A reproducible synthetic strategy was developed for facile large-scale (200 mg) synthesis of surface silanized magnetite (Fe3O4) nanoparticles (NPs) for biological applications. After further coupling a phosphate-specific affinity ligand, these functionalized magnetic NPs were used for the highly specific enrichment of phosphoproteins from a complex biological mixture. Moreover, correlating the surface silane density of the silanized magnetite NPs to their resultant enrichment performance established a simple and reliable quality assurance control to ensure reproducible synthesis of these NPs routinely in large scale and optimal phosphoprotein enrichment performance from batch-to-batch. Furthermore, by successful exploitation of a top-down phosphoproteomics strategy that integrates this high throughput nanoproteomics platform with online liquid chromatography (LC) and tandem mass spectrometry (MS/MS), we were able to specifically enrich, identify, and characterize endogenous phosphoproteins from highly complex human cardiac tissue homogenate. This nanoproteomics platform possesses a unique combination of scalability, specificity, reproducibility, and efficiency for the capture and enrichment of low abundance proteins in general, thereby enabling downstream proteomics applications.
Lanthanide-based luminescent anti-counterfeiting materials are widely used in various kinds of products. However, the emission color of traditional lanthanide-based luminescent materials usually remains nearly unaltered upon different excitation lights, which may only work for single-level anti-counterfeiting. Herein, the NaYbF4:2%Er@NaYF4 core/shell nanoplates (NPs) with “chameleon-like” optical behavior are developed. These NPs display single-band red or green downshifting (DS) emission upon excitation at 377 or 490 nm, respectively. Upon 980 nm excitation, the color of upconversion (UC) emission can be finely tuned from green to yellow, and to red with increasing the excitation power density from 0.1 to 4.0 W/cm2. The proposed materials readily integrate the advantages of excitation wavelength-dependent DS single-band emissions and sensitive excitation power-dependent UC multicolor emissions in one and the same material, which has never been reported before. Particularly, the proposed NPs exhibit excellent performance as security labels on trademark tag and security ink on painting, thus revealing the great potential of these lanthanide-doped fluoride NPs in multilevel anti-counterfeiting applications.
The morphology and structural stability of metal/2D semiconductor interfaces strongly affect the performance of 2D electronic devices and synergistic catalysis. However, the structural evolution at the interfaces has not been well explored particularly at atomic resolution. In this work, we study the structural evolution of Au nanoparticles (NPs) on few-layer MoS2 by high resolution transmission electron microscope (HRTEM) and quantitative high-angle annular dark field scanning TEM. It is found that in the transition of Au from nanoparticles to dendrites, a dynamically epitaxial alignment between Au and MoS2 lattices is formed, and Moiré patterns can be directly observed in HRTEM images due to the mismatch between Au and MoS2 lattices. This epitaxial alignment can occur in ambient conditions, and can also be accelerated by the irradiation of high-energy electron beam. In situ observation clearly reveals the rotation of Au NPs, the atom migration inside Au NPs, and the transfer of Au atoms between neighboring Au NPs, finally leading to the formation of epitaxially aligned Au dendrites on MoS2. The structural evolution of metal/2D semiconductor interfaces at atomic scale can provide valuable information for the design and fabrication of the metal/2D semiconductor nano-devices with desired physical and chemical performances.
We propose a process of quantum-confined ion superfluid (QISF), which is enthalpy-driven confined ordered fluid, to explain the transmission of nerve signals. The ultrafast Na+ and K+ ions transportation through all sodium-potassium pump nanochannels simultaneously in the membrane is without energy loss, and leads to QISF wave along the neuronal axon, which acts as an information medium in the ultrafast nerve signal transmission. The QISF process will not only provide a new view point for a reasonable explanation of ultrafast signal transmission in the nerves and brain, but also challenge the theory of matter wave for ions, molecules and particles.
Electrochemical N2 reduction offers a promising alternative to the Haber-Bosch process for sustainable NH3 synthesis at ambient conditions, but it needs efficient catalysts for the N2 reduction reaction (NRR). Here, we report that FeOOH quantum dots decorated graphene sheet acts as a superior catalyst toward enhanced electrocatalytic N2 reduction to NH3 under ambient conditions. In 0.1 M LiClO4, this hybrid attains a large NH3 yield rate and a high Faradaic efficiency of 27.3 µg·h−1·mg−1cat. and 14.6% at −0.4 V vs. reversible hydrogen electrode, respectively, rivalling the current efficiency of all Fe-based NRR electrocatalysts in aqueous media. It also shows strong durability during the electrolytic process.
