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1.
Adv Mater ; 35(11): e2209386, 2023 Mar.
Artículo en Inglés | MEDLINE | ID: mdl-36433641

RESUMEN

Dual-atom catalysts (DACs) have become an emerging platform to provide more flexible active sites for electrocatalytic reactions with multi-electron/proton transfer, such as the CO2  reduction reaction (CRR). However, the introduction of asymmetric dual-atom sites causes complexity in structure, leaving an incomprehensive understanding of the inter-metal interaction and catalytic mechanism. Taking NiCu DACs as an example, herein, a more rational structural model is proposed, and the distance-dependent inter-metal interaction is investigated by combining theoretical simulations and experiments, including density functional theory computation, aberration-corrected transmission electron microscopy, synchrotron-based X-ray absorption fine structure, and Monte Carlo experiments. A distance threshold around 5.3 Å between adjacent NiN4  and CuN4  moieties is revealed to trigger effective electronic regulation and boost CRR performance on both selectivity and activity. A universal macro-descriptor rigorously correlating the inter-metal distance and intrinsic material features (e.g., metal loading and thickness) is established to guide the rational design and synthesis of advanced DACs. This study highlights the significance of identifying the inter-metal interaction in DACs, and helps bridge the gap between theoretical study and experimental synthesis of atomically dispersed catalysts with highly correlated active sites.

2.
Angew Chem Int Ed Engl ; 60(33): 18178-18184, 2021 Aug 09.
Artículo en Inglés | MEDLINE | ID: mdl-34240788

RESUMEN

Monitoring and controlling the reconstruction of materials under working conditions is crucial for the precise identification of active sites, elucidation of reaction mechanisms, and rational design of advanced catalysts. Herein, a Bi-based metal-organic framework (Bi-MOF) for electrochemical CO2 reduction is selected as a case study. In situ Raman spectra combined with ex situ electron microscopy reveal that the intricate reconstruction of the Bi-MOF can be controlled using two steps: 1) electrolyte-mediated dissociation and conversion of Bi-MOF to Bi2 O2 CO3 , and 2) potential-mediated reduction of Bi2 O2 CO3 to Bi. The intentionally reconstructed Bi catalyst exhibits excellent activity, selectivity, and durability for formate production, and the unsaturated surface Bi atoms formed during reconstruction become the active sites. This work emphasizes the significant impact of pre-catalyst reconstruction under working conditions and provides insight into the design of highly active and stable electrocatalysts through the regulation of these processes.

3.
Chem Commun (Camb) ; 55(12): 1730-1733, 2019 Feb 05.
Artículo en Inglés | MEDLINE | ID: mdl-30657476

RESUMEN

It is significant to in situ monitor membrane proteins at the single-cell level for understanding the cell function. Herein, an integrated platform was designed and constructed for highly efficient cell capture and in situ sensitive SERS determination of HER2 activity in cells through rational spatial organization of multi-functional cyclic RGD nanopatterns at a disordered mesoporous gold film via electrochemical activation.


Asunto(s)
Células Neoplásicas Circulantes/metabolismo , Péptidos Cíclicos/química , Receptor ErbB-2/química , Línea Celular Tumoral , Oro/química , Humanos , Microscopía Electrónica de Transmisión , Microscopía Fluorescente , Células Neoplásicas Circulantes/química , Péptidos Cíclicos/metabolismo , Porosidad , Receptor ErbB-2/metabolismo , Espectrometría Raman
4.
Analyst ; 142(22): 4215-4220, 2017 Nov 06.
Artículo en Inglés | MEDLINE | ID: mdl-29058010

RESUMEN

Developing a sensitive and accurate method for Furin activity is still the bottleneck for understanding the role played by Furin in cell-surface systems and even in Alzheimer's disease. In this work, a ratiometric electrochemical biosensor was developed for sensitive and accurate determination of Furin activity in the cell based on dual signal amplification stemming from a peptide with multiple response sites and the antifouling gold nano-bellflowers (GBFs). A new peptide, HS-CMRVRR↓YKDFDFG (P3), was designed for the first time to be selectively cleaved by Furin at site↓. More importantly, this peptide P3 constitutes three amino acid residues with the -COOH group subsequently used to bind with the response molecule of ferrocene, and can remarkably improve the determination sensitivity by about 2.3 fold. Meanwhile, GBFs stabilized by PEG were taken as a second element to magnify the signal of the ferrocene group via a large ratio surface area and good conductivity, as well as an antibiofouling nanosurface to reduce the biofouling of the electrode surface in cells. This double amplification strategy can greatly enhance the sensitivity of Furin detection by 6.5-fold, which is favorable for detection of low amounts of Furin. In addition, 5'-MB-GGCGCGA(T)13-SH-3' was co-assembled as an inner reference to provide a built-in element to correct the determination error resulting from a complicated analysis environment. Finally, this sensitive and accurate Furin biosensor was successfully applied to detect Furin activity in Furin overexpressed U251 and MDA-MB-468 cells. As far as we know, this is the first report to mention an electrochemical strategy to detect Furin activity in cells.


Asunto(s)
Técnicas Biosensibles , Técnicas Electroquímicas , Furina/análisis , Nanotecnología , Línea Celular Tumoral , Electrodos , Oro , Humanos , Nanoestructuras , Péptidos/química
5.
PLoS One ; 9(9): e108614, 2014.
Artículo en Inglés | MEDLINE | ID: mdl-25275619

RESUMEN

BACKGROUND: In China, spouse caregivers of cancer patients (SCCPs) are involved in all aspects of patient care and experience psychological distress which could result in sleep disturbance and fatigue. However, few studies have explored the differences between SCCPs and the general population, or what factors affect SCCPs' sleep. This study aims to (1) Compare the differences in sleep disturbances and fatigue severity between SCCPs and the age- and gender-matched general population, and (2) Identify selected personal characteristics, including coping style that affect sleep disturbances in SCCPs. METHODOLOGY/PRINCIPAL FINDINGS: The Stress and Coping Model was used to guide this study. Participants were recruited from the northeast part of China and included 600 people from the general population and 300 SCCPs. Participants completed a socio-demographic form, Fatigue Scale-14, trait Coping Style Questionnaire, and Symptom Checklist-90. RESULTS: The majority of the participants were middle age, most of whom (78.7%) spent more than 8 hours each day taking care of their spouses. Compared to the general population, the SCCPs experienced significant sleep disturbances with a mean of 7.30 (SD = 1.27), and fatigue severity with a mean of 8.11 (SD = 3.25). Among the selected SCCPs' personal characteristics, current poor health status (ß = 0.14, P<0.001), having a spouse under mixed treatment (ß = 0.13, p<0.001), and financial burden (ß = 0.14, P<0.001) are the significant predictors for sleep disturbances. Positive coping is the predictor for fewer sleep disturbances (ß = 0.27, P<0.001). Those who reported sleep disturbances also experienced higher physical and mental fatigue severity (P<0.001). CONCLUSION: Intervention to improve coping style in SCCPs is needed. Further research is also needed to explore the other mediators and moderators that regulate sleep disturbance and health outcomes in the SCCPs.


Asunto(s)
Cuidadores/psicología , Neoplasias/patología , Trastornos del Sueño-Vigilia/psicología , Esposos/psicología , Adulto , China , Demografía , Fatiga/complicaciones , Femenino , Humanos , Masculino , Persona de Mediana Edad , Trastornos del Sueño-Vigilia/complicaciones
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