ABSTRACT
The interactions between gold nanoclusters (AuNCs) and proteins have been extensively investigated. Nevertheless, the structure-activity relationship between gold nanoclusters and proteins in terms of ligand isomerization remained unclear. Here, interactions between Au25NCs modified with para-, inter- and ortho-mercaptobenzoic acid (p/m/o-MBA-Au25NCs) and human serum albumin (HSA) were analyzed. The results of the multispectral approach showed that all three gold nanoclusters bound to the site I in dynamic modes to increase the stability of HSA. There were significant differences in the binding intensity, thermodynamic parameters, main driving forces, and binding ratios between these three gold nanoclusters and HSA, which might be related to the existence forms of the three ligands on the surface of AuNCs. Due to the different polarities of AuNCs themselves, the impact of three AuNCs on the microenvironment of amino acid residues in HSA was also different. It could be seen that ligand isomerization significantly affected the interactions between gold nanoclusters and proteins. This work will provide theoretical guidance for ligand selection and biological applications of metal nanoclusters.
Subject(s)
Gold , Metal Nanoparticles , Serum Albumin, Human , Thermodynamics , Gold/chemistry , Humans , Metal Nanoparticles/chemistry , Ligands , Serum Albumin, Human/chemistry , Serum Albumin, Human/metabolism , Structure-Activity Relationship , Isomerism , Protein BindingABSTRACT
Twisted moiré superlattice is featured with its moiré potential energy, the depth of which renders an effective approach to strengthening the exciton-exciton interaction and exciton localization toward high-performance quantum photonic devices. However, it remains as a long-standing challenge to further push the limit of moiré potential depth. Herein, owing to the pz orbital induced band edge states enabled by the unique sp-C in bilayer γ-graphdiyne (GDY), an ultradeep moiré potential of â¼289 meV is yielded. After being twisted into the hole-to-hole layer stacking configuration, the interlayer coupling is substantially intensified to augment the lattice potential of bilayer GDY up to 475%. The presence of lateral constrained moiré potential shifts the spatial distribution of electrons and holes in excitons from the regular alternating mode to their respective separated and localized mode. According to the well-established wave function distribution of electrons contained in excitons, the AA-stacked site is identified to serve for exciton localization. This work extends the materials systems available for moiré superlattice design further to serial carbon allotropes featured with benzene ring-alkyne chain coupling, unlocking tremendous potential for twistronic-based quantum device applications.
ABSTRACT
Tracking the dynamic surface evolution of metal halide perovskite is crucial for understanding the corresponding fundamental principles of photoelectric properties and intrinsic instability. However, due to the volatility elements and soft lattice nature of perovskites, several important dynamic behaviors remain unclear. Here, an ultra-high vacuum (UHV) interconnection system integrated by surface-sensitive probing techniques has been developed to investigate the freshly cleaved surface of CH3NH3PbBr3 in situ under given energy stimulation. On this basis, the detailed three-step chemical decomposition pathway of perovskites has been clarified. Meanwhile, the evolution of crystal structure from cubic phase to tetragonal phase on the perovskite surface has been revealed under energy stimulation. Accompanied by chemical composition and crystal structure evolution, electronic structure changes including energy level position, hole effective mass, and Rashba splitting have also been accurately determined. These findings provide a clear perspective on the physical origin of optoelectronic properties and the decomposition mechanism of perovskites.
ABSTRACT
Silver nanoclusters (AgNCs) have been widely applied in the field of biology, drug therapy and cell imaging in the last decade. In order to study the biosafety of AgNCs, GSH-AgNCs and DHLA-AgNCs were synthesized using glutathione (GSH) and dihydrolipoic acid (DHLA) as ligands, and their interactions with calf thymus DNA (ctDNA) from abstraction to visualization were studied. The results of spectroscopy, viscometry and molecular docking demonstrated that GSH-AgNCs mainly bound to ctDNA in a groove mode, while DHLA-AgNCs were both groove and intercalation binding. Fluorescence experiments suggested that the quenching mechanism of both AgNCs to the emission of ctDNA-probe were both in static mode, and thermodynamic parameters demonstrated that the main forces between GSH-AgNCs and ctDNA were hydrogen bonds and van der Waals forces, while hydrogen bonds and hydrophobic forces contributed to the binding of DHLA-AgNCs to ctDNA. The binding strength demonstrated that DHLA-AgNCs bound to ctDNA more strongly than that of GSH-AgNCs. The results of circular dichroism (CD) spectroscopy reflected small effects of both AgNCs on the structure of ctDNA. This study will support the theoretical foundation for the biosafety of AgNCs and have a guiding significance for the preparation and application of AgNCs.
