Two-dimensional materials provide extraordinary opportunities for exploring phenomena arising in atomically thin crystals. Beginning with the first isolation of graphene, mechanical exfoliation has ...been a key to provide high-quality two-dimensional materials, but despite improvements it is still limited in yield, lateral size and contamination. Here we introduce a contamination-free, one-step and universal Au-assisted mechanical exfoliation method and demonstrate its effectiveness by isolating 40 types of single-crystalline monolayers, including elemental two-dimensional crystals, metal-dichalcogenides, magnets and superconductors. Most of them are of millimeter-size and high-quality, as shown by transfer-free measurements of electron microscopy, photo spectroscopies and electrical transport. Large suspended two-dimensional crystals and heterojunctions were also prepared with high-yield. Enhanced adhesion between the crystals and the substrates enables such efficient exfoliation, for which we identify a gold-assisted exfoliation method that underpins a universal route for producing large-area monolayers and thus supports studies of fundamental properties and potential application of two-dimensional materials.
Metal binding to microbial extracellular polymeric substances (EPS) greatly influences the distribution of heavy metals in microbial aggregates, soil and aquatic systems in nature. In this work, the ...thermodynamic characteristics of the binding between aqueous metals (with copper ion as an example) and EPS of activated sludge were investigated. Isothermal titration calorimetry was employed to estimate the thermodynamic parameters for the binding of Cu2+ onto EPS, while three-dimensional excitation-emission matrix (EEM) fluorescence spectroscopy with parallel factor analysis was used for quantifying the complexation of Cu2+ with the EPS. The binding mechanisms were further explored by X-ray absorption fine structure (XAFS) and Fourier transform infrared (FTIR) spectroscopy analysis. The results show that the proteins and humic substances in EPS were both strong ligands for Cu2+. The binding capacity N, binding constant K, binding enthalpy ΔH were calculated as 5.74 × 10−2 mmol/g, 2.18 × 105 L/mol, and −11.30 kJ/mol, respectively, implying that such a binding process was exothermic and thermodynamically favorable. The binding process was found to be driven mainly by the entropy change of the reaction. A further investigation shows that Cu2+ bound with the oxygen atom in the carboxyl groups in the EPS molecules of activated sludge. This study facilitates a better understanding about the roles of EPS in protecting microbes against heavy metals.
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► Thermodynamic characteristics of binding of Cu2+ to EPS are investigated. ► The binding process is exothermic and thermodynamically favorable. ► Cu2+ binds with the O atom in the carboxyl groups in EPS.
As a 100% atom-economy process, direct oxidation of methane into methanol remains as a grand challenge due to the dilemma between activation of methane and over-oxidation of methanol. Here, we report ...that water enabled mild oxidation of methane into methanol with >99% selectivity over Au single atoms on black phosphorus (Au
/BP) nanosheets under light irradiation. The mass activity of Au
/BP nanosheets reached 113.5 μmol g
in water pressured with 33 bar of mixed gas (CH
:O
= 10:1) at 90 °C under light irradiation (1.2 W), while the activation energy was 43.4 kJ mol
. Mechanistic studies revealed that water assisted the activation of O
to generate reactive hydroxyl groups and •OH radicals under light irradiation. Hydroxyl groups reacted with methane at Au single atoms to form water and CH
* species, followed by oxidation of CH
* via •OH radicals into methanol. Considering the recycling of water during the whole process, we can also regard water as a catalyst.
The active site of the industrial Cu/ZnO/Al2O3 catalyst used in CO2 hydrogenation to methanol has been debated for decades. Grand challenges remain in the characterization of structure, composition, ...and chemical state, both microscopically and spectroscopically, and complete theoretical calculations are limited when it comes to describing the intrinsic activity of the catalyst over the diverse range of structures that emerge under realistic conditions. Here a series of inverse model catalysts of ZnO on copper hydroxide were prepared where the size of ZnO was precisely tuned from atomically dispersed species to nanoparticles using atomic layer deposition. ZnO decoration boosted methanol formation to a rate of 877 gMeOH kgcat−1 h−1 with ≈80 % selectivity at 493 K. High pressure in situ X‐ray absorption spectroscopy demonstrated that the atomically dispersed ZnO species are prone to aggregate at oxygen‐deficient ZnO ensembles instead of forming CuZn metal alloys. By modeling various potential active structures, density functional theory calculations and microkinetic simulations revealed that ZnO/Cu interfaces with oxygen vacancies, rather than stoichiometric interfaces, Cu and CuZn alloys were essential to catalytic activation.
High‐pressure in situ X‐ray absorption spectroscopy disclosed the structure evolution of isolated Zn species to oxygen‐deficient ZnO ensembles on an atomically dispersed ZnO/Cu catalyst during methanol synthesis from CO2. Density functional theory calculations further revealed that oxygen vacancies at the interfaces play an important role in the active site.
Immunogenic cell death (ICD)-associated immunogenicity can be evoked through reactive oxygen species (ROS) produced via endoplasmic reticulum (ER) stress. In this study, we generate a double ...ER-targeting strategy to realize photodynamic therapy (PDT) photothermal therapy (PTT) immunotherapy. This nanosystem consists of ER-targeting pardaxin (FAL) peptides modified-, indocyanine green (ICG) conjugated- hollow gold nanospheres (FAL-ICG-HAuNS), together with an oxygen-delivering hemoglobin (Hb) liposome (FAL-Hb lipo), designed to reverse hypoxia. Compared with non-targeting nanosystems, the ER-targeting naosystem induces robust ER stress and calreticulin (CRT) exposure on the cell surface under near-infrared (NIR) light irradiation. CRT, a marker for ICD, acts as an 'eat me' signal to stimulate the antigen presenting function of dendritic cells. As a result, a series of immunological responses are activated, including CD8
T cell proliferation and cytotoxic cytokine secretion. In conclusion, ER-targeting PDT-PTT promoted ICD-associated immunotherapy through direct ROS-based ER stress and exhibited enhanced anti-tumour efficacy.
Drug use and relapse involve learned associations between drug-associated environmental cues and drug effects. Extinction procedures in the clinic can suppress conditioned responses to drug cues, but ...the extinguished responses typically reemerge after exposure to the drug itself (reinstatement), the drug-associated environment (renewal), or the passage of time (spontaneous recovery). We describe a memory retrieval-extinction procedure that decreases conditioned drug effects and drug seeking in rat models of relapse, and drug craving in abstinent heroin addicts. In rats, daily retrieval of drug-associated memories 10 minutes or 1 hour but not 6 hours before extinction sessions attenuated drug-induced reinstatement, spontaneous recovery, and renewal of conditioned drug effects and drug seeking. In heroin addicts, retrieval of drug-associated memories 10 minutes before extinction sessions attenuated cue-induced heroin craving 1, 30, and 180 days later. The memory retrieval-extinction procedure is a promising nonpharmacological method for decreasing drug craving and relapse during abstinence.
This study aimed to determine the levels of health-related behaviours (physical activity, screen exposure and sleep status) among Chinese students from primary, secondary and high schools during the ...pandemic of COVID-19, as well as their changes compared with their status before the pandemic. A cross-sectional online survey of 10,933 students was conducted among 10 schools in Guangzhou, China, between 8th and 15th March, 2020. After getting the informed consent from student's caregivers, an online questionnaire was designed and used to obtain time spending on health-related behaviours during the pandemic of COVID-19, as well as the changes compared with 3 months before the pandemic, which was completed by students themselves or their caregivers. Students were stratified by regions (urban, suburban, exurban), gender (boys and girls), and grades (lower grades of primary school, higher grades of primary schools, secondary schools and high schools). Data were expressed as number and percentages and Chi-square test was used to analyse difference between groups. Overall, the response rate of questionnaire was 95.3% (10,416/10,933). The median age of included students was 13.0 (10.0, 16.0) years and 50.1% (n = 5,219) were boys. 41.4%, 53.6% and 53.7% of total students reported less than 15 min per day in light, moderate and vigorous activities and 58.7% (n = 6,113) reported decreased participation in physical activity compared with the time before pandemic. Over 5 h of screen time spending on online study was reported by 44.6% (n = 4,649) of respondents, particular among high school students (81.0%). 76.9% of students reported increased screen time compared with the time before pandemic. Inadequate sleep was identified among 38.5% of students and the proportion was highest in high school students (56.9%). Our study indicated that, during the COVID-19 pandemic, the school closure exerted tremendous negative effects on school-aged children's health habits, including less physical activity, longer screen exposure and irregular sleeping pattern.
Atherosclerotic cardio-cerebrovascular disease and death remain the leading cause of morbidity and mortality worldwide. Defective efferocytosis, the clearance of apoptotic cells by macrophages, is ...thought to lead to increased inflammation and necrotic core formation in atherosclerotic lesions. However, very little is known about the role of long noncoding RNA (lncRNA) during this process. Here we show that lncRNA myocardial infarction associated transcript (MIAT) was markedly elevated in the serum of patients with symptoms of vulnerable atherosclerotic plaque and the macrophages of necrotic cores in an advanced atherosclerosis mouse model. MIAT knockdown attenuated atherosclerosis progression, reduced necrotic core size, and increased plaque stability in vivo. Furthermore, MIAT knockdown promoted clearance of apoptotic cells by macrophages in vivo and in vitro. Mechanistic studies revealed that MIAT acted as a micro RNA (miRNA) sponge to positively modulate the expression of anti-phagocytic molecule CD47 through sponging miR-149-5p. Together, these findings identified a macrophage MIAT/miR-149-5p /CD47 pathway as a key factor in the development of necrotic atherosclerotic plaques.
Typically, volume expansion of the electrodes after intercalation of active ions is highly undesirable yet inetvitable, and it can significantly reduce the adhesion force between the electrodes and ...current collectors. Especially in aluminum‐ion batteries (AIBs), the intercalation of large‐sized AlCl4− can greatly weaken this adhesion force and result in the detachment of the electrodes from the current collectors, which seems an inherent and irreconcilable problem. Here, an interesting concept, the “dead zone”, is presented to overcome the above challenge. By incorporating a large number of OH− and COOH− groups onto the surface of MXene film, a rich negative‐charge region is formed on its surface. When used as the current collector for AIBs, it shields a tiny area of the positive electrode (adjacent to the current collector side) from AlCl4− intercalation due to the repulsion force, and a tiny inert layer (dead zone) at the interface of the positive electrode is formed, preventing the electrode from falling off the current collector. This helps to effectively increase the battery's cycle life to as high as 50 000 times. It is believed that the proposed concept can be an important reference for future development of current collectors in rocking chair batteries.
A stable, lightweight, durable, and low‐cost current collector, MXene (Ti3C2Tx) film, is achieved for aluminum‐ion batteries. A large number of OH− and COOH− groups are incorporated onto the surface of the MXene film to form rich negative charges region on its surface, which shields the positive electrode material from AlCl4− intercalation in its “dead zone.”
A therapeutic carrier in the second near‐infrared (NIR) window is created that features magnetic target, magnetic resonance imaging (MRI) diagnosis, and photothermal therapy functions through the ...manipulation of a magnet and NIR laser. A covellite‐based CuS in the form of rattle‐type Fe3O4@CuS nanoparticles is developed to conduct photoinduced hyperthermia at 808 and 1064 nm of the first and second NIR windows, respectively. The Fe3O4@CuS nanoparticles exhibit broad NIR absorption from 700 to 1300 nm. The in vitro photothermal results show that the laser intensity obtained using 808 nm irradiation required a twofold increase in its magnitude to achieve the same damage in cells as that obtained using 1064 nm irradiation. Because of the favorable magnetic property of Fe3O4, magnetically guided photothermal tumor ablation is performed for assessing both laser exposures. According to the results under the fixed laser intensity and irradiation spot, exposure to 1064 nm completely removed tumors showing no signs of relapse. On the other hand, 808 nm irradiation leads to effective inhibition of growth that remained nearly unchanged for up to 30 d, but the tumors are not completely eliminated. In addition, MRI is performed to monitor rattle‐type Fe3O4@CuS localization in the tumor following magnetic attraction.
An effective, near‐infrared (NIR)‐responsive rattle‐type Fe3O4@CuS nanoparticle is developed to conduct magnetically guided photothermal tumor ablation and magnetic resonance imaging diagnosis through magnetic targeting. Based on the broad NIR absorption from 700 to 1300 nm, photothermal tumor ablation is evaluated by radiation at 808 and 1064 nm of the first and second NIR windows, respectively.
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