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1.
Plant J ; 116(1): 128-143, 2023 10.
Artículo en Inglés | MEDLINE | ID: mdl-37347678

RESUMEN

The transition from vegetative to reproductive development (floral transition) is a costly process in annual plants requiring increased investments in metabolic resources. The Arabidopsis thaliana (Arabidopsis) PHD finger protein EDM2 and RRM domain proteins EDM3 and IBM2 are known to form chromatin-associated complexes controlling transcript processing. We are reporting that distinct splice isoforms of EDM3 and IBM2 cooperate in the coordination of the floral transition with basal immune responses. These cooperating splice isoforms, termed EDM3L and IBM2L, control the intensity of basal immunity and, via a separate pathway, the timing of the floral transition. During the developmental phase prior to the floral transition expression of EDM3L and IBM2L strongly and gradually increases, while these isoforms simultaneously down-regulate expression of the floral suppressor gene FLC and promote the transition to reproductive growth. At the same time these accumulating EDM3 and IBM2 splice isoforms gradually suppress basal immunity against the virulent Noco2 isolate of the pathogenic oomycete Hyaloperonospora arabidopsidis and down-regulate expression of a set of defense-associated genes and immune receptor genes. We are providing clear evidence for a functional link between the floral transition and basal immunity in the annual plant Arabidopsis. Coordination of these two biological processes, which compete for metabolic resources, is likely critical for plant survival and reproductive success.


Asunto(s)
Proteínas de Arabidopsis , Arabidopsis , Arabidopsis/metabolismo , Proteínas de Arabidopsis/genética , Proteínas de Arabidopsis/metabolismo , Factores de Transcripción/metabolismo , Proteínas con Motivos de Reconocimiento de ARN/genética , Proteínas con Motivos de Reconocimiento de ARN/metabolismo , Flores , Inmunidad , Regulación de la Expresión Génica de las Plantas , Proteínas de Dominio MADS/genética , Histona Demetilasas con Dominio de Jumonji/metabolismo
2.
Small ; : e2400042, 2024 Apr 11.
Artículo en Inglés | MEDLINE | ID: mdl-38600889

RESUMEN

Modulating the coordination environment of the metal active center is an effective method to boost the catalytic performances of metal-organic frameworks (MOFs) for oxygen evolution reaction (OER). However, little attention has been paid to the halogen effects on the ligands engineering. Herein, a series of MOFs X─FeNi-MOFs (X = Br, Cl, and F) is constructed with different coordination microenvironments to optimize OER activity. Theoretical calculations reveal that with the increase in electronegativity of halogen ions in terephthalic acid molecular (TPA), the Bader charge of Ni atoms gets larger and the Ni-3d band center and O-2p bands move closer to the Fermi level. This indicates that an increase in ligand negativity of halogen ions in TPA can promote the adsorption ability of catalytic sites to oxygen-containing intermediates and reduce the activation barrier for OER. Experimental also demonstrates that F─FeNi-MOFs exhibit the highest catalytic activity with an ultralow overpotential of 218 mV at 10 mA cm-2, outperforming most otate-of-the-art Fe/Co/Ni-based MOFs catalysts, and the enhanced mass activity by seven times compared with that for the sample before ligands engineering. This work opens a new avenue for the realization of the modulation of NiFe─O bonding by halogen ion in TPA and improves the OER performance of MOFs.

3.
Chemistry ; 30(17): e202303918, 2024 Mar 20.
Artículo en Inglés | MEDLINE | ID: mdl-38102982

RESUMEN

The photoluminescent properties of lanthanide complexes have been thoroughly investigated; however, there have been much fewer studies showcasing their potential use in ionizing radiation detection. In this work, we delve into the photo- and radio-induced luminescence of a series of lanthanide-bearing organic-inorganic hybrids and their potential as a platform for X-ray scintillation and imaging. The judicious synergy between lanthanide cations and 2,6-di(1H-pyrazol-1-yl)isonicotinate (bppCOO-) ligands affords six new materials with three distinct structures. Notably, Eu-bppCOO-1 and Tb-bppCOO-2 display sharp fingerprint X-ray-excited luminescence (XEL), the intensities of which can be linearly correlated with the X-ray dose rates over a broad dynamic range (0.007-4.55 mGy s-1). Moreover, the X-ray sensing efficacies of Eu-bppCOO-1 and Tb-bppCOO-2 were evaluated, showing that Tb-bppCOO-2 features a lower detection limit of 4.06 µGy s-1 compared to 14.55 µGy s-1 of Eu-bppCOO-1. Given the higher X-ray sensitivity and excellent radiation stability of Tb-bppCOO-2, we fabricated a flexible scintillator film for X-ray imaging by embedding finely ground Tb-bppCOO-2 in the polydimethylsiloxane (PDMS) polymer. The resulting scintillator film can be utilized for high-resolution X-ray imaging with a spatial resolution of approximately 7 lp mm-1.

4.
Mov Disord ; 39(5): 798-813, 2024 May.
Artículo en Inglés | MEDLINE | ID: mdl-38465843

RESUMEN

BACKGROUND: Colony-stimulating factor 1 receptor (CSF1R)-related disorder (CRD) is a rare autosomal dominant disease. The clinical and genetic characteristics of Chinese patients have not been elucidated. OBJECTIVE: The objective of the study is to clarify the core features and influence factors of CRD patients in China. METHODS: Clinical and genetic-related data of CRD patients in China were collected. Mini-Mental State Examination (MMSE), Montreal Cognitive Assessment (MoCA), and Sundal MRI Severity Score were evaluated. Whole exome sequencing was used to analyze the CSF1R mutation status. Patients were compared between different sexes, mutation types, or mutation locations. RESULTS: A total of 103 patients were included, with a male-to-female ratio of 1:1.51. The average age of onset was (40.75 ± 8.58). Cognitive impairment (85.1%, 86/101) and parkinsonism (76.2%, 77/101) were the main clinical symptoms. The most common imaging feature was bilateral asymmetric white matter changes (100.0%). A total of 66 CSF1R gene mutants (22 novel mutations) were found, and 15 of 92 probands carried c.2381 T > C/p.I794T (16.30%). The MMSE and MoCA scores (17.0 [9.0], 11.90 ± 7.16) of female patients were significantly lower than those of male patients (23.0 [10.0], 16.36 ± 7.89), and the white matter severity score (20.19 ± 8.47) of female patients was significantly higher than that of male patients (16.00 ± 7.62). There is no statistical difference in age of onset between male and female patients. CONCLUSIONS: The core manifestations of Chinese CRD patients are progressive cognitive decline, parkinsonism, and bilateral asymmetric white matter changes. Compared to men, women have more severe cognitive impairment and imaging changes. c.2381 T > C/p.I794T is a hotspot mutation in Chinese patients. © 2024 International Parkinson and Movement Disorder Society.


Asunto(s)
Mutación , Fenotipo , Receptores de Factor Estimulante de Colonias de Granulocitos y Macrófagos , Humanos , Masculino , Femenino , Adulto , Persona de Mediana Edad , China/epidemiología , Receptores de Factor Estimulante de Colonias de Granulocitos y Macrófagos/genética , Mutación/genética , Genotipo , Disfunción Cognitiva/genética , Imagen por Resonancia Magnética , Trastornos Parkinsonianos/genética , Anciano , Edad de Inicio , Adulto Joven , Receptor de Factor Estimulante de Colonias de Macrófagos
5.
Hum Factors ; 66(4): 1276-1301, 2024 Apr.
Artículo en Inglés | MEDLINE | ID: mdl-36625335

RESUMEN

OBJECTIVE: This paper proposes an objective method to measure and identify trust-change directions during takeover transitions (TTs) in conditionally automated vehicles (AVs). BACKGROUND: Takeover requests (TORs) will be recurring events in conditionally automated driving that could undermine trust, and then lead to inappropriate reliance on conditionally AVs, such as misuse and disuse. METHOD: 34 drivers engaged in the non-driving-related task were involved in a sequence of takeover events in a driving simulator. The relationships and effects between drivers' physiological responses, takeover-related factors, and trust-change directions during TTs were explored by the combination of an unsupervised learning algorithm and statistical analyses. Furthermore, different typical machine learning methods were applied to establish recognition models of trust-change directions during TTs based on takeover-related factors and physiological parameters. RESULT: Combining the change values in the subjective trust rating and monitoring behavior before and after takeover can reliably measure trust-change directions during TTs. The statistical analysis results showed that physiological parameters (i.e., skin conductance and heart rate) during TTs are negatively linked with the trust-change directions. And drivers were more likely to increase trust during TTs when they were in longer TOR lead time, with more takeover frequencies, and dealing with the stationary vehicle scenario. More importantly, the F1-score of the random forest (RF) model is nearly 77.3%. CONCLUSION: The features investigated and the RF model developed can identify trust-change directions during TTs accurately. APPLICATION: Those findings can provide additional support for developing trust monitoring systems to mitigate both drivers' overtrust and undertrust in conditionally AVs.


Asunto(s)
Conducción de Automóvil , Humanos , Confianza , Automatización , Proyectos de Investigación , Frecuencia Cardíaca , Accidentes de Tránsito , Tiempo de Reacción/fisiología
6.
Small ; 19(10): e2206782, 2023 Mar.
Artículo en Inglés | MEDLINE | ID: mdl-36534835

RESUMEN

Monitoring and shielding of X-ray radiation are of paramount importance across diverse fields. However, they are frequently realized in separate protocols and a single material integrating both functions remained elusive. Herein, a hexanuclear cluster [Th6 (µ3 -OH)4 (µ3 -O)4 (H2 O)6 ](pba)6 (HCOO)6 (Th-pba-0D) incorporating high-Z thorium cations and 3-(pyridin-4-yl)benzoate ligands that can function as a brand-new dual-module platform for visible detection and efficient shielding of ionizing radiation is demonstrated. Th-pba-0D exhibits rather unique reversible radiochromism upon alternating X-ray and UV irradiation. Moreover, the millimeter scale crystal size of Th-pba-0D renders the penetration depth of X-ray visible to naked eye and leads to the unearthing of its high X-ray attenuation efficiency. Indeed, the shielding efficacy of Th-pba-0D is comparable to that of lead glass containing 40% PbO, and a Th-pba-0D pellet with a thickness of merely 1.2 mm can shield 99.73% X-ray (16 keV). These studies portend the possible utilization of thorium-bearing materials as a bifunctional platform for radiation detection and shielding.

7.
Langmuir ; 39(33): 11864-11878, 2023 Aug 22.
Artículo en Inglés | MEDLINE | ID: mdl-37556763

RESUMEN

Fe-based amorphous coatings are ideal materials for surface protection due to their outstanding mechanical properties and corrosion resistance. However, coating defects are inevitably formed during the preparation of coatings by thermal spray technology, which seriously affects the corrosion performance. Inspired by bionics, conceiving superhydrophobic surfaces with liquid barrier properties has become a new idea for the corrosion protection of metal surfaces. In this work, based on surface hydroxylation, we designed a superhydrophobic Fe-based amorphous coating with corrosion resistance by chemical etching combined with a thermally driven preparation strategy. The obtained superhydrophobic coatings exhibit liquid repellency (contact angle >150°) and excellent corrosion resistance (corrosion current density and passive current density reduced by 3 orders of magnitude). The results revealed that the superhydrophobic behavior stems from the construction of hydroxyl-induced surface micro-/nanomultilevel aggregates (cluster structures). The hydrophobic agent layer deposited on the surface of cluster aggregates and the nanoparticle elements that constitute the clusters dominate the corrosion resistance of the coating. This work provides an effective guide to the design of high-corrosion-resistant Fe-based amorphous alloy coatings and promotes their engineering applications.

8.
Inorg Chem ; 62(21): 8158-8165, 2023 May 29.
Artículo en Inglés | MEDLINE | ID: mdl-37186814

RESUMEN

Actinide-bearing metal-organic frameworks (MOFs) encompass intriguing structures and properties, but the radioactivity of actinide cripples their applications. Herein, we have constructed a new thorium-based MOF (Th-BDAT) as a bifunctional platform for the adsorption and detection of radioiodine, a more radioactive fission product that can readily spread through the atmosphere in its molecular form or via solution as anionic species. The iodine capture within the framework of Th-BDAT from both the vapor phase and the cyclohexane solution has been verified, showing that Th-BDAT features maximum I2 adsorption capacities (Qmax) of 959 and 1046 mg/g, respectively. Notably, the Qmax of Th-BDAT toward I2 from cyclohexane solution ranks among the highest value for Th-MOFs reported to date. Furthermore, incorporating highly extended and π-electron-rich BDAT4- ligands renders Th-BDAT as a luminescent chemosensor whose emission can be selectively quenched by iodate with a detection limit of 1.367 µM. Our findings thus foreshadow promising directions that might unlock the full potential of actinide-based MOFs from the point of view of practical application.

9.
Eur J Nutr ; 62(7): 2919-2928, 2023 Oct.
Artículo en Inglés | MEDLINE | ID: mdl-37402817

RESUMEN

PURPOSE: There were only two definitions of iodine-deficient (water iodine concentration < 10 µg/L) and iodine-excess areas (water iodine concentration > 100 µg/L) in China before 2020. Areas with water iodine concentration between 10 and 100 µg/L implement the same policy as iodine-deficient areas to provide iodized salt. The definition of iodine-adequate areas was formulated in 2020 for the first time. The paper aims to investigate the coverage rate of iodized salt (CR) in different areas defined according to the latest national standards, evaluate the iodine status of local women, and provide a basis for the revision and improvement of relevant policies. METHODS: A total of 1948 women aged 18-60 were recruited from the iodine extra-high areas (IEHA), iodine-excess areas (IEA), iodine-adequate areas (IAA), inland iodine-deficient areas (IIDA), and coastal iodine-deficient areas (CIDA). Information on daily diet was collected with the Food Frequency Questionnaire. Drinking water, salt, food, and urine samples were collected and tested in our laboratory. Based on the recommended daily iodine intake, we assessed whether the subjects' daily iodine intake levels were adequate. RESULTS: The CR and the median urinary iodine concentrations (UICs) were 4.02% and 98.03 µg/L in CIDA, 89.74% and 144.93 µg/L in IIDA, 26.55% and 178.60 µg/L in IAA, 8.78% and 446.5 µg/L in IEA, 3.95% and 605.4 µg/L in IEHA, respectively. The differences among these five areas were statistically significant (P < 0.0001). The daily dietary iodine intakes were mainly from drinking water in IAA (63.92%), IEA (92.29%), and IEHA (92.93%), and were mainly from iodized salt in IIDA (59.22%) and food in CIDA (86.6%). CONCLUSION: Women in IAA and IIDA were in an adequate iodine state. Women in IEA and IEHA were in an iodine-excess state, and it is necessary to carry out water improvements projects. Women in CIDA were in a slight iodine-deficient state, and health education on scientific iodine fortification should be strengthened to increase iodine intake.


Asunto(s)
Agua Potable , Yodo , Humanos , Femenino , Cloruro de Sodio Dietético/orina , Yodo/orina , Estado Nutricional , Encuestas y Cuestionarios , China
10.
Plant Cell Rep ; 42(6): 1071-1088, 2023 Jun.
Artículo en Inglés | MEDLINE | ID: mdl-37024635

RESUMEN

KEY MESSAGE: TFL1-like genes of the basal eudicot Platanus acerifolia have conserved roles in maintaining vegetative growth and inhibiting flowering, but may act through distinct regulatory mechanism. Three TERMINAL FLOWER 1 (TFL1)-like genes were isolated and characterized from London plane tree (Platanus acerifolia). All genes have conserved genomic organization and characteristic of the phosphatidylethanolamine-binding protein (PEBP) family. Sequence alignment and phylogenetic analysis indicated that two genes belong to the TFL1 clade, designated as PlacTFL1a and PlacTFL1b, while another one was grouped in the BFT clade, named as PlacBFT. qRT-PCR analysis showed that all three genes primarily expressed in vegetative phase, but the expression of PlacTFL1a was much higher and wider than that of PlacTFL1b, with the latter only detected at relatively low expression levels in apical and lateral buds in April. PlacBFT was mainly expressed in young stems of adult trees followed by juvenile tissues. Ectopic expression of any TFL1-like gene in Arabidopsis showed phenotypes of delayed or repressed flowering. Furthermore, overexpression of PlacTFL1a gene in petunia also resulted in extremely delayed flowering. In non-flowering 35:PlacTFL1a transgenic petunia plants, the FT-like gene (PhFT) gene was significantly upregulated and AP1 homologues PFG, FBP26 and FBP29 were significantly down-regulated in leaves. Yeast two-hybrid analysis indicated that only weak interactions were detected between PlacTFL1a and PlacFDL, and PlacTFL1a showed no interaction with PhFDL1/2. These results indicated that the TFL1-like genes of Platanus have conserved roles in repressing flowering, but probably via a distinct regulatory mechanism.


Asunto(s)
Proteínas de Arabidopsis , Arabidopsis , Proteínas de Plantas/genética , Proteínas de Plantas/metabolismo , Filogenia , Flores , Proteínas de Arabidopsis/genética , Arabidopsis/genética , Arabidopsis/metabolismo , Plantas Modificadas Genéticamente/metabolismo , Regulación de la Expresión Génica de las Plantas/genética
11.
Eur Spine J ; 32(7): 2396-2401, 2023 07.
Artículo en Inglés | MEDLINE | ID: mdl-37150768

RESUMEN

PURPOSE: To evaluate the influence of K-line on the outcome of open-door laminoplasty versus anterior cervical corpectomy decompression and fusion (ACCF) for patients with more than two levels of ossification of the posterior longitudinal ligament (OPLL). METHODS: 60 patients undergoing open-door laminoplasty and 62 patients undergoing ACCF from January 2013 to January 2020 with more than 2 years of follow-up were included. Eighty-four cases with the ossification mass not beyond the K-line were grouped as K-line (+), while thirty-eight cases were grouped as K-line (-). The operation time, intraoperative blood loss, hospital stay, preoperative, postoperative, and last follow-up JOA scores, and postoperative complications were investigated. RESULTS: The improvement rate of JOA scores after posterior approaches in cases of group K-line (+) and K-line (-) was 72.4% and 53.1%, respectively, which showed a significant difference (P < 0.01). In group K-line (+), the improvement of JOA scores for open-door laminoplasty was 73.4% and 71.8% for ACCF, which showed no significant difference (P > 0.05). In group K-line (-), the improvement of JOA scores for ACCF was 52.1% and 42.9% for open-door laminoplasty, which showed a significant difference (P < 0.05). The incidence of C5 palsy was significantly lower in cases with ACCF than in cases with open-door laminoplasty (P < 0.05). CONCLUSION: For patients with more than two levels of OPLL, preoperative K-line (+) predicates a better outcome than K-line (-). For cases with K-line (-), ACCF provides better neurologic function recovery. For patients with K-line (+), open-door laminoplasty provides the same neurologic function recovery of ACCF.


Asunto(s)
Laminoplastia , Osificación del Ligamento Longitudinal Posterior , Fusión Vertebral , Humanos , Ligamentos Longitudinales/cirugía , Osificación del Ligamento Longitudinal Posterior/cirugía , Osificación del Ligamento Longitudinal Posterior/complicaciones , Resultado del Tratamiento , Osteogénesis , Vértebras Cervicales/diagnóstico por imagen , Vértebras Cervicales/cirugía , Estudios Retrospectivos
12.
PLoS Genet ; 16(9): e1008993, 2020 09.
Artículo en Inglés | MEDLINE | ID: mdl-32925902

RESUMEN

Plant NLR-type receptors serve as sensitive triggers of host immunity. Their expression has to be well-balanced, due to their interference with various cellular processes and dose-dependency of their defense-inducing activity. A genetic "arms race" with fast-evolving pathogenic microbes requires plants to constantly innovate their NLR repertoires. We previously showed that insertion of the COPIA-R7 retrotransposon into RPP7 co-opted the epigenetic transposon silencing signal H3K9me2 to a new function promoting expression of this Arabidopsis thaliana NLR gene. Recruitment of the histone binding protein EDM2 to COPIA-R7-associated H3K9me2 is required for optimal expression of RPP7. By profiling of genome-wide effects of EDM2, we now uncovered additional examples illustrating effects of transposons on NLR gene expression, strongly suggesting that these mobile elements can play critical roles in the rapid evolution of plant NLR genes by providing the "raw material" for gene expression mechanisms. We further found EDM2 to have a global role in NLR expression control. Besides serving as a positive regulator of RPP7 and a small number of other NLR genes, EDM2 acts as a suppressor of a multitude of additional NLR genes. We speculate that the dual functionality of EDM2 in NLR expression control arose from the need to compensate for fitness penalties caused by high expression of some NLR genes by suppression of others. Moreover, we are providing new insights into functional relationships of EDM2 with its interaction partner, the RNA binding protein EDM3/AIPP1, and its target gene IBM1, encoding an H3K9-demethylase.


Asunto(s)
Proteínas de Arabidopsis/genética , Proteínas NLR/genética , Receptores Inmunológicos/genética , Factores de Transcripción/genética , Arabidopsis , Proteínas de Arabidopsis/metabolismo , Epigénesis Genética , Expresión Génica , Regulación de la Expresión Génica de las Plantas , Genes de Plantas , Histona Demetilasas con Dominio de Jumonji/genética , Histona Demetilasas con Dominio de Jumonji/metabolismo , Proteínas NLR/biosíntesis , Proteínas NLR/metabolismo , Dedos de Zinc PHD , Plantas Modificadas Genéticamente , Dominios Proteicos , Proteínas de Unión al ARN/genética , Factores de Transcripción/metabolismo
13.
Int J Mol Sci ; 24(13)2023 Jun 29.
Artículo en Inglés | MEDLINE | ID: mdl-37446023

RESUMEN

Heat stress is an increasingly significant abiotic stress factor affecting crop yield and quality. This study aims to uncover the regulatory mechanism of sweet corn response to heat stress by integrating transcriptome and metabolome analyses of seedlings exposed to normal (25 °C) or high temperature (42 °C). The transcriptome results revealed numerous pathways affected by heat stress, especially those related to phenylpropanoid processes and photosynthesis, with 102 and 107 differentially expressed genes (DEGs) identified, respectively, and mostly down-regulated in expression. The metabolome results showed that 12 or 24 h of heat stress significantly affected the abundance of metabolites, with 61 metabolites detected after 12 h and 111 after 24 h, of which 42 metabolites were detected at both time points, including various alkaloids and flavonoids. Scopoletin-7-o-glucoside (scopolin), 3-indolepropionic acid, acetryptine, 5,7-dihydroxy-3',4',5'-trimethoxyflavone, and 5,6,7,4'-tetramethoxyflavanone expression levels were mostly up-regulated. A regulatory network was built by analyzing the correlations between gene modules and metabolites, and four hub genes in sweet corn seedlings under heat stress were identified: RNA-dependent RNA polymerase 2 (RDR2), UDP-glucosyltransferase 73C5 (UGT73C5), LOC103633555, and CTC-interacting domain 7 (CID7). These results provide a foundation for improving sweet corn development through biological intervention or genome-level modulation.


Asunto(s)
Transcriptoma , Zea mays , Zea mays/metabolismo , Plantones/metabolismo , Regulación de la Expresión Génica de las Plantas , Respuesta al Choque Térmico/genética , Metaboloma , Perfilación de la Expresión Génica/métodos
14.
Molecules ; 28(3)2023 Feb 02.
Artículo en Inglés | MEDLINE | ID: mdl-36771128

RESUMEN

A reversible solid oxide cell (RSOC) integrating solid oxide fuel (SOFC) and a solid oxide electrolysis cell (SOEC) usually utilizes compressive seals. In this work, the vermiculite seals of various thickness and compressive load during thermal cycles and long-term operation were investigated. The leakage rates of seals were gradually increased with increasing thickness and input gas pressure. The thinner seals had good sealing performance. The compressive load was carried out at thinner seals, the possible holes were squeezed, and finally the leakage rates were lower. With a fixed input gas pressure of 1 psi, 2 psi, and 3 psi, the leakage rates of 0.50 mm vermiculite remained at around 0.009 sccm/cm, 0.017 sccm/cm and 0.028 sccm/cm during twenty thermal cycles, while the leakage rates remained at around 0.011 sccm/cm for about 240 h. Simultaneously, elemental diffusions between seals and components were limited, implying good compatibility. Furthermore, the open circuit voltage (OCV) remained at around 1.04 V during 17 thermal cycles, which is close to Nernst potentials. The stack performance confirmed that the vermiculite seals can meet the structural support and sealing requirements. Therefore, the vermiculite shows good promise for application in stacks during thermal cycles and long-term operation.

15.
J Am Chem Soc ; 144(8): 3449-3457, 2022 03 02.
Artículo en Inglés | MEDLINE | ID: mdl-35057612

RESUMEN

Developing materials that possess colorimetric responses to external stimuli is a promising strategy for addressing the current challenges in radiation dosimetry. Currently, colorimetric ionizing-radiation-responsive materials remain underexplored, and those with multistimuli response are rare. Herein, the integration of thorium cation and photoresponsive terpyridine carboxylate ligand gives rise to a thorium nanocluster, Th-101, which displays the second case of fluorochromic response and unprecedented piezochromic behavior among all actinide materials. The emission color of Th-101 exhibits a gradual transition from blue to cyan to green upon irradiation with accumulated dose, which renders colorimetric dosimetry of ionizing radiation based on a red-green-blue (RGB) concept. Further fabricating Th-101 into a custom-built optoelectronic device allows for on-site quantification of radiation dose with merits of ease of operation, rapid readout, and cost-effectiveness.


Asunto(s)
Colorantes Fluorescentes , Torio , Colorimetría
16.
J Am Chem Soc ; 144(1): 416-423, 2022 Jan 12.
Artículo en Inglés | MEDLINE | ID: mdl-34878269

RESUMEN

Electronic structure modulation among multiple metal sites is key to the design of efficient catalysts. Most studies have focused on regulating 3d transition-metal active ions through other d-block metals, while few have utilized f-block metals. Herein, we report a new class of catalyst, namely, UCoO4 with alternative CoO6 and 5f-related UO6 octahedra, as a unique example of a 5f-covalent compound that exhibits enhanced electrocatalytic oxygen evolution reaction (OER) activity because of the presence of the U 5f-O 2p-Co 3d network. UCoO4 exhibits a low overpotential of 250 mV at 10 mA cm-2, surpassing other unitary cobalt-based catalysts ever reported. X-ray absorption spectroscopy revealed that the Co2+ ion in pristine UCoO4 was converted to high-valence Co3+/4+, while U6+ remained unchanged during the OER, indicating that only Co was the active site. Density functional theory calculations demonstrated that the OER activity of Co3+/4+ was synergistically enhanced by the covalent bonding of U6+-5f in the U 5f-O 2p-Co 3d network. This study opens new avenues for the realization of electronic structure manipulation via unique 5f involvement.

17.
Small ; 18(11): e2103259, 2022 03.
Artículo en Inglés | MEDLINE | ID: mdl-35297184

RESUMEN

It is a great challenge to develop efficient room-temperature sensing materials and sensors for nitric oxide (NO) gas, which is a biomarker molecule used in the monitoring of inflammatory respiratory diseases. Herein, Hemin (Fe (III)-protoporphyrin IX) is introduced into the nitrogen-doped reduced graphene oxide (N-rGO) to obtain a novel sensing material HNG-ethanol. Detailed XPS spectra and DFT calculations confirm the formation of carbon-iron bonds in HNG-ethanol during synthesis process, which act as electron transport channels from graphene to Hemin. Owing to this unique chemical structure, HNG-ethanol exhibits superior gas sensing properties toward NO gas (Ra /Rg  = 3.05, 20 ppm) with a practical limit of detection (LOD) of 500 ppb and reliable repeatability (over 5 cycles). The HNG-ethanol sensor also possesses high selectivity against other exhaled gases, high humidity resistance, and stability (less than 3% decrease over 30 days). In addition, a deep understanding of the gas sensing mechanisms is proposed for the first time in this work, which is instructive to the community for fabricating sensing materials based on graphene-iron derivatives in the future.


Asunto(s)
Grafito , Porfirinas , Transporte de Electrón , Hierro , Óxido Nítrico , Temperatura
18.
Inorg Chem ; 61(48): 19417-19424, 2022 Dec 05.
Artículo en Inglés | MEDLINE | ID: mdl-36403146

RESUMEN

The development of actinide materials has provided new strategies for the utilization of nuclear waste, such as depleted uranium, a mildly radioactive waste in the nuclear power industry, which could be a precious resource for many fields, especially water splitting. The catalytic performance of water splitting is limited by the slow kinetics of the oxygen evolution reaction (OER), and it is extremely challenging to design efficient OER catalysts that are highly stable and inexpensive. Here, we design and describe a series of U5-35%-Co3O4 electrocatalysts, which were synthesized using uranyl nitrate as a precursor via a simple and scalable method. Interestingly, when the U/Co molar ratio was 20%, a UCoO4/Co3O4 heterojunction formed with high catalytic efficiency and excellent long-term electrolytic stability. The UCoO4/Co3O4 heterojunction catalyst shows a lower overpotential (280 mV) at a current density of 10 mA cm-2, and the slope of Tafel is 43.8 mV decade-1 in a 0.1 M KOH alkaline solution. Soft X-ray absorption spectroscopy shows that the cooperative effect of UCoO4 and Co3O4 can improve the electrochemical activity of the material. This study produced an active U/Co-based catalyst for OER, which provides a simple, scalable, low-cost, and highly efficient catalyst for overall water splitting.

19.
Inorg Chem ; 61(19): 7467-7476, 2022 May 16.
Artículo en Inglés | MEDLINE | ID: mdl-35514048

RESUMEN

Effective detections of radionuclides including uranium and its predominant fission products, for example, iodine, are highly desired owing to their radiotoxicity and potential threat to human health. However, traditional analytical techniques of radionuclides are instrument-demanding, and chemosensors targeted for sensitization of radionuclides remain limited. In this regard, we report a sensitive and selective sensor of UO22+ and I- based on the unique quenching behavior of a luminescent Zr-based metal-organic framework, Zr6O4(OH)4(OH)6(H2O)6(TCPE)1.5·(H2O)24(C3H7NO)9 (Zr-TCPE). Immobilization of the luminescent tetrakis(4-carboxyphenyl)ethylene (TCPE4-) linkers by Zr6 nodes enhances the photoluminescence quantum yield of Zr-TCPE, which facilitates the effective sensing of radionuclides in a "turn-off" manner. Moreover, Zr-TCPE can sensitively and selectively recognize UO22+ and I- ions with the lowest limits of detection of 0.67 and 0.87 µg/kg, respectively, of which the former one is much lower than the permissible value (30 µg/L) defined by the U.S. EPA. In addition, Zr-TCPE features excellent hydrolytic stability and can withstand pH conditions ranging from 3 to 11. To facilitate real-world applications, we have further fabricated polyvinylidene fluoride-integrating Zr-TCPE as luminescence-based sensor membranes for on-site sensing of UO22+ and I-.


Asunto(s)
Estructuras Metalorgánicas , Uranio , Humanos , Iones , Luminiscencia
20.
Phys Chem Chem Phys ; 24(7): 4620-4625, 2022 Feb 16.
Artículo en Inglés | MEDLINE | ID: mdl-35132975

RESUMEN

Orthorhombic KFeO2 has a unique structure where K+ cations can migrate inside the Fe-O skeleton, thus making it a promising material for heterogeneous catalysis and electrochemical energy storage devices. However, KFeO2 is sensitive to conditions such as moisture and carbon dioxide, which would trigger severe phase evolution and consequently deteriorate the performance. In this work, we investigated the phase evolution using freshly prepared KFeO2 and KFeO2 after exposure to ambient air and after immersion in water, respectively. We found that the phase evolution of KFeO2 was composed of K-redistribution and phase transition, both of which originated from K+ extraction. We observed that K+ cations were extracted after exposing KFeO2 to ambient air, resulting in the formation of K2CO3·1.5 H2O outside KFeO2 and lattice expansion inside KFeO2. We also observed that water molecules were crucial to K+ extraction when calculating the function between potassium and the adjacent oxygen atoms via ab initio molecular dynamics simulations. Moreover, we successfully reinserted K+ cations into lattice expanded KFeO2 by high-temperature calcination at 900 °C; such a reversible extraction-insertion process would have great potential for application in catalyst reactivation and rechargeable high-temperature batteries.

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