictably, increasing calcination temperature also influences the lattice parameters of the Cr(2)O(3) crystal, and this rearrangement in the lattice parameter leads to changes in the value of the Néel temperature. A spin-flop transition has been observed at a magnetic field smaller than that of bulk material.

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We have studied the factors that affect the formation of different metallosupramolecular architectures by metal direct self-assembly. A synthetic route has been developed to obtain mesocates or dihelicates selectively. For this purpose a series of five bisthiosemicarbazone ligands derived from 1,3-diacetylbenzene were designed and synthesised. Namely H(2)L(Me), H(2)L(Et), H(2)L(Ph), H(2)L(PhN) and H(2)L(PhOMe) with different substituents on the 4-N terminal position of the thiosemicarbazone strands. The Co(II), Zn(II) and Cd(II) complexes of these ligands were prepared by an electrochemical procedure. Crystallographic studies revealed the formation of mesocates for Co(II) and Zn(II) metal ions whereas the Cd(II) complexes gave a bishelical supramolecular structure. Therefore these bisthiosemicarbazone ligands enable the selective isolation of mesocate or dihelicate complexes by using a specific metal ion.

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The coordinative chemistry of the tridentate half-salen ligand 5-(dimethylamino)-N-(2-((2-hydroxybenzylidene)amino)phenyl)naphthalene-1-sulfonamide (H(2)L, 1) has been studied by means of an electrochemical method. All of the complexes have been characterised using analytical and spectroscopic techniques. Ligand 1 and two nickel (6 and 7), copper (9), zinc (12) and cadmium (14) metal complexes have been studied by crystallography. Complexes 6 and 7 are octahedral and tetrahedral nickel(II) complexes, respectively, and both contain an [L](2-) molecule that behaves in an [N(2)O] tridentate manner. Nickel(II) completes its coordination kernel with three water molecules in complex 6, whereas in complex 7 the nickel ion is further bound to a molecule of dansylamine arising from a hydrolysis process. The copper(II) complex 9 is a monomeric compound that contains a bideprotonated ligand thread and a dimethylsulfoxide molecule coordinated through the sulfur atom. The zinc complex 12 is an unusual pentanuclear cluster compound whose structure consists of four anionic ligand units and two hydroxo anions bound to five zinc(II) centres. The appearance of the hydroxo anions in this complex provides new evidence for water reduction electrochemically promoted by zinc metal under mild conditions. The cadmium complex 14 is a dimeric compound that comprises two molecules of the anionic ligand and two dimethylsulfoxide molecules. The great structural variety exhibited by all these complexes demonstrates that the introduction of asymmetry in a salen skeleton by incorporating a dansyl pendant increases the versatility of the resulting ligand on coordination. All complexes are luminescent in solution at room temperature in acetonitrile solutions.

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A unique case of a grid-of-mesocates sequentially assembled by supramolecular cobalt(II) meso-helical units connected through hydrogen bonding is reported.