Subject(s)
DNA , Silver , Molecular Docking Simulation , Ligands , DNA/chemistry , Thermodynamics , Glutathione , Spectrometry, Fluorescence , Circular DichroismABSTRACT
Although CsPbI3 perovskites have shown tremendous potential in the photovoltaic field owing to their excellent thermal stability, the device performance is seriously restricted by severe photovoltage loss. The buried titanium oxide/perovskite interface plays a critical role in interfacial charge transport and perovskite crystallization, which is closely related to open-circuit voltage deficit stemming from nonradiative recombination. Herein, target molecules named 3-sulphonatopropyl acrylate potassium salts are deliberately employed with special functional groups for modifying the buried interface, giving rise to favorable functions in terms of passivating interfacial defects, optimizing energetic alignment, and facilitating perovskite crystallization. Experimental characterizations and theoretical calculations reveal that the buried interface modification inhibits the electron transfer barrier and simultaneously improves perovskite crystal quality, thereby reducing trap-assisted charge recombination and interfacial energetic loss. Consequently, the omnibearing modification regarding the buried interface endows the devices with an impressive efficiency of 20.98%, achieving a record-low VOC deficit of 0.451 V. The as-proposed buried interface modification strategy renders with a universal prescription to push the limit of VOC deficit, showing a promising future in developing high-performance all-inorganic perovskite photovoltaics.
ABSTRACT
Vacancy defect engineering has been well leveraged to flexibly shape comprehensive physicochemical properties of diverse catalysts. In particular, growing research effort has been devoted to engineering chalcogen anionic vacancies (S/Se/Te) of 2D transition metal dichalcogenides (2D TMDs) toward the ultimate performance limit of electrocatalytic hydrogen evolution reaction (HER). In spite of remarkable progress achieved in the past decade, systematic and in-depth insights into the state-of-the-art vacancy engineering for 2D-TMDs-based electrocatalysis are still lacking. Herein, this review delivers a full picture of vacancy engineering evolving from aggregated to atomic configurations covering their development background, controllable manufacturing, thorough characterization, and representative HER application. Of particular interest, the deep-seated correlations between specific vacancy regulation routes and resulting catalytic performance improvement are logically clarified in terms of atomic rearrangement, charge redistribution, energy band variation, intermediate adsorption-desorption optimization, and charge/mass transfer facilitation. Beyond that, a broader vision is cast into the cutting-edge research fields of vacancy-engineering-based single-atom catalysis and dynamic structure-performance correlations across catalyst service lifetime. Together with critical discussion on residual challenges and future prospects, this review sheds new light on the rational design of advanced defect catalysts and navigates their broader application in high-efficiency energy conversion and storage fields.
ABSTRACT
The catalytic activity of transition metal-based catalysts is overwhelmingly dependent on the geometric configuration. Identification and interpretation of different geometric configurations' contributions to catalytic activity plays a pivotal role in catalytic performance elevation. Spinel structured AB2X4, consisting of tetrahedral (A2+-X)Td and octahedral (B3+-X)Oh geometric configurations, is a prototypical category of multi-geometric-configuration featured catalysts. However, it is still under debate about the predominant geometric configuration responsible for spinel catalyst activity, and the mechanistic origin of specific activity discrepancy among varied geometric configurations also remains ambiguous. Herein, CoTd2+ and CoOh3+ in Co3O4 are replaced by catalytically inert Zn2+ and Al3+ to yield ZnCo2O4 and CoAl2O4, respectively, thus ensuring the manipulable exposure of monotypic active configurations. By means of pulse voltammetry and in situ extended X-ray absorption fine structure, (Co3+-O)Oh is identified to be dominant for alkaline HER. In-depth theoretical investigation in combination with X-ray absorption spectroscopy further interprets the synergistic effect between Co and O sites in (Co3+-O)Oh configuration on water reduction kinetics upon both water dissociation and hydrogen desorption steps. Furthermore, specific facet dependence of catalytic activity is also deciphered based on precise facet exposure identification and serial theoretical analysis. This work unambiguously figures out the subtle geometric configuration dependence of spinel catalyst activity for water reduction and highlights the synergistic relationship among different components confined in geometric configuration, thereby shedding new light on the rational design of advanced catalysts from the atomic level of geometric configuration optimization.
ABSTRACT
π electron configuration plays a pivotal role in metal-free carbon catalysts, and its delocalization degree overwhelmingly dominates catalytic activity. However, precise and targeted regulation of inherent π electrons still remain challenging. Here, one chemical-bond-targeted physical clipping strategy is proposed and effectively adopted in the cutting-edge carbon material system of graphdiyne (GDY) as a concept-of-proof. The delocalized electrons are expected to be periodically reformatted for substantially enhancing π electron delocalization. Via theoretical screening and well-designed experiments, periodical interruption of Csp-Csp2 bonds in GDY can render sp-C sites with decent activity, ultimately yielding top-ranking electrocatalytic performance without intentionally introducing external decoration. The as-proposed concept endows a universal prescription to push the limit of delocalization degree, thus shedding novel light on the rational design of decent metal-free catalysts.
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BACKGROUND: Living near green spaces may benefit various health outcomes. However, no studies have investigated the greenness-bone linkage in the general population. Moreover, to which extent ambient air pollution (AAP), physical activity (PA), and body mass index (BMI) mediate this relationship remains unclear. We aimed to explore the association between greenness and bone strength and the potential mediating roles of AAP, PA, and BMI in Chinese adults. METHODS: This cross-sectional analysis enrolled 66,053 adults from the China Multi-Ethnic Cohort in 2018-2019. The normalized difference vegetation index (NDVI) and enhanced vegetation index (EVI) were employed to define residential greenness. The calcaneus quantitative ultrasound index (QUI) was used to indicate bone strength. Multiple linear regression models and mediation analyses were used to estimate the residential greenness-bone strength association and potential pathways operating through AAP (represented by PM2.5 [particulate matter <2.5 µm in diameter]), PA, and BMI. Stratification analyses were performed to identify susceptible populations. RESULTS: Higher residential exposure to greenness was significantly associated with an increase in QUI, with changes (95% confidence interval) of 3.28 (3.05, 3.50), 3.57 (3.34, 3.80), 2.68 (2.46, 2.90), and 2.93 (2.71, 3.15) for every interquartile range increase in NDVI500m, NDVI1000m, EVI500m, and EVI1000m, respectively. Sex, urbanicity, annual family income, smoking, and drinking significantly modified the association of greenness-bone strength, with more remarkable associations in males, urban residents, subjects from wealthier families, smokers, and drinkers. For the NDVI500m/EVI500m-QUI relationship, the positive mediating roles of PM2.5 and PA were 6.70%/8.50 and 2.43%/2.69%, respectively, whereas those negative for BMI and PA-BMI were 0.88%/1.06% and 0.05%/0.05%, respectively. CONCLUSION: Living in a greener area may predict higher bone strength, particularly among males, urban residents, wealthier people, smokers, and drinkers. AAP, PA, BMI, and other factors may partially mediate the positive association. Our findings underscore the importance of optimizing greenness planning and management policies.
Subject(s)
Air Pollution , Adult , Air Pollution/analysis , Body Mass Index , China/epidemiology , Cross-Sectional Studies , Humans , Male , Particulate Matter/analysisABSTRACT
Facing the constant scaling down and thus increasingly severe self-heating effect, developing ultrathin and heat-insensitive ferroelectric devices is essential for future electronics. However, conventional ultrathin ferroelectrics and most 2D ferroelectric materials (2DFMs) are not suitable for high-temperature operation due to their low Curie temperature. Here, by using few-layer α-In2 Se3 , a special 2DFM with high Curie temperature, van der Waals (vdW) ferroelectric tunnel junction (FTJ) memories that deliver outstanding and reliable performance at both room and high temperatures are constructed. The vdW FTJs offer a large on/off ratio of 104 at room temperature and still reveal excellent on/off ratio at an ultrahigh temperature of 470 K, which will fail down other 2DFMs. Moreover, long retention and reliable cyclic endurance at high temperature are achieved, showing robust thermal stability of the vdW FTJ memory. The observations of this work demonstrate an exciting promise of α-In2 Se3 for reliable service in high temperature either from self-heating or harsh environments.
ABSTRACT
The employment of microwave absorbents is highly desirable to address the increasing threats of electromagnetic pollution. Importantly, developing ultrathin absorbent is acknowledged as a linchpin in the design of lightweight and flexible electronic devices, but there are remaining unprecedented challenges. Herein, the self-assembly VS4/rGO heterostructure is constructed to be engineered as ultrathin microwave absorbent through the strategies of architecture design and interface engineering. The microarchitecture and heterointerface of VS4/rGO heterostructure can be regulated by the generation of VS4 nanorods anchored on rGO, which can effectively modulate the impedance matching and attenuation constant. The maximum reflection loss of 2VS4/rGO40 heterostructure can reach - 43.5 dB at 14 GHz with the impedance matching and attenuation constant approaching 0.98 and 187, respectively. The effective absorption bandwidth of 4.8 GHz can be achieved with an ultrathin thickness of 1.4 mm. The far-reaching comprehension of the heterointerface on microwave absorption performance is explicitly unveiled by experimental results and theoretical calculations. Microarchitecture and heterointerface synergistically inspire multi-dimensional advantages to enhance dipole polarization, interfacial polarization, and multiple reflections and scatterings of microwaves. Overall, the strategies of architecture design and interface engineering pave the way for achieving ultrathin and enhanced microwave absorption materials.
ABSTRACT
Ultrathin 2D semiconductor devices are considered to have beyond-silicon potential but are severely troubled by the high Schottky barriers of the metal-semiconductor contacts, especially for p-type semiconductors. Due to the severe Fermi-level pinning effect and the lack of conventional semimetals with high work functions, their Schottky hole barriers are hardly removed. Here, an all-van-der-Waals barrier-free hole contact between p-type tellurene semiconductor and layered 1T'-WS2 semimetal is reported, which achieves a zero Schottky barrier height of 3 ± 9 meV and a high field-effect mobility of ≈1304 cm2 V-1 s-1 . The formation of such contacts can be attributed to the higher work function of ≈4.95 eV of the 1T'-WS2 semimetal, which is in sharp contrast with low work function (4.1-4.7 eV) of conventional semimetals. The study defines an available strategy for eliminating the Schottky barrier of metal-semiconductor contacts, facilitating 2D-semiconductor-based electronics and optoelectronics to extend Moore's law.
ABSTRACT
Fundamental understanding of ion migration inside perovskites is of vital importance for commercial advancements of photovoltaics. However, the mechanism for external ions incorporation and its effect on ion migration remains elusive. Herein, taking K+ and Cs+ co-incorporated mixed halide perovskites as a model, the impact of external ions on ion migration behavior has been interpreted via multiple dimensional characterization aspects. The space-effect on phase segregation inhibition has been revealed by the photoluminescence evolution and in situ dynamic cathodoluminescence behaviors. The plane-effect on current suppression along grain boundary has been evidenced via visualized surface current mapping, local current hysteresis, and time-resolved current decay. And the point-effect on activation energy incremental for individual ions has been also probed by cryogenic electronic quantification. All these results sufficiently demonstrate the passivated ion migration results in the eventually improved phase stability of perovskite, of which the origin lies in various ion migration energy barriers.
ABSTRACT
Rubidium cation (Rb+ ) addition is witnessed to play a pivotal role in boosting the comprehensive performance of organic-inorganic hybrid perovskite solar cells. However, the origin of such success derived from irreplaceable superiorities brought by Rb+ remains ambiguous. Herein, grain-boundary-including atomic models are adopted for the accurate theoretical analysis of practical Rb+ distribution in perovskite structures. The spatial distribution, covering both the grain interiors and boundaries, is thoroughly identified by virtue of synchrotron-based grazing-incidence X-ray diffraction. On this basis, the prominent elevation of the halogen vacancy formation energy, improved charge-carrier dynamics, and the electronic passivation mechanism in the grain interior are expounded. As evidenced by the increased energy barrier and suppressed microcurrent, the critical role of Rb+ addition in blocking the diffusion pathway along grain boundaries, inhibiting halide phase segregation, and eventually enhancing intrinsic stability is elucidated. Hence, the linkage avalanche effect of occupied location dominated by subtle changes in Rb+ concentration on electronic defects, ion migration, and phase stability is completely investigated in detail, shedding a new light on the advancement of high-efficiency cascade-incorporating strategies and perovskite compositional engineering.
ABSTRACT
Single-atom catalysis has been recognized as a pivotal milestone in the development history of heterogeneous catalysis by virtue of its superior catalytic performance, ultrahigh atomic utilization, and well-defined structure. Beyond single-atom protrusions, two more motifs of single-atom substitutions and single-atom vacancies along with synergistic single-atom motif assemblies have been progressively developed to enrich the single-atom family. On the other hand, besides traditional carbon material based substrates, a wide variety of 2D transitional metal dichalcogenides (TMDs) have been emerging as a promising platform for single-atom catalysis owing to their diverse elemental compositions, variable crystal structures, flexible electronic structures, and intrinsic activities toward many catalytic reactions. Such substantial expansion of both single-atom motifs and substrates provides an enriched toolbox to further optimize the geometric and electronic structures for pushing the performance limit. Concomitantly, higher requirements have been put forward for synthetic and characterization techniques with related technical bottlenecks being continuously conquered. Furthermore, this burgeoning single-atom catalyst (SAC) system has triggered serial scientific issues about their changeable single atom-2D substrate interaction, ambiguous synergistic effects of various atomic assemblies, as well as dynamic structure-performance correlations, all of which necessitate further clarification and comprehensive summary. In this context, this Review aims to summarize and critically discuss the single-atom engineering development in the whole field of 2D TMD based catalysis covering their evolution history, synthetic methodologies, characterization techniques, catalytic applications, and dynamic structure-performance correlations. In situ characterization techniques are highlighted regarding their critical roles in real-time detection of SAC reconstruction and reaction pathway evolution, thus shedding light on lifetime dynamic structure-performance correlations which lay a solid theoretical foundation for the whole catalytic field, especially for SACs.
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OBJECTIVE: To externally validate the Ovarian-adnexal Reporting and Data System (O-RADS) and evaluate its performance in differentiating benign from malignant adnexal masses (AMs) compared with the Gynecologic Imaging Reporting and Data System (GI-RADS) and Assessment of Different NEoplasias in the adneXa (ADNEX). METHODS: A retrospective analysis was performed on 734 cases from the Second Affiliated Hospital of Fujian Medical University. All patients underwent transvaginal or transabdominal ultrasound examination. Pathological diagnoses were obtained for all the included AMs. O-RADS, GI-RADS, and ADNEX were used to evaluate AMs by two sonologists, and the diagnostic efficacy of the three systems was analyzed and compared using pathology as the gold standard. We used the kappa index to evaluate the inter-reviewer agreement (IRA). RESULTS: A total of 734 AMs, including 564 benign masses, 69 borderline masses, and 101 malignant masses were included in this study. O-RADS (0.88) and GI-RADS (0.90) had lower sensitivity than ADNEX (0.95) (P < .05), and the PPV of O-RADS (0.98) was higher than that of ADNEX (0.96) (P < .05). These three systems showed good IRA. CONCLUSION: O-RADS, GI-RADS, and ADNEX showed little difference in diagnostic performance among resident sonologists. These three systems have their own characteristics and can be selected according to the type of center, access to patients' clinical data, or personal comfort.
Subject(s)
Adnexal Diseases , Ovarian Neoplasms , Adnexal Diseases/diagnostic imaging , Data Systems , Female , Humans , Ovarian Neoplasms/pathology , Retrospective Studies , Sensitivity and Specificity , Ultrasonography/methodsABSTRACT
OBJECTIVE: To investigate whether physicians with short-term training can use a modified lung ultrasound scoring system for coronavirus disease 2019 (COVID-19) pneumonia to assess lung damage in pregnant women. METHODS: Sixteen consecutively hospitalized third-trimester pregnant women with pregnancy-induced hypertension, preeclampsia, rheumatoid arthritis or connective tissue disease were selected as the study subjects for the simulation of COVID-19 pneumonia. Two physicians (imaging and internal medicine) without ultrasonic experience performed lung examinations on pregnant women after six days of lung ultrasound training, and their consistency with examinations by the expert was assessed. In addition, 54 healthy third-trimester pregnant women and 54 healthy nonpregnant women of the same age who were continuously treated in the outpatient clinic of this hospital were selected for comparisons of abnormalities on lung ultrasound. RESULTS: (1) Third trimester pregnant women with pregnancy-induced hypertension, preeclampsia, rheumatoid arthritis or connective tissue disease had the same lung ultrasound patterns as those associated with COVID-19 pneumonia. (2) There was no statistically significant difference between the scores of the two trained doctors and the expert when the modified ultrasound scoring system was used (p > .05). (3) The evaluations of the two trained doctors and the expert showed good consistency (kappa value = 0.833-0.957). (4) The incidence of abnormal ultrasound manifestations of the pleura and lung parenchyma was higher among healthy third-trimester pregnant women than among healthy women of the same age (p < .001). CONCLUSIONS: After receiving short-term training, imaging and internal medicine physicians can use the modified lung ultrasound scoring system to evaluate pregnant women's pulmonary damage, but caution is needed to avoid false-positive results among pregnant women with suspected COVID-19 pneumonia.