DNA is a self-assembled, double stranded natural molecule that can chelate and align nickel ions between its base pairs. The fabrication of a DNA-guided nickel ion chain (Ni-DNA) device was successful, as indicated by the conducting currents exhibiting a Ni ion redox reaction-driven negative differential resistance effect, a property unique to mem-elements (1). The redox state of nickel ions in the Ni-DNA device is programmable by applying an external bias with different polarities and writing times (2). The multiple states of Ni-DNA-based memristive and memcapacitive systems were characterized (3). As such, the development of Ni-DNA nanowire device-based circuits in the near future is proposed.
Two-dimensional (2D) nanomaterials have attracted a great deal of attention since the discovery of graphene in 2004, due to their intriguing physicochemical properties and wide-ranging applications in catalysis, energy-related devices, electronics and optoelectronics. To maximize the potential of 2D nanomaterials for their technological applications, controlled assembly of 2D nanobulding blocks into integrated systems is critically needed. This mini review summarizes the reported strategies of 2D materials-based assembly into integrated functional nanostructures, from in-situ assembly method to post-synthesis assembly. The applications of 2D assembled integrated structures are also covered, especially in the areas of energy, electronics and sensing, and we conclude with discussion on the remaining challenges and potential directions in this emerging field.
Nanoparticles (NPs) which are innovation and research focus in drug delivery systems, still have some disadvantages limiting its application in clinical use, such as short circulation time, recognition and clearance by reticuloendothelial system (RES) and passive targeting in certain organs. However, the recent combination of natural components and nanotechnology has offered new solutions to address these problems. A novel biomimetic platform consisting of nanoparticle core and membrane shell, such as cell membrane, exosome or vesicle vastly improves properties of nanoparticles. These coated nanoparticles can replicate the unique functions of the membrane, such as prolonged blood circulation, active targeting capability and enhanced internalization. In this review, we focus on the newest development of biological-camouflaged nanoparticles and mainly introduce its application related to cancer therapy and toll-like receptor.
Utilizing vacuum-tuned-atmosphere induced dip coating method, we achieve the cross-dimensional macroscopic diverse self-assemblies by using one building block with one chemical functionality. Coordinated modulating the vacuum degree, colloid concentration and evaporation atmosphere, Au@Ag core/shell NCs can controllably assemble into diverse multi-dimensional superstructures. Under 0.08 MPa, we obtained the two-dimensional (2D) stepped superstructures with continuously tunable step width. In addition, we generated a series of tailorable nanoscale-roughened 2D Au@Ag NCs superstructures at 0.04 MPa, which exhibited the label-free ultrasensitive SERS detection for the different mutants of IAPP8-37 proteins. Under 0.01 MPa, we obtained the cross-dimensional tailorable Au@Ag NCs assemblies from random to macroscale 2D and three-dimensional (3D) densest superstructures by adjusting the capping ligand-environmental molecule interactions. This is a flexible method to generate as-prepared Au@Ag core/shell NCs into well-defined macroscopic diverse superstructures and to promote the exploitation into biological applications.
Elliptical metallic nanohole arrays possess much higher transmission and enhanced sensitivity compared with circular nanohole arrays. However, fabricating elliptical metallic nanohole arrays in large area with highly tunable aspect ratio remains a challenge. Herein, a brand-new method combining stretchable imprinting with colloidal lithography is figured out to fabricate deep-elliptical-silver-nanowell arrays (d-EAgNWAs). In this method, large area highly ordered silicon nanopillar arrays fabricated by colloidal lithography were taken as a master to transfer large area polydimethylsiloxane (PDMS) nanohole arrays. Benefit from the high elasticity of PDMS mold, the aspect ratio of d-EAgNWAs achieved can be facilely regulated from 1.7 to 5.0. Through optimization of polarization direction and the structural parameters including nanowell depth, aspect ratio, and hole size, the sensing performance of d-EAgNWAs was finally improved up to 1,414.1 nm/RIU. The best sensing behaved d-EAgNWAs were employed as an immunoassay platform finally to prove their great potential in label-free biosensing.
Subtle structural changes during electrochemical processes often relate to the degradation of electrode materials. Characterizing the minute-variations in complementary aspects such as crystal structure, chemical bonds, and electron/ion conductivity will give an in-depth understanding on the reaction mechanism of electrode materials, as well as revealing pathways for optimization. Here, vanadium pentoxide (V2O5), a typical cathode material suffering from severe capacity decay during cycling, is characterized by in-situ X-ray diffraction (XRD) and in-situ Raman spectroscopy combined with electrochemical tests. The phase transitions of V2O5 within the 0–1 Li/V ratio are characterized in detail. The V–O and V–V distances became more extended and shrank compared to the original ones after charge/discharge process, respectively. Combined with electrochemical tests, these variations are vital to the crystal structure cracking, which is linked with capacity fading. This work demonstrates that chemical bond changes between the transition metal and oxygen upon cycling serve as the origin of the capacity fading.
All-inorganic cesium lead halide perovskite quantum dots (QDs) have been a promising candidate for optoelectronic devices in recent years, such as light-emitting diodes, photodetectors and solar cells, owing to their superb optoelectronic properties. Still, the stability issue of nanocrystals is a bottleneck for their practical application. Herein, we report a facile method for the synthesis of a series of phosphine ligand modified CsPbBr3 QDs with high PL intensity. By introducing organic phosphine ligands, the tolerance of CsPbBr3 QDs to ethanol, water and UV light was dramatically improved. Moreover, the phosphine ligand modified QD films deposited on the glass subtracts exhibit superior PL intensity and optical stability to those of pristine QD based films.
Atherosclerotic plaque rupture results in thrombus formation and vessel occlusion, and is the leading cause of death worldwide. There is a pressing need to identify plaque vulnerability for the treatment of carotid and coronary artery diseases. Nanomaterials with enzyme-like properties have attracted significant interest by providing biological, diagnostic and prognostic information about the diseases. Here we showed that bioengineered magnetoferritin nanoparticles (M-HFn NPs) functionally mimic peroxidase enzyme and can intrinsically recognize plaque-infiltrated active macrophages, which drive atherosclerotic plaque progression and rupture and are significantly associated with the plaque vulnerability. The M-HFn nanozymes catalyze the oxidation of colorimetric substrates to give a color reaction that visualizes the recognized active macrophages for one-step pathological identification of plaque vulnerability. We examined 50 carotid endarterectomy specimens from patients with symptomatic carotid disease and demonstrated that the M-HFn nanozymes could distinguish active macrophage infiltration in ruptured and high-risk plaque tissues, and M-HFn staining displayed a significant correlation with plaque vulnerability (r = 0.89, P < 0.0001).
Benzaldehyde byproduct is an imperative intermediate in the production of fine chemicals and additives. Tuning selectivity to benzaldehyde is therefore critical in alcohol oxidation reactions at the industrial level. Herein, we report a simple but innovative method for the synthesis of palladium hydride and nickel palladium hydride nanodendrites with controllable morphology, high stability, and excellent catalytic activity. The synthesized dendrites can maintain the palladium hydride phase even after their use in the chosen catalytic reaction. Remarkably, the high surface area morphology and unique interaction between nickel-rich surface and palladium hydride (β-phase) of these nanodendrites are translated in an enhanced catalytic activity for benzyl alcohol oxidation reaction. Our Ni/PdH0.43 nanodendrites demonstrated a high selectivity towards benzaldehyde of about 92.0% with a conversion rate of 95.4%, showing higher catalytic selectivity than their PdH0.43 counterparts and commercial Pd/C. The present study opens the door for further exploration of metal/metal-hydride nanostructures as next-generation catalytic materials.
We describe a route to the preparation of (metal yolk)/(porous ceria shell) nanostructures through the heterogeneous growth of ceria on porous metal nanoparticles followed by the calcination-induced shrinkage of the nanoparticles. The approach allows for the control of the ceria shell thickness, the metal yolk composition and size, which is difficult to realize through common templating approaches. The yolk/shell nanostructures with monometallic Pt and bimetallic PtAg yolks featuring plasmon-induced broadband light absorption in the visible region are rationally designed and constructed. The superior photocatalytic activities of the obtained nanostructures are demonstrated by the selective oxidation of benzyl alcohol under visible light. The excellent activities are ascribed to the synergistic effects of the metal yolk and the ceria shell on the light absorption, electron-hole separation and efficient mass transfer. Our synthesis of the (metal yolk)/(porous ceria shell) nanostructures points out a way to the creation of sophisticated heteronanostructures for high-performance photocatalysis.
Triple-negative breast cancer (TNBC) is one type of the most aggressive breast cancers with poor prognosis. It is of great urgency to develop new therapeutics for treating TNBC. Based on current treatment guideline and genetic information of TNBC, a combinational therapy platform integrating chemotherapy drugs and mRNA encoding tumor suppressor proteins may become an efficacious strategy. In this study, we developed paclitaxel amino lipid (PAL) derived nanoparticles (NPs) to incorporate both chemotherapy drugs and P53 mRNA. The PAL P53 mRNA NPs showed superior properties compared to Abraxane® and Lipusu® used in the clinic including high paclitaxel loading capacity (24 wt.%, calculated by paclitaxel in PAL), PAL encapsulation efficiency (94.7% ± 6.8%) and mRNA encapsulation efficiency (88.7% ± 0.7%). Meanwhile, these NPs displayed synergetic cytotoxicity of paclitaxel and P53 mRNA in cultured TNBC cells. More importantly, we demonstrated in vivo anti-tumor efficacy of PAL P53 mRNA NPs in an orthotopic TNBC mouse model. Overall, these chemotherapy drugs derived mRNA NPs provide a new platform to integrate chemotherapy and personalized medicine using tumor genetic information, and therefore represent a promising approach for TNBC treatment.
Atomically thin transition metal dichalcogenides (TMDs) have distinct opto-electronic properties including enhanced luminescence and high on-off current ratios, which can be further modulated by making more complex TMD heterostructures. However, resolution limits of conventional optical methods do not allow for direct nanoscale optical-structural correlation measurements in these materials, particularly of buried interfaces in TMD heterostructures. Here we use, for the first time, electron beam induced cathodoluminescence in a scanning transmission electron microscope (CL-STEM) to measure optical properties of monolayer TMDs (WS2, MoS2 and WSSe alloy) encapsulated between layers of hBN. We observe dark areas resulting from localized (~ 100 nm) imperfect interfaces and monolayer folding, which shows that the intimate contact between layers in this application-relevant heterostructure is required for proper inter layer coupling. We also realize a suitable imaging method that minimizes electron-beam induced changes and provides measurement of intrinsic properties. To overcome the limitation of small electron interaction volume in TMD monolayer (and hence low photon yield), we find that encapsulation of TMD monolayers with hBN and subsequent annealing is important. CL-STEM offers to be a powerful method to directly measure structure-optical correspondence in lateral or vertical heterostructures and alloys.
In this work, homogeneous Ni0.33Co0.67Se hollow nanoprisms were synthesized successfully in virtue of Kirkendall effect. It is the first time for bimetallic Ni-Co compounds Ni0.33Co0.67Se to be used in lithium-ion batteries (LIBs). Impressively, the Ni0.33Co0.67Se hollow nanoprisms show superior specific capacity (1,575 mAh/g at the current density of 100 mA/g) and outstanding rate performance (850 mAh/g at 2,000 mA/g) as anode material for LIBs. This work proves the potential of bimetallic chalcogenide compounds as high performance anode materials for LIBs.
Structure–activity relationship (SAR) is the key problem of nanoscience, thus to fabricate novel and well-defined nanostructure will provide a new insight on catalyst preparation method. Highly active and low cost electrocatalysts for oxygen evolution reaction (OER) are of great importance for future renewable energy conversion and storage. Herein, NiFe-based layered double hydroxides with laminar structure (NFLS) were successfully fabricated via a one-step hydrothermal approach by using sodium dodecyl sulfate as surfactant. The as-fabricated NFLS showed a well-defined periodic layered-stacking geometry with a scale down to 1-nm. Benefitting from the unique structure, NFLS exhibited an excellent catalytic activity towards OER with current densities of 10 mA·cm−2 at overpotential of 197 mV. The synergistic effect of Ni and Fe plays a key role in electrode reactions. The present work provides a new insight to improve the OER performance by rational design of electrocatalysts with unique structures.
Platinum (Pt)-based electrocatalyst with low Pt content and high electrocatalytic performance is highly desired in fuel cell applications. Herein, we demonstrated that platinum-nickel (Pt-Ni) nanowires with an average composition of PtNi3 and a fishbone structure can be readily synthesized and used as an efficient electrocatalyst toward methanol oxidation reaction (MOR). The PtNi3 fishbone-like nanowires (PtNi3-FBNWs) present features such as richer Pt on the surface than in the bulk, high-index facets on the rough surface, and polyhedral facets at the ends of side chains. Such compositional and structural features could be determinative to the enhanced performance in the electrocatalysis of MOR. Compared with commercial 20% Pt/carbon black (Pt/C), the specific activity and mass activity of the PtNi3-FBNWs are enhanced by approximately 4.76 and 3.02 times, respectively. The stability of electrocatalysis is significantly improved as well. Such comprehensive enhancement indicates that the PtNi3-FBNWs would be a promising candidate toward MOR in fuel cells.