Small Methods最新文献

The development of metasurfaces necessitates the rapid fabrication of nanoarrays on diverse substrates at large scales, the preparation of patterned nanoarrays on both planar and curved surfaces, and even the creation of nanoarrays on prefabricated structures to form multiscale metastructures. However, conventional fabrication methods fall short of these rigorous requirements. In this work, a novel self-assembly hybrid manufacturing (SAHM) method is introduced for the rapid and scalable fabrication of shape-controllable nanoarrays on various rigid and flexible substrates. This method can be easily integrated with other fabrication techniques, such as lithography and screen printing, to produce patterned nanoarrays on both planar and non-developable surfaces. Utilizing the SAHM method, nanoarrays are fabricated on prefabricated micropillars to create multiscale pillar-nanoarray metastructures. Measurements indicate that these multiscale metastructures can manipulate electromagnetic waves across a range of wavelengths. Therefore, the SAHM method demonstrates the potential of multiscale structures as a new paradigm for the design and fabrication of metasurfaces.

Controlling the polymorphism of metal nanocrystals is a promising strategy for enhancing properties and discovering new phenomena. However, previous studies on Rh nanocrystals have focused on their thermodynamically stable face-centered-cubic (fcc) phase. Herein, a facile synthesis of Rh-based nanocrystals featuring the metastable hexagonal close-packed (hcp) phase is reported by using Ru seeds in their native hcp phase to template the deposition of Rh atoms. The success of such phase-controlled synthesis relies on the templating effect promoted by the small lattice mismatch between Ru and Rh and the slow dropwise titration of the precursor at an elevated temperature, ensuring the layer-by-layer growth mode and thus the formation of a conformal hcp-Rh shell. Faster injection rate of Rh(III) precursor leads to the formation of a rough Rh shell in the conventional fcc phase due to accelerated reaction kinetics. Considering both thermodynamic and kinetic aspects of this system, the hcp-Rh phase is favored when the low surface energy from smooth overlayers balances the high bulk energy of the metastable phase, achieved through tight control of reaction rates and deposition patterns. These Ru_hcp@Rh_hcp core-shell nanocrystals demonstrate thermal stability up to 400 °C, while exhibiting higher catalytic activity toward ethanol oxidation reaction compared to Ru_hcp@Rh_fcc counterparts.

It is imperative to design robust single atom catalysts (SACs) that maintain the stability of the active component under diverse reaction conditions and prevent aggregation or deactivation. Confining the single atom active site within sub-nanometer (sub-1-nm) spaces has proven effective in enhancing the stability and activity of the catalyst, owing to the strong constraints and regulations imposed on atomic behavior at this scale. Bimetallic bond atomic sites, comprising two distinct metal compositions, often exhibit unique electronic structures and catalytic properties. Designing SACs under reaction-induced conditions, such as varying temperatures, pressures, and atmospheres, can facilitate a deeper understanding of the formation and migration behavior of active sites in real reactions, as well as the optimization mechanisms for performance enhancement. The objective of this review is to promote a robust SAC design strategy that encapsulates bimetallic bonding active sites within sub-1-nm spaces and investigates catalyst preparation and performance under reaction-induced conditions. This design strategy is anticipated to bolster the catalytic activity and stability of the catalyst while also offering fresh perspectives and optimization avenues for the catalytic processes involved in practical chemical reactions.

The construction of highly efficient and self-supported electrocatalysts with abundant active sites for pH-universal hydrogen evolution reaction (HER) and alkaline water splitting is significantly challenging. Herein, Co and MoC nanoparticles embedded in nitrogen-doped carbon nanofibers (Co-MoC/NCNFs) which display a bamboo-like morphology are prepared by electrospinning followed by the carbonization method. The electrospun MoC possesses an ultrasmall size (≈5 nm) which can provide more active sites during electrocatalysis, while the introduction of Co greatly optimizes the electronic structure of MoC. Both endow the Co-MoC/NCNFs with superior HER performances over a wide pH range, with low overpotentials of 86, 116, and 145 mV to achieve a current density of 10 mA cm^-2 in alkaline, acidic, and neutral media, respectively. Additionally, the catalyst exhibits remarkable alkaline oxygen evolution reaction (OER) activity with an overpotential of 254 mV to reach 10 mA cm^-2. Density functional theory calculations confirm that electron transfer from Co to MoC regulates the adsorption free energy for hydrogen, thereby promoting HER. Moreover, an electrolyzer assembled with Co-MoC/NCNFs requires only a cell voltage of 1.59 V at 10 mA cm^-2 in 1 m KOH. This work opens new pathways for the design of high-efficiency electrocatalysts for energy conversion applications.

Cell membrane nanoparticles have attracted increasing interest in nanomedicine because they allow to exploit the complexity of cell membrane interactions for drug delivery. Several methods are used to obtain plasma membrane to generate cell membrane nanoparticles. Here, an optimized method combining nitrogen cavitation in isotonic buffer and sucrose gradient fractionation is presented. The method allows to obtain cell membrane fractions of high purity from both suspension and adherent cells. Comparison with other common methods for membrane extraction, where mechanical lysis using cell homogenizers is performed in isotonic or hypotonic buffers, shows that the optimized procedure yields high purity membrane in a robust and reproducible way. Procedures to mix the purified membrane with synthetic lipids to obtain cell membrane liposomes (CMLs) are presented and indications on how to optimize these steps are provided. CMLs made using crude membrane isolates or the purified membrane fractions show different uptake by cells. The CMLs made with the optimized procedure and liposomes of the same composition but without cell membrane components are thoroughly characterized and compared for their size, zeta potential, bilayer and mechanical properties to confirm membrane protein inclusion in the CMLs. Cell uptake studies confirm that the inclusion of membrane components modifies liposome interactions with cells.

Oxygen production within human cells plays a critical role in cellular metabolism and is implicated in various diseases, including cancer. Investigating cellular heterogeneity under oxygen stimulation is crucial for elucidating disease mechanisms and advancing early therapeutic design. In this study, the platinum-based wireless nanopore electrode (WNE) with a diameter of ≈200 nm is employed as a powerful tool to produce oxygen molecules near the cell nucleus. The oxygen production can be quantitatively controlled by adjusting the applied voltage. Through delivering oxygen near the cancer cell nucleus, this technique shows the capacity to alleviate the hypoxia microenvironment, a key factor in chemotherapy resistance. Furthermore, by modulating oxygen levels within individual living cells and delivering chemotherapeutic agents to the cancer cell nucleus, this approach offers significant potential for single-cell manipulation and the investigation of cellular heterogeneity under oxygen stimulation.

The MOF-guest relationship is broken down in elementary phases, descriptors, and parameters. These descriptors and parameters allow precise descriptions of processes, whether they occur at the point when the guest enters the MOF, during the stay, or at the point of exiting. Description of these three phases is possible according to the location of the guest inside the MOF, the activity between MOF and guest, whether stimuli can be used, and whether a selective action can be exercised. The vocabulary provided herein can be useful to better formulate requirements when designing host-guest interactions in, and building new classes of, intelligent materials.

Hepatocellular carcinoma (HCC) is typically characterized by rich vascularity, with angiogenesis playing a crucial role in its growth and invasion. Molecular imaging of specific receptors in blood vessels is crucial in HCC diagnosis. In particular, in vivo imaging utilizing the second near-infrared (NIR-II) window offers improved tissue penetration, reduced light scattering, and lower autofluorescence. Despite the great potential of the NIR-II window, developing safe and effective probes to provide better imaging performance for HCC is urgently needed. In this study, NIR-II imaging integrated with a vascular endothelial growth factor receptor (VEGFR)-targeted probe generated by combining a VEGFR-targeted peptide with indocyanine green (ICG) is used to characterize HCC-related angiogenesis at a resolution of 56.0 µm. For the first time, liver metabolic curves and parameters of liver function reserve (LFR) are obtained by fitting NIR-II fluorescence signals with high spatiotemporal resolution, showing significant differences between HCC mice and controls. Moreover, unlike ICG, the targeting probe has a targeted effect on blood vessels in vivo. The tumor-to-normal (T/N) ratio in NIR-II imaging reaches up to 3.30 after post-injection of the targeting probe. The results indicate that the VEGFR-targeted probe is a powerful tool for NIR-II fluorescence imaging to enhance early diagnosis of HCC.

This study reveals a local strain-dependent etching behavior that enables the formation of distinguished etching patterns in differently strained chemical vapor deposited (CVD) 2D molybdenum disulfide (MoS₂) monolayers. It is demonstrated that when the local tensile strain of CVD 2D MoS₂ is as uniformly low as ɛ ≈ 0.33% or less, the oxidative etching pattern possesses conventional triangular etching pits (TEPs), while when the local tensile strain is as uniformly high as ɛ ≈ 0.55% or larger, the oxidative etching pattern consist of uniformly oriented hexagonal etching channels (HECs). More interestingly, when the CVD 2D MoS₂ monolayer has heterogenous strain distribution from ɛ ≈ 0.55% (center region) to ɛ ≈ 0.33% (perimeter region), the oxidative etching pattern comprise of non-uniformly hexagonal-mixed-parallel etching channels (HPECs). The further characterization and analysis reveal the formation mechanism of such strain-dependent etching patterns is built on the local strain-related fractures propagation under oxidative etching, as well as the anisotropy fractures-based oxidative etching kinetics. This study may enhance the understanding of the relationship between etching and growth features of 2D TMDs, and paves the way to etching-nanostructured (or defect) engineering of 2D TMDs and other 2D materials for potential applications in electrocatalysis and optoelectronics.

Van der Waals (vdW) heterostructures comprising of transition metal dichalcogenides (TMDs) and hexagonal boron nitride (h-BN) are promising building blocks for novel 2D devices. The vdW epitaxy provides a straightforward integration method for fabricating high-quality TMDs/h-BN vertical heterostructures. In this work, the vdW epitaxy of high-quality single-crystal HfSe₂ on epitaxial h-BN/sapphire substrates by chemical vapor deposition is demonstrated. The epitaxial HfSe₂ layers exhibit a uniform and atomically sharp interface with the underlying h-BN template, and the epitaxial relationship between HfSe₂ and h-BN/sapphire is determined to HfSe₂ (0001)[1 $\overline{2}$ 10]//h-BN (0001)[1 $\overline{1}$ 00]//sapphire (0001)[1 $\overline{1}$ 00]. Impressively, the full width at half maximum of the rocking curve for the epitaxial HfSe₂ layer on single-crystal h-BN is as narrow as 9.6 arcmin, indicating an extremely high degree of out-plane orientation and high crystallinity. Benefitting from the high crystalline quality of HfSe₂ epilayers and the weak interfacial scattering of HfSe₂/h-BN, the photodetector fabricated from the vdW epitaxial HfSe₂ on single-crystal h-BN shows the best performance with an on/off ratio of 1 × 10⁴ and a responsivity up to 43 mA W^-1. Furthermore, the vdW epitaxy of other TMDs such as HfS₂, ZrS₂, and ZrSe₂ is also experimentally demonstrated on single-crystal h-BN, suggesting the broad applicability of the h-BN template for the vdW epitaxy.