Globally, cancer is growing at an alarming pace, which calls for development of more efficient cancer treatments. Conventional chemotherapy and radiotherapy have become crucial first-line clinical treatments for cancer. However, along with their wide usage, limited therapeutic effects, severe adverse reactions, unaffordable costs, and complicated operations lead to failures of these treatments. Moreover, the emergence of multidrug resistance inhibits the longtime usage of chemotherapeutics. One of the major causes of treatment failure is the insufficient sensitivity of cancer cells to therapeutic drugs or treatments. With the rigorous development of nanotechnology, tailored nanoparticles can efficiently sensitize malignant cells by inducing intracellular structural and functional changes, which could affect vital intracellular processes such as metabolism, signal conduction, proliferation, cell death as well as intracellular drug delivery. Here, we review recent advances in nanomaterial-assisted sensitization of oncotherapy, and challenges and strategies in the development of nanomedical approaches.
Biotemplated metal nanoclusters have garnered much attention owing to their wide range of potential applications in biosensing, bioimaging, catalysis, and nanomedicine. Here, we report the synthesis of stable, biocompatible, water-soluble, and highly fluorescent bovine serum albumin-templated cadmium nanoclusters (CdNCs) through a facile one-pot green method. We covalently conjugated hyaluronic acid (HA) to the CdNCs to form a pH-responsive, tumortargeting theranostic nanocarrier with a sustained release profile for doxorubicin (DOX), a model anticancer drug. The nanocarrier showed a DOX encapsulation efficiency of about 75.6%. DOX release profiles revealed that 74% of DOX was released at pH 5.3, while less than 26% of DOX was released at pH 7.4 within the same 24-h period. The nanocarrier selectively recognized MCF-7 breast cancer cells expressing CD44, a cell surface receptor for HA, whereas no such recognition was observed with HA receptor-negative HEK293 cells. Biocompatibility of the nanocarrier was evaluated through cytotoxicity assays with HEK293 and MCF-7 cells. The nanocarrier exhibited very low to no cytotoxicity, whereas the DOX-loaded nanocarrier showed considerable cellular uptake and enhanced MCF-7 breast cancer cell-killing ability. We also confirmed the feasibility of using the highly fluorescent nanoconjugate for bioimaging of MCF-7 and HeLa cells. The superior targeted drug delivery efficacy, cellular imaging capability, and low cytotoxicity position this nanoconjugate as an exciting new nanoplatform with promising biomedical applications.
In this paper, we demonstrate that for colloidal CdSe/CdS nanoplatelets, a rectangular shape induces emission asymmetry, in terms of both polarization and emission patterns. Polarimetry and emission pattern analyses are combined to provide information on the orientation of the transition dipoles involved in the nanoplatelet emission. It is shown that for rectangular nanoplatelets, the emission is polarized and the emission patterns are anisotropic, whereas they remain nonpolarized and isotropic for square nanoplatelets. This can be appropriately described by the dielectric antenna effect induced by the elongated shape of the rectangular platelet.
Solid polymer electrolytes are light-weight, flexible, and non-flammable and provide a feasible solution to the safety issues facing lithium-ion batteries through the replacement of organic liquid electrolytes. Substantial research efforts have been devoted to achieving the next generation of solid-state polymer lithium batteries. Herein, we provide a review of the development of solid polymer electrolytes and provide comprehensive insights into emerging developments. In particular, we discuss the different molecular structures of the solid polymer matrices, including polyether, polyester, polyacrylonitrile, and polysiloxane, and their interfacial compatibility with lithium, as well as the factors that govern the properties of the polymer electrolytes. The discussion aims to give perspective to allow the strategic design of state-of-the-art solid polymer electrolytes, and we hope it will provide clear guidance for the exploration of high-performance lithium batteries.
Understanding how small molecules interface with amyloid fibrils at the nanoscale is of importance for developing therapeutic treatments against amyloid-based diseases. Here, we show for the first time that human islet amyloid polypeptides (IAPP) in the fibrillar form are polymorphic, ambidextrous, and possess multiple periodicities. Upon interfacing with the small molecule epigallocatechin gallate (EGCG), IAPP aggregation was rendered off-pathway and assumed a form with soft and disordered clusters, while mature IAPP fibrils displayed kinks and branching but conserved the twisted fibril morphology. These nanoscale phenomena resulted from competitive interactions between EGCG and the IAPP amyloidogenic region, as well as end capping of the fibrils by the small molecule. This information is crucial in delineating IAPP toxicity implicated in type 2 diabetes and for developing new inhibitors against amyloidogenesis.
An innovative spongy nanographene (SG) shell for a silicon substrate was prepared by low-temperature chemical vapor deposition on a hierarchical nickel nanotemplate. The SG-functionalized silicon (Si@SG) composite shows outstanding properties, which may be helpful to overcome issues affecting current silicon anodes used in lithium ion batteries such as poor conductivity, large volume expansion and high mass transfer resistance. The hