Search

Andreas Hein Willius,1 Marisa Torres Hidalgo,2 Pablo Arroyo Zuñiga,1 Margarita Quezada Venegas,1 Christian Arriagada Díaz,3 Eduardo Valenzuela Abarca,4 Ernesto San Martín Gutierrez,5 Paula Bedregal6 1Project DEPPAS-FONDEF (ID17AM0038), Faculty of Medicine, Pontifical Catholic University of Chile, Santiago, Región Metropolitana, Chile; 2Faculty of Medicine, Pontifical Catholic University of Chile, Santiago, Región Metropolitana, Chile; 3School of Social Work, Faculty of Psychology, Universidad San Sebastián, Santiago, Chile; 4Department of Internal Medicine, Geriatric Program, Faculty of Medicine, Pontifical Catholic University of Chile, Santiago, Región Metropolitana, Chile; 5Interdisciplinary Laboratory for Social Statistics, Faculty of Mathematics, Pontifical Catholic University of Chile, Santiago, Región Metropolitana, Chile; 6Department of Public Health, Faculty of Medicine, Pontifical Catholic University of Chile, Santiago, Región Metropolitana, ChileCorrespondence: Andreas Hein WilliusDepartamento de Salud Pública, Escuela de Medicina, Pontificia Universidad Católica de Chile, Diagonal Paraguay 362, Santiago, Región Metropolitana, Segundo Piso, ChileTel +569 5624 0699Email aahein@uc.clAims: DEPPAS (“Dispositivo Electrónico Personal y Portable en Salud” or Personal, Portable Electronic Health Device in English) is a portable device in form of a bracelet that allows storing electronic health records of older adults experiencing chronic illnesses. The device seeks to support the vital sustainability of older adults by storing critical health information when electronic or paper records have been lost as a consequence of a disaster. Older adults are particularly vulnerable to experience negative consequences in this context. The present study explores the end-user acceptability of DEPPAS in order to inform the next design stages of the device.Methods: Twenty home-dwelling urban male and female older adults enrolled in a chronic health management program were invited to participate in two focus groups. A prototype of DEPPAS was presented and reactions to health service disruption scenarios were explored. Focus groups were transcribed. Content analysis based on the Technology Acceptance Model was conducted.Results: Older adults are acutely aware of their vulnerable health status. Participants report overall positive reactions to DEPPAS. The device was associated with feelings of relief and an increased sense of control over their health management. DEPPAS is perceived as useful, usable, and safe. Even though concerns regarding confidentiality were raised, benefits are perceived as more relevant than potential risks. Participants agree that its usefulness could be extended beyond disaster situations to everyday health care management. Implications for future development and limitations are discussed.Conclusion: The conceptual design DEPPAS shows a high level of acceptability by this end user and a high potential to be integrated with other complementary technologies (e.g. GPS, medication reminders) that could significantly contribute to improving health management in disaster situations.Keywords: wearable health devices, portable electronic health records, acceptability, older adults

Programmed electrical stimulation (PES) of the heart was evaluated as a method of identifying patients at risk of sudden death post-myocardial infarction (post-MI). Eighty-four patients (mean age, 56 ± 10 years) underwent PES 6 to 8 weeks post-MI. PES was performed at the right ventricular apex at twice diastolic threshold. Prior to stimulation patients were studied with exercise stress testing, 24-hour Holter monitoring and radionuclide ejection fraction. The patients were placed into two groups, according to their responses to electrical stimulation. Group 1:65 patients in whom no arrhythmias were induced or who had repetitive responses that lasted less than six cycles; Group 2: 19 patients in whom ventricular tachycardia was induced. At the end of follow-up (20 ± 9 months) six patients from Group 1 had died. Complex ventricular ectopy and ventricular tachycardia were more frequently detected on Holter in Group 2 (9/19) than in Group 1 (14/65) (p < 0.03). The results of exercise testing and radionuclide ejection fraction did not correlate with the response to PES. However all but one of the patients who died had a left ventricular ejection fraction (LVEF) under 40% and four out of six patients had ventricular tachycardia on Holter monitor. We draw the conclusion that PES did not contribute to the identification of high-risk patients post-MI, as none of the 19 patients in whom ventricular tachycardia was induced died during follow-up. In addition, high-risk patients were characterized by poor ventricular function and complex ventricular arrhythmias on Holter recording. [ABSTRACT FROM AUTHOR]

Context: This study investigates the ethylene insertion reaction mechanism for polymerization catalysis, aiming to discern differences between Ni-α-imine ketone-type catalyst and their SiO 2 -supported counterpart. The reaction force analysis unveils a more intricate mechanism with SiO 2 support, shedding light on unexplored factors and elucidating the observed lower catalytic activity. Furthermore, reactivity indexes suggest earlier ethylene activation in the supported catalyst, potentially enhancing overall selectivity. Finally, the reaction electronic flux analysis provides detailed insights into the electronic activity at each step of the reaction mechanism. In sum, this study offers a comprehensive understanding of the ethylene insertion reaction mechanism in both molecular and supported catalysts, underscoring the pivotal role of structural and electronic factors in catalytic processes., Methods: Density functional theory (DFT) calculations were conducted using the ωB97XD functional and the 6-31 + G(d,p) basis sets with Gaussian16 software. Computational techniques utilized in this study encompassed the IRC method, reaction force analysis, and evaluation of electronic descriptors such as electronic chemical potential, molecular hardness, and electrophilicity reactivity indexes. Additionally, reaction electronic flux analysis was employed to investigate electronic activity along the reaction coordinate., (© 2024. The Author(s), under exclusive licence to Springer-Verlag GmbH Germany, part of Springer Nature.)

The measurement of isometric muscle torque with hand-held dynamometry is a technique little studied in the pediatric setting for the evaluation of maximal isometric muscle strength., Objective: to determine the reliability of hand-held dynamometry to obtain the maximal isometric torque of upper and lower limb muscle groups in Chilean children and adolescents., Patients and Methods: Crosssectional study. Seventy-two participants aged between 7 and 15 years were selected from a school in Talca. Maximal isometric torque was recorded in 15 muscle groups of upper and lower limbs through hand-held dynamometry. Intra- and inter-rater evaluation was used, applying the intraclass correlation coefficient (ICC) to determine the reliability of the tests and Bland-Altman plots to evaluate concordance., Results: The results demonstrated good to excellent inter-rater reliability (ICC = 0.850.98) and intra-rater reliability (ICC = 0.87-0.98). Only two groups, hip extensors and abductors, showed good inter-rater reliability (ICC = 0.85 and ICC = 0.88, respectively); and one group, the ankle dorsiflexors, showed good intra-rater reliability (ICC = 0.87). 100% of the tests presented at least 95.8% inter- and intra-rater agreement on the Bland-Altman plots., Conclusion: The evaluation of isometric muscle torque using hand-held dynamometry is a reliable procedure for use in different growth periods.

A β-cyclodextrin (β-CD) nanosponge (NS) was synthesized using diphenyl carbonate (DPC) as a cross-linker to encapsulate the antitumor drug cyclophosphamide (CYC), thus obtaining the NSs-CYC system. The formulation was then associated with magnetite nanoparticles (MNPs) to develop the MNPs-NSs-CYC ternary system. The formulations mentioned above were characterized to confirm the deposition of the MNPs onto the organic matrix and that the superparamagnetic nature of the MNPs was preserved upon association. The association of the MNPs with the NSs-drug complex was confirmed through field emission scanning electron microscopy, energy dispersive spectroscopy, transmission electron microscopy, X-ray photoelectron spectroscopy, dynamic light scattering, ζ-potential, atomic absorption spectroscopy, X-ray powder diffraction, selected area electron diffraction, and vibrating-sample magnetometer. The superparamagnetic properties of the ternary system allowed the release of CYC by utilizing magnetic hyperthermia upon the exposure of an alternating magnetic field (AMF). The drug release experiments were carried out at different frequencies and intensities of the magnetic field, complying with the "Atkinson-Brezovich criterion". The assays in AMF showed the feasibility of release by controlling hyperthermia of the drug, finding that the most efficient conditions were F = 280 kHz, H = 15 mT, and a concentration of MNPs of 5 mg/mL. CYC release was temperature-dependent, facilitated by local heat generation through magnetic hyperthermia. This phenomenon was confirmed by DFT calculations. Furthermore, the ternary systems outperformed the formulations without MNPs regarding the amount of released drug. The MTS (3-(4,5-dimethylthiazol-2-yl)-5-(3-carboxymethoxyphenyl)-2-(4-sulfophenyl)-2 H -tetrazolium) assays demonstrated that including CYC within the magnetic NS cavities reduced the effects on mitochondrial activity compared to those observed with the free drug. Finally, the magnetic hyperthermia assays showed that the tertiary system allows the generation of apoptosis in HeLa cells, demonstrating that the MNPs embedded maintain their properties to generate hyperthermia. These results suggest that using NSs associated with MNPs could be a potential tool for a controlled drug delivery in tumor therapy since the materials are efficient and potentially nontoxic.

A solventless and acid-catalyzed condensation of meso -perfluoroalkyl-dipyrromethanes with selected benzaldehydes was used to prepare ten different bilanes that were isolated before their oxidation into trans -A 2 B-corroles bearing two meso -perfluoroalkyl groups. Macrocycles bearing long chains (C 3 F 7 or C 7 F 15 ) are key precursors to afford ABC-corroles having a meso -acyl substituent when subjected to a mild and basic hydrolysis affecting one of the alkyl substituents.

Nanoplastics (NPLs) persist in aquatic habitats, leading to incremental research on their interaction mechanisms with metalloids in the environment. In this regard, it is known that plastic debris can reduce the number of water-soluble arsenicals in contaminated environments. Here, the arsenic interaction mechanism with pure NPLs, such as polyethylene terephthalate (PET), aliphatic polyamide (PA), polyvinyl chloride (PVC), polyethylene (PE), polypropylene (PP), and polystyrene (PS) is evaluated using computational chemistry tools. Our results show that arsenic forms stable monolayers on NPLs through surface adsorption, with adsorption energies of 9-24 kcal/mol comparable to those on minerals and composite materials. NPLs exhibit varying affinity towards arsenic based on their composition, with As(V) adsorption showing higher stability than As(III). The adsorption mechanism results from a balance between electrostatics and dispersion forces (physisorption), with an average combined contribution of 87%. PA, PET, PVC, and PS maximize the electrostatic effects over dispersion forces, while PE and PP maximize the dispersion forces over electrostatic effects. The electrostatic contribution is attributed to hydrogen bonding and the activation of terminal O-C, C-H, and C-Cl groups of NPLs, resulting in several pairwise interactions with arsenic. Moreover, NPLs polarity enables high mobility in aqueous environments and fast mass transfer. Upon adsorption, As(III) keeps the NPLs polarity, while As(V) limits subsequent uptake but ensures high mobility in water. The solvation process is destabilizing, and the higher the NPL polarity, the higher the solvation energy penalty. Finally, the mechanistic understanding explains how temperature, pressure, pH, salinity, and aging affect arsenic adsorption. This study provides reliable quantitative data for sorption and kinetic experiments on plastic pollution and enhances our understanding of interactions between water contaminants., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier Ltd. All rights reserved.)

Urban wastewaters comprise different hydrophobic pollutants such as microplastics (MPs), pharmaceuticals, and personal care products. Among these pollutants, triclosan (TCS) shows a worrying interaction ability with MPs; recent studies show MPs serve as a vector between TCS and aquatic environments, whose interaction is still being studied to understand their combined toxicity and transport ability. Using computational chemistry tools, this work evaluates the TCS-MPs interaction mechanism, including pristine polymers, i.e., aliphatic polyamides (PA), polyethylene (PE), polystyrene (PS), polyvinyl chloride (PVC), and polyethylene terephthalate (PET). Our results show that TCS adsorption on MPs solely occurs via physisorption, where PA reaches the higher adsorption ability. Remarkably, MPs reach higher or comparable adsorption stability than carbon-based materials, boron nitrides, and minerals, indicating their worrying transport properties. Also, the adsorption capacity is strongly influenced by entropy changes rather than thermal effects, which determine the different sorption capacities among polymers and agree well with reported sorption capacities from adsorption kinetic experiments in the literature. MPs show a polar and highly susceptible surface to establish electrostatics and dispersion effects on TCS. Accordingly, the TCS-MPs interaction mechanism arises from the interplay between electrostatics and dispersion forces, with a combined contribution of 81-93 %. Specifically, PA and PET maximize the electrostatic effects, while PE, PP, PVC, and PS maximize the dispersion effects. From the chemical viewpoint, TCS-MPs complexes interact by a series of pairwise interactions such as Van der Waals, hydrogen bonding, C-H⋯π, C-H⋯C-H, C-Cl⋯C-H, and C-Cl⋯Cl-C. Finally, the mechanistic information explains the effects of temperature, pressure, aging, pH, and salinity on TCS adsorption. This study quantitatively elucidates the interaction mechanism of TCS-MP systems, which were hard to quantify to date, and explains the TCS-MPs sorption performance for sorption/kinetic studies., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 Elsevier B.V. All rights reserved.)

Today, the high concentrations of copper found in water resources result in an urgent problem to solve since human health and aquatic ecosystems have been affected. Functionalized crosslinked polyketone resins (XLPK) have demonstrated high performance for the uptake of heavy metals in water solutions. In addition, its green chemical synthesis makes these resins very attractive as sorbents for metal ions contained in wastewater. XLPK are not soluble in aqueous media and do not require any catalyst, solvent, or harsh conditions to carry out the uptake process. In this paper, a series of functionalized XLPK with pending amino-derivatives namely; butylamine (BA), amino 2-propanol (A2P), 4-(aminomethyl) benzoic acid (HAMC), 6-aminohexanoic acid (PAMBA), and 1,2 diamino propane (DAP) directly attached to the pyrrole backbone of the polymers and crosslinked by di-amine derivatives was investigated using Density Functional Theory (DFT) calculations. Our computational analysis revealed that dipole-dipole interactions played a crucial role in enhancing the adsorption of Cu 2+ ions onto XLPKs. The negatively charged ketone moieties and functional groups within XLPKs were identified as key adsorption sites for the selective binding of Cu 2+ ions. Additionally, we found that XLPKs exhibited strong electrostatic interactions primarily through the -NH 2 and -C=O groups. Evaluation of the adsorption energies in XLPK-Cu(II) complexes showed that the DAP-Cu(II) complex exhibited the highest stability, attributed to strong Cu(II)-N binding facilitated by the amino moiety (-NH 2 ). The remaining XLPKs displayed binding modes involving oxygen atoms (Cu(II)-O) within the ketone moieties in the polymer backbone. Furthermore, the complexation and thermochemical analysis emphasized the role of the coordinator atom (N or O) and the coordinating environment, in which higher entropic effects involved in the adsorption of Cu 2+ ions onto XLPKs describes a lower spontaneity of the adsorption process. The adsorption reactions were favored at lower temperatures and higher pressures. These findings provide valuable insights into the reactivity and adsorption mechanisms of functionalized and crosslinked polyketones for Cu 2+ uptake, facilitating the design of high-performance polymeric resins for water treatment applications.

Alteration in the buffering capacity of the proteostasis network is an emerging feature of Alzheimer's disease (AD), highlighting the occurrence of endoplasmic reticulum (ER) stress. The unfolded protein response (UPR) is the main adaptive pathway to cope with protein folding stress at the ER. Inositol-requiring enzyme-1 (IRE1) operates as a central ER stress sensor, enabling the establishment of adaptive and repair programs through the control of the expression of the transcription factor X-box binding protein 1 (XBP1). To artificially enforce the adaptive capacity of the UPR in the AD brain, we developed strategies to express the active form of XBP1 in the brain. Overexpression of XBP1 in the nervous system using transgenic mice reduced the load of amyloid deposits and preserved synaptic and cognitive function. Moreover, local delivery of XBP1 into the hippocampus of an 5xFAD mice using adeno-associated vectors improved different AD features. XBP1 expression corrected a large proportion of the proteomic alterations observed in the AD model, restoring the levels of several synaptic proteins and factors involved in actin cytoskeleton regulation and axonal growth. Our results illustrate the therapeutic potential of targeting UPR-dependent gene expression programs as a strategy to ameliorate AD features and sustain synaptic function., Competing Interests: Declaration of interests The authors declare that no conflicts of interest exist., (Copyright © 2023. Published by Elsevier Inc.)

Non-covalent hybrid materials based on graphene and A 3 -type copper corrole complexes were computationally investigated. The corroles complexes contain strong electron-withdrawing fluorinated substituents at the meso positions. Our results show that the non-innocent character of corrole moiety modulates the structural, electronic, and magnetic properties once the hybrid systems are held. The graphene-corrole hybrids displayed outstanding stability via the interplay of dispersion and electrostatic driving forces, while graphene act as an electron reservoir. The hybrid structures exposed an intriguing magneto-chemical performance, compared to the isolated counterparts, that evidenced how structural and electronic effects contributed to the magnetic response for both ferromagnetic and antiferromagnetic cases. Directional spin polarization and spin transfer from the corrole to the graphene surface participate in the amplification. Finally, there are relations between the spin transfer, the magnetic response, and the copper distorted ligand field, offering exciting hints about modulating the magnetic response. Therefore, this work shows that copper corroles emerged as versatile building blocks for graphene hybrid materials, especially in applications requiring a magnetic response., (© 2023 Wiley-VCH GmbH.)

Microplastics (MPs) have been detected in the hydrosphere, with hazardous implications in transporting coexisting water pollutants. Our knowledge about the interaction mechanisms that MPs establish with organic pollutants are still growing, which is essential to understand the adsorption properties of MPs and their relative stability with adsorbates. Here, we used classical (force field methods) and ab-initio (density functional theory) computational chemistry tools to characterize the interaction mechanisms between Polystyrene-MPs (PS-MPs) and pharmaceuticals/personal care products (PPCPs). Adsorption conformations and energies, thermochemistry, binding, and energy decomposition analyses were performed to obtain the quantitative mechanistic information. Our results show that PS-MPs have permanent dipoles, increasing the interaction with neutral PPCPs while repelling the charged pollutants; in all cases, a stable physisorption takes place. Moreover, PS-MPs increase their solubility upon pollutant adsorption due to an increase in the dipole moment, increasing their co-transport ability in aqueous environments. The stability of the PS-MPs/PPCPs complexes is further confirmed by thermochemical and molecular dynamics trajectory analysis as a function of temperature and pressure. The interaction mechanism of high pKa pollutants (pKa > 5) is due to a balanced contribution of electrostatic and dispersion forces, while the adsorption of low pKa pollutants (pKa < 5) maximizes the electrostatic forces, and steric repulsion effects explain their relative lower adsorption stability. In this regard, several pairwise intermolecular interactions are recognized as a source of stabilization in the PS-MPs/PPCPs binding: hydrogen bonding, π-π, OH⋯π, and CH⋯π, CCl⋯CH and CH⋯CH interactions. The ionic strength in solution slightly affects the adsorption stability of neutral PPCPs, while the sorption of charged pollutants is enhanced. This mechanistic information provides quantitative data for a better understanding of the interactions between organic pollutants and MPs, serving as valuable information for sorption/kinetic studies., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2022 Elsevier B.V. All rights reserved.)

Microplastics and endocrine disruptors (EDs) are contaminants of emerging concerns and ubiquitously present in aquatic ecosystems, establishing interactions that still are the subject of investigation due to their implications in the cotransport of pollutants. Then, we conducted mechanistic studies based on state-of-art computational chemistry methods to quantitatively understand the interaction mechanisms whereby polystyrene micro or nanoplastics (PS-MPs) interact with representative classes of EDs in water (Ethynylestradiol, Estradiol, and Bisphenol A). The results showed that PS-MPs increase their charge distribution when forming microparticles in water, giving a permanent dipole that explains their increasing solubility in aqueous conditions. In agreement with experimental assessments, the PS-MPs favorably adsorb EDs with adsorption energies larger than 15 kcal/mol, even with comparable stability to nanostructured materials for adsorption, removal, and/or analysis of pollutants. The adsorption occurs via physisorption without covalent binding, bond breaking, or structural preparation energies, where the molecular structure of EDs can favor inner or outer surface adsorption depending on the molecular structure of the adsorbates. A balanced contribution of dispersion and electrostatic stabilizing effects determines the interaction mechanisms, accounting for a whole contribution of 88-90%. The electrostatic contribution emerges from the favorable alignment of the PS-MPs and EDs dipoles upon interaction due to the mild charge transfer between them in solution. In contrast, the dispersion contribution emerges from electron-electron interactions due to the permanent dipoles in adsorbates and adsorbents. Furthermore, thermochemical analyses clarify the role of temperature and pressure effects on the relative adsorption stability among EDs in aquatic environments. Therefore, modeling the adsorption process contributes to new knowledge on the sorption properties of PS-MPs, providing a mechanistic basis to understand the cotransport of pollutants in water environments and their impacts on environmental pollution., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 Elsevier Ltd. All rights reserved.)