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1.
J Am Chem Soc ; 146(6): 4078-4086, 2024 Feb 14.
Artículo en Inglés | MEDLINE | ID: mdl-38300153

RESUMEN

Electronic waste recycling is a recognized global challenge that requires new strategies to bind and release critical materials selectively, such as cobalt present in lithium-ion batteries. To address this challenge, hierarchical 3D-printed porous polymer scaffolds bearing supramolecular receptors were prepared using vat photopolymerization and their cobalt binding profiles were examined as a function of matrix polarity. By combining high-resolution digital light processing (DLP) with polymerization-induced phase separation (PIPS), functional acrylic copolymer networks with micrometer-level precision of geometry and nanometer-level pores were generated. Covalent integration of a methacrylate-functionalized bisdicyclohexyl acetamide (BDCA-MA) receptor enabled binding and release of cobalt(II) chloride (CoCl2) via a solvent polarity switch mechanism involving a change in solvent from ethanol to water. The present structures proved reusable as shown by sustained high binding efficiency over five bind and release cycles. This platform represents a "green" and energy conscious method for future electronic waste recycling.

2.
Neurogenetics ; 25(2): 131-139, 2024 Apr.
Artículo en Inglés | MEDLINE | ID: mdl-38460076

RESUMEN

Twin and family studies have established the genetic contribution to idiopathic generalized epilepsy (IGE). The genetic architecture of IGE is generally complex and heterogeneous, and the majority of the genetic burden in IGE remains unsolved. We hypothesize that gene-gene interactions contribute to the complex inheritance of IGE. CNTN2 (OMIM* 615,400) variants have been identified in cases with familial adult myoclonic epilepsy and other epilepsies. To explore the gene-gene interaction network in IGE, we took the CNTN2 gene as an example and investigated its co-occurrent genetic variants in IGE cases. We performed whole-exome sequencing in 114 unrelated IGE cases and 296 healthy controls. Variants were qualified with sequencing quality, minor allele frequency, in silico prediction, genetic phenotype, and recurrent case numbers. The STRING_TOP25 gene interaction network analysis was introduced with the bait gene CNTN2 (denoted as A). The gene-gene interaction pair mode was presumed to be A + c, A + d, A + e, with a leading gene A, or A + B + f, A + B + g, A + B + h, with a double-gene A + B, or other combinations. We compared the number of gene interaction pairs between the case and control groups. We identified three pairs in the case group, CNTN2 + PTPN18, CNTN2 + CNTN1 + ANK2 + ANK3 + SNTG2, and CNTN2 + PTPRZ1, while we did not discover any pairs in the control group. The number of gene interaction pairs in the case group was much more than in the control group (p = 0.021). Taking together the genetic bioinformatics, reported epilepsy cases, and statistical evidence in the study, we supposed CNTN2 as a candidate pathogenic gene for IGE. The gene interaction network analysis might help screen candidate genes for IGE or other complex genetic disorders.


Asunto(s)
Contactinas , Epilepsia Generalizada , Epistasis Genética , Redes Reguladoras de Genes , Predisposición Genética a la Enfermedad , Adolescente , Adulto , Niño , Femenino , Humanos , Masculino , Adulto Joven , Estudios de Casos y Controles , Contactinas/genética , Epilepsia Generalizada/genética , Secuenciación del Exoma , Frecuencia de los Genes
3.
J Med Virol ; 96(5): e29648, 2024 May.
Artículo en Inglés | MEDLINE | ID: mdl-38727032

RESUMEN

The effects of COVID-19 vaccination on short-term and long-term cerebrovascular risks among COVID-19 survivors remained unknown. We conducted a national multi-center retrospective cohort study with 151 597 vaccinated and 151 597 unvaccinated COVID-19 patients using the TriNetX database, from January 1, 2020 to December 31, 2023. Patients baseline characteristics were balanced with propensity score matching (PSM). The outcomes were incident cerebrovascular diseases occurred between 1st and 30th days (short-term) after COVID-19 diagnosis. Nine subgroup analyses were conducted to explore potential effect modifications. We performed six sensitivity analyses, including evaluation of outcomes between 1st to 180th days, accounting for competing risk, and incorporating different variant timeline to test the robustness of our results. Kaplan-Meier curves and Log-Rank tests were performed to evaluate survival difference. Cox proportional hazards regressions were adopted to estimate the PSM-adjusted hazard ratios (HR). The overall short-term cerebrovascular risks were lower in the vaccinated group compared to the unvaccinated group (HR: 0.66, 95% CI: 0.56-0.77), specifically cerebral infarction (HR: 0.62, 95% CI: 0.48-0.79), occlusion and stenosis of precerebral arteries (HR: 0.74, 95% CI: 0.53-0.98), other cerebrovascular diseases (HR: 0.57, 95% CI: 0.42-0.77), and sequelae of cerebrovascular disease (HR: 0.39, 95% CI:0.23-0.68). Similarly, the overall cerebrovascular risks were lower in those vaccinated among most subgroups. The long-term outcomes, though slightly attenuated, were consistent (HR: 0.80, 95% CI: 0.73-0.87). Full 2-dose vaccination was associated with a further reduced risk of cerebrovascular diseases (HR: 0.63, 95% CI: 0.50-0.80) compared to unvaccinated patients. Unvaccinated COVID-19 survivors have significantly higher cerebrovascular risks than their vaccinated counterparts. Thus, clinicians are recommended to monitor this population closely for stroke events during postinfection follow-up.


Asunto(s)
Vacunas contra la COVID-19 , COVID-19 , Trastornos Cerebrovasculares , Vacunación , Humanos , Trastornos Cerebrovasculares/epidemiología , Trastornos Cerebrovasculares/etiología , COVID-19/prevención & control , COVID-19/epidemiología , Femenino , Masculino , Estudios Retrospectivos , Persona de Mediana Edad , Vacunas contra la COVID-19/administración & dosificación , Vacunas contra la COVID-19/efectos adversos , Anciano , Vacunación/estadística & datos numéricos , Sobrevivientes/estadística & datos numéricos , Adulto , SARS-CoV-2/inmunología , Factores de Riesgo , Modelos de Riesgos Proporcionales
4.
Postgrad Med J ; 2024 Mar 20.
Artículo en Inglés | MEDLINE | ID: mdl-38507113

RESUMEN

BACKGROUND: Despite previous concerns about ocular side effects related to amiodarone, the relationship between amiodarone and cataract remains uncertain. Therefore, this study aimed to assess the potential association between amiodarone use and the subsequent risk of cataract, taking into account potential confounders. METHODS: This population-based, active comparator-controlled cohort study utilized the data from the Taiwan National Health Insurance program and involved adults over 40 years old between 2001 and 2013. We analyzed 12 055 new amiodarone users and contrasted them with a propafenone user cohort. The primary outcome was the incidence of cataract. Inverse-probability treatment-weighting (IPTW) was further used to eliminate the potential confounding effects, and Cox proportional-hazard regression analyses were performed to calculate the risk of cataract. Serial subgroup analyses were also performed. RESULTS: In the main analysis, amiodarone users did not exhibit a significant causal relationship in both full cohort [adjusted hazard ratio (aHR): 0.994, 95% confidence interval (CI): 0.913-1.082] and IPTW cohort (IPTW-aHR 0.977, 95% CI: 0.900-1.060). Furthermore, it is important to highlight a significantly reduced risk of cataract among patients with heart failure (IPTW-aHR 0.708, 95% CI: 0.554-0.905) and during the 2-year follow-up period (IPTW-aHR 0.889, 95% CI: 0.794-0.996), implying potential advantages linked to the use of amiodarone. CONCLUSIONS: The study found no increased risk of cataract with amiodarone, one of the most frequently used antiarrhythmic medications, compared to the use of propafenone. Future research is recommended to explore potential mechanisms and their implications for clinical practice.

5.
J Am Chem Soc ; 145(47): 25545-25552, 2023 Nov 29.
Artículo en Inglés | MEDLINE | ID: mdl-37962982

RESUMEN

Herein, we report a manganese-catalyzed three-component coupling of ß-H containing alcohols, methanol, and phosphines for the synthesis of γ-hydroxy phosphines via a borrowing hydrogen strategy. In this development, methanol serves as a sustainable C1 source. A variety of aromatic and aliphatic substituted alcohols and phosphines could undergo the dehydrogenative cross-coupling process efficiently and deliver the corresponding ß-phosphinomethylated alcohol products in moderate to good yields. Mechanistic studies suggest that this transformation proceeds in a sequential manner including catalytic dehydrogenation, aldol condensation, Michael addition, and catalytic hydrogenation.

6.
J Am Chem Soc ; 145(26): 14387-14394, 2023 Jul 05.
Artículo en Inglés | MEDLINE | ID: mdl-37343135

RESUMEN

Described in this work are calix[4]pyrrole-based ion-pair receptors, cis/trans-1 and cis/trans-2, designed for the extraction of sodium hydroxide. An X-ray diffraction analysis of a single crystal of the cis-1·NaOH isomer isolated from a mixture of cis/trans-1 revealed a unique dimeric supramolecular structure. An average dimer in toluene-d8 solution was inferred on the basis of diffusion-ordered spectroscopy (DOSY). Support for the proposed stoichiometry came from density functional theory (DFT) calculations. The structural stability of the dimeric cis-1·NaOH complex in toluene solution was further confirmed by ab initio molecular dynamics (AIMD) simulation with explicit representation of solvent. Under conditions of liquid-liquid extraction (LLE), purified receptors cis- and trans-2 were both found to remove NaOH from a pH 11.01 aqueous source phase into toluene with extraction efficiencies (E%) of 50-60% when used equimolar to NaOH. However, in all cases, precipitation was observed. Complexities associated with precipitation could be avoided by immobilization of the receptors onto a chemically inert poly(styrene) resin by means of solvent impregnation. The use of solvent-impregnated resins (SIRs) eliminated precipitation in solution while retaining the extraction efficiency toward NaOH. This allowed both the pH and salinity of the alkaline source phase to be lowered.

7.
Neurogenetics ; 24(3): 161-169, 2023 07.
Artículo en Inglés | MEDLINE | ID: mdl-37022522

RESUMEN

Gene sub-region encoded protein domain is the basic unit for protein structure and function. The DMD gene is the largest coding gene in humans, with its phenotype relevant to idiopathic generalized epilepsy. We hypothesized variants clustered in sub-regions of idiopathic generalized epilepsy genes and investigated the relationship between the DMD gene and idiopathic generalized epilepsy. Whole exome sequencing was performed in 106 idiopathic generalized epilepsy individuals. DMD variants were filtered with variant type, allele frequency, in silico prediction, hemizygous or homozygous status in the population, inheritance mode, and domain location. Variants located at the sub-regions were selected by the subRVIS software. The pathogenicity of variants was evaluated by the American College of Medical Genetics and Genomics criteria. Articles on functional studies related to epilepsy for variants clustered protein domains were reviewed. In sub-regions of the DMD gene, two variants were identified in two unrelated cases with juvenile absence epilepsy or juvenile myoclonic epilepsy. The pathogenicity of both variants was uncertain significance. Allele frequency of both variants in probands with idiopathic generalized epilepsy reached statistical significance compared with the population (Fisher's test, p = 2.02 × 10-6, adjusted α = 4.52 × 10-6). The variants clustered in the spectrin domain of dystrophin, which binds to glycoprotein complexes and indirectly affects ion channels contributing to epileptogenesis. Gene sub-region analysis suggests a weak association between the DMD gene and idiopathic generalized epilepsy. Functional analysis of gene sub-region helps infer the pathogenesis of idiopathic generalized epilepsy.


Asunto(s)
Epilepsia Generalizada , Epilepsia , Humanos , Epilepsia Generalizada/genética , Frecuencia de los Genes , Fenotipo
8.
J Org Chem ; 88(11): 7489-7497, 2023 Jun 02.
Artículo en Inglés | MEDLINE | ID: mdl-37114576

RESUMEN

A designed method for the preparation of 3-aminomethylated maleimides via Morita-Baylis-Hillman (MBH) reaction was developed. This phosphine-catalyzed coupling adopted maleimides and 1,3,5-triazinanes as the substrate, giving a series of 3-aminomethylated maleimide derivatives with a double bond retained on the maleimide ring in 41-90% yield. Acylation, isomerization, and Michael addition of the obtained products demonstrated the synthetic application of the present protocol. The results of control experiments indicated that phosphorus ylide formation and elimination take place during the reaction pathway.

9.
Angew Chem Int Ed Engl ; 62(17): e202215882, 2023 Apr 17.
Artículo en Inglés | MEDLINE | ID: mdl-36847452

RESUMEN

Herein, we report a manganese-catalyzed three-component coupling of secondary alcohols, primary alcohols and methanol for the synthesis of ß,ß-methylated/alkylated secondary alcohols. Using our method, a series of 1-arylethanol, benzyl alcohol derivatives, and methanol undergo sequential coupling efficiently to construct assembled alcohols with high chemoselectivity in moderate to good yields. Mechanistic studies suggest that the reaction proceeds via methylation of a benzylated secondary alcohol intermediate to generate the final product.

10.
J Org Chem ; 87(5): 3762-3769, 2022 Mar 04.
Artículo en Inglés | MEDLINE | ID: mdl-35168325

RESUMEN

A convenient and practical hydrosulfonylation and disulfonylation of substituted maleimides was realized using sulfonyl hydrazides as the sulfur reagent and tert-butyl hydroperoxide as the oxidant. The advantages of the reactions include mild and transition-metal-free reaction conditions, good functional group tolerance, and readily available starting materials. The radical species-induced pathway is also demonstrated by mechanistic studies.

11.
J Org Chem ; 87(22): 15661-15669, 2022 11 18.
Artículo en Inglés | MEDLINE | ID: mdl-36317696

RESUMEN

By employing Cu(CH3CN)4PF6 as the catalyst and tert-butyl hydroperoxide as the oxidant, we realized a three-component radical selenosulfonation of substituted maleimides, sulfonyl hydrazides, and diphenyl diselenides, providing a series of 3,4-selenosulfonylated succinimides in moderate to good yields. This reaction features broad substrate scopes, high functional-group tolerability, and feasibility of gram-scale synthesis, enabling one-step construction of C-SO2 and C-Se bonds under mild reaction conditions. Preliminary mechanistic studies support the free-radical-induced pathway.


Asunto(s)
Cobre , Yodo , Cobre/química , Maleimidas , Estructura Molecular , Hidrazinas/química , Catálisis
12.
J Org Chem ; 87(5): 2711-2720, 2022 Mar 04.
Artículo en Inglés | MEDLINE | ID: mdl-35018783

RESUMEN

An efficient annulation method for the synthesis of polysubstituted dihydrofurans from 1,3-dicarbonyl compounds and maleimides is described. The reactions can afford furo[2,3-c]pyrrole derivatives with satisfactory yields. The developed strategy realizes the direct oxidative double C(sp3)-H functionalization in the presence of copper(I) salts and 2-(tert-butylperoxy)-2-methylpropane. Meanwhile, this protocol features a mild reaction condition and simple catalytic system. A reaction mechanism involving a single electron oxidation is also proposed.

13.
Crit Care ; 26(1): 349, 2022 11 12.
Artículo en Inglés | MEDLINE | ID: mdl-36371256

RESUMEN

BACKGROUND: Several biomarkers have been proposed to predict the occurrence of acute kidney injury (AKI); however, their efficacy varies between different trials. The aim of this study was to compare the predictive performance of different candidate biomarkers for AKI. METHODS: In this systematic review, we searched PubMed, Medline, Embase, and the Cochrane Library for papers published up to August 15, 2022. We selected all studies of adults (> 18 years) that reported the predictive performance of damage biomarkers (neutrophil gelatinase-associated lipocalin (NGAL), kidney injury molecule-1 (KIM-1), liver-type fatty acid-binding protein (L-FABP)), inflammatory biomarker (interleukin-18 (IL-18)), and stress biomarker (tissue inhibitor of metalloproteinases-2 × insulin-like growth factor-binding protein-7 (TIMP-2 × IGFBP-7)) for the occurrence of AKI. We performed pairwise meta-analyses to calculate odds ratios (ORs) and 95% confidence intervals (CIs) individually. Hierarchical summary receiver operating characteristic curves (HSROCs) were used to summarize the pooled test performance, and the Grading of Recommendations, Assessment, Development and Evaluations criteria were used to appraise the quality of evidence. RESULTS: We identified 242 published relevant studies from 1,803 screened abstracts, of which 110 studies with 38,725 patients were included in this meta-analysis. Urinary NGAL/creatinine (diagnostic odds ratio [DOR] 16.2, 95% CI 10.1-25.9), urinary NGAL (DOR 13.8, 95% CI 10.2-18.8), and serum NGAL (DOR 12.6, 95% CI 9.3-17.3) had the best diagnostic accuracy for the risk of AKI. In subgroup analyses, urinary NGAL, urinary NGAL/creatinine, and serum NGAL had better diagnostic accuracy for AKI than urinary IL-18 in non-critically ill patients. However, all of the biomarkers had similar diagnostic accuracy in critically ill patients. In the setting of medical and non-sepsis patients, urinary NGAL had better predictive performance than urinary IL-18, urinary L-FABP, and urinary TIMP-2 × IGFBP-7: 0.3. In the surgical patients, urinary NGAL/creatinine and urinary KIM-1 had the best diagnostic accuracy. The HSROC values of urinary NGAL/creatinine, urinary NGAL, and serum NGAL were 91.4%, 85.2%, and 84.7%, respectively. CONCLUSIONS: Biomarkers containing NGAL had the best predictive accuracy for the occurrence of AKI, regardless of whether or not the values were adjusted by urinary creatinine, and especially in medically treated patients. However, the predictive performance of urinary NGAL was limited in surgical patients, and urinary NGAL/creatinine seemed to be the most accurate biomarkers in these patients. All of the biomarkers had similar predictive performance in critically ill patients. Trial registration CRD42020207883 , October 06, 2020.


Asunto(s)
Lesión Renal Aguda , Interleucina-18 , Adulto , Humanos , Lipocalina 2/orina , Inhibidor Tisular de Metaloproteinasa-2 , Creatinina , Lesión Renal Aguda/terapia , Biomarcadores , Hospitales
14.
Psychol Res ; 86(2): 443-451, 2022 Mar.
Artículo en Inglés | MEDLINE | ID: mdl-33839908

RESUMEN

Aging is accompanied by an increase in the probability of false memory. However, what role sleep plays in the age effect in false memory is less understood. Our study utilized a simplified conjoint recognition (SCR)-based Deese-Roediger-McDermott (DRM) paradigm to investigate the role of sleep on false memory in young and older adults. The results showed that sleep effect in false memory was modulated by age, manifested as sleep increased young adults' falsely recognized critical lures, while it reduced older adults'. In addition, in a more fine-grained analysis, the results of multinomial processing tree (MPT) modeling further revealed that young adults were more likely to retrieve memory based on gist traces than older adults, and young adults were more susceptible to guess a probe as "old" than older adults in the sleep condition. Combined findings from the number and ratio of falsely recognized critical lures and the MPT modeling, the current study suggested that sleep might increase young adults' false memory via gist extraction, while it decreased older adults' false memory via verbatim trace consolidation. The study contributes to a comprehensive view on the age-by-sleep effect on false recognition, with the segregation of cognitive components of verbatim memory, gist memory, and response bias.


Asunto(s)
Memoria , Recuerdo Mental , Anciano , Envejecimiento/fisiología , Humanos , Memoria/fisiología , Recuerdo Mental/fisiología , Reconocimiento en Psicología/fisiología , Sueño/fisiología , Adulto Joven
15.
Biomacromolecules ; 22(12): 4988-4999, 2021 12 13.
Artículo en Inglés | MEDLINE | ID: mdl-34724615

RESUMEN

Autograft is currently the gold standard in the clinical treatment of peripheral nerve injury (PNI), which, however, is limited by the availability of a donor nerve and secondary injuries. Nerve guidance conduits (NGC) provide a suitable microenvironment to promote the regeneration of injured nerves, which could be the substitutes for autografts. In this study, nerve growth factor (NGF) encapsulated chitosan nanoparticles (CSNPs) were first constructed in situ in an oxidized bacterial cellulose (OBC) conduit using the ion gel method after the introduction of a CS/NGF solution under pressure to enable a sustainable release of NGF. A novel NGF@CSNPs/OBC nanocomposite with antibacterial activity, biodegradability, and porous microstructure was successfully developed. In vitro experiments showed that the nanocomposite promoted the adhesion and proliferation of Schwann cells. When the nanocomposite was applied as NGC to repair the sciatic nerve defect of rats, a successful repair of the 10 mm nerve defect was observed after 4 weeks. At week 9, the diameter, morphology, histology, and functional recovery of the regenerated nerve was comparable to the autografts, indicating that the NGC effectively promoted the regeneration and function recovery of the nerve. In summary, the NGF@CSNPs/OBC as a novel NGC provides great potential in the treatment of PNI.


Asunto(s)
Quitosano , Nanopartículas , Factor de Crecimiento Nervioso , Regeneración Nerviosa , Animales , Quitosano/química , Nanopartículas/química , Factor de Crecimiento Nervioso/farmacología , Ratas , Nervio Ciático/lesiones , Nervio Ciático/fisiología
16.
Inorg Chem ; 60(20): 15808-15817, 2021 Oct 18.
Artículo en Inglés | MEDLINE | ID: mdl-34618431

RESUMEN

The trend in affinity of two 1,2-hydroxypyridinonate lanthanide(III) receptors-LnIII-2,2-Li-HOPO and LnIII-3,3-Gly-HOPO (LnIII = LaIII, PrIII, NdIII, SmIII, EuIII, GdIII, TbIII, DyIII, HoIII, ErIII, TmIII, YbIII, and LuIII)-for phosphate across the series was investigated by luminescence spectroscopy via competition against the central europium(III) analog. Regardless of the ligand, the rare earth receptors display a steep and continuous increase in affinity for their phosphate guest across the series, with the later lanthanides displaying the highest affinity for the oxyanion. This trend mirrors that of the stability of the lanthanide receptors, which also increases significantly and continuously from LaIII to LuIII. For these two ligands, the ionic radius of a rare earth, a parameter directly linked to its Lewis acidity, correlates strongly with its affinity for anions, regardless of whether that anion is the one coordinating it (in this case the 1,2-hydroxypyridinonate ligand) or the guest targeted by the lanthanide receptor (in this case phosphate). These observations are indicative of a lack of steric hindrance for coordination of phosphate. Advantageously, increased efficacy of the lanthanide receptor comes with increased stability. The remarkably high stability of LuIII-2,2-Li-HOPO, combined with its high affinity for phosphate, makes it a particularly promising candidate for translational application to medical or environmental sequestration of phosphate since the higher stability will further reduce the risk of the rare earth leaching during anion separation. The unusually large difference in stability between lanthanide complexes (the LuIII complex of 2,2-Li-HOPO is at least 7 orders of magnitude more stable than the LaIII one) bodes well for potential applications in rare earth separation.

17.
BMC Womens Health ; 21(1): 167, 2021 04 20.
Artículo en Inglés | MEDLINE | ID: mdl-33879147

RESUMEN

BACKGROUND: Catamenial pneumothorax is characterized by spontaneous recurring pneumothorax during menstruation, which is a common clinical manifestation of thoracic endometriosis syndrome. There are still controversies about its pathogenesis. CASE PRESENTATION: A 43-year-old woman with a history of endometriosis came to our hospital due to recurring pneumothorax during menstruation. Uniportal Video-assisted Thoracoscopic Surgery (VATS) exploration was performed on the eve of menstruating. We thoroughly explored the diaphragm, visceral and parietal pleura: The lung surface was scattered with yellowish-brown implants; no bullae were found; multiple diaphragmatic defects were found on the dome. And surprisingly, we caught a fascinating phenomenon: Bubbles were slipping into pleural cavity through diaphragmatic defects. We excised the diaphragmatic lesions and wedge resected the right upper lung lesion; cleared the deposits and flushed the thoracic cavity with pure iodophor. Diaphragmatic lesions confirmed the presence of endometriosis, and interestingly enough, microscopically, endometrial cells were shedding with impending menses. After a series of intraoperative operations and postoperative endocrine therapy, the disease did not recur after a period of follow-up. CONCLUSION: We have witnessed the typical signs of catamenial pneumothorax at the accurate timing: Not only observed the process of gas migration macroscopically, but also obtained pathological evidence of diaphragmatic periodic perforation microscopically, which is especially precious and confirms the existing theory that retrograde menstruation leads to diaphragmatic endometriosis, and the diaphragmatic fenestration is obtained due to the periodic activities of ectopic endometrium.


Asunto(s)
Endometriosis , Neumotórax , Adulto , Endometriosis/complicaciones , Endometriosis/cirugía , Femenino , Humanos , Menstruación , Neumotórax/etiología , Neumotórax/cirugía , Cirugía Torácica Asistida por Video
18.
Neurobiol Learn Mem ; 171: 107204, 2020 05.
Artículo en Inglés | MEDLINE | ID: mdl-32145405

RESUMEN

Sleep plays a crucial role in memory consolidation. However, the influence of sleep on emotional memory consolidation in older adults, especially in the context of associative memory, which is more cognitively demanding than item memory, remains elusive. For this study we recruited young and older adults, and randomly assigned them into the sleep or wake condition. They were administrated a visual-spatial associative memory task, which required them to remember a picture and its location. We measured memory performance for positive, neutral, and negative stimuli before and after a 12-h interval of being awake or asleep. An accuracy analysis indicated a beneficial effect of sleep on location memory regardless of age and valence. In addition, in a more fine-grained analysis, the drift rate from diffusion modeling showed that sleep facilitated the consolidation of negative stimuli in young adults, while this emotion bias shifted to positive stimuli in older adults. Moreover, negative correlations were observed between the change of memory performance and sleep characteristics in older adults, indicating that more sleep results in fewer negative memories. Our results provide a relatively weak support for an age-related emotional bias in the context of associative memory, manifested in the absence of an age-by-valence interaction in accuracy, whilst a modeling parameter in consideration of both accuracy and response time yielded evidence consistent with the predictions of the socioemotional selectivity theory.


Asunto(s)
Aprendizaje por Asociación/fisiología , Consolidación de la Memoria/fisiología , Memoria/fisiología , Sueño/fisiología , Vigilia/fisiología , Factores de Edad , Anciano , Femenino , Humanos , Masculino , Persona de Mediana Edad , Pruebas Neuropsicológicas , Adulto Joven
19.
Inorg Chem ; 59(6): 4096-4108, 2020 Mar 16.
Artículo en Inglés | MEDLINE | ID: mdl-32105456

RESUMEN

To evaluate the effect of ligand geometry on the coordination number, number of inner-sphere water molecules, and affinity for anions of the corresponding lanthanide complex, six tris-bidentate 1,2-hydroxypyridonate (HOPO) europium(III) complexes with different cap sizes were synthesized and characterized. Wider or more flexible ligand caps, such as in EuIII-TREN-Gly-HOPO and EuIII-3,3-Gly-HOPO, enable the formation of nine-coordinate europium(III) complexes bearing three inner-sphere water molecules. In contrast, smaller or more rigid caps, such as in EuIII-TREN-HOPO, EuIII-2,2-Li-HOPO, EuIII-3,3-Li-HOPO, and EuIII-2,2-Gly-HOPO, favor eight-coordinate europium(III) complexes that have only two inner-sphere water molecules. Notably, there is no correlation between the number of inner-sphere water molecules and the affinity of the Eu(III) complexes for phosphate. Some q = 2 (EuIII-TREN-HOPO, EuIII-3,3-Li-HOPO, and EuIII-2,2-Gly-HOPO) and some q = 3 (EuIII-TREN-Gly-HOPO) complexes have no affinity for anions, whereas one q = 2 complex (EuIII-2,2-Li-HOPO) and one q = 3 complex (EuIII-3,3-Gly-HOPO) have a high affinity for phosphate. For the latter two systems, each inner-sphere water molecule is replaced with a phosphate anion, resulting in the formation of EuLPi2 and EuLPi3 adducts, respectively.

20.
J Org Chem ; 84(17): 11032-11041, 2019 Sep 06.
Artículo en Inglés | MEDLINE | ID: mdl-31333030

RESUMEN

A regioselective synthesis of polysubstituted dihydropyrazoles and pyrazoles through an iodine-catalyzed oxidative cyclization strategy of aldehyde hydrazones with electron-deficient olefins is described. The protocol adopts very mild reaction conditions and provides desirable yields. The reaction is supposed to proceed via a cascade C-H functionalization, C-N bond formation, and oxidation sequential processes. The overall simplicity and regioselectivity of the catalytic system make this approach a valuable and step-economical tool to construct a C-C bond for the synthesis of Mefenpyr-Diethyl.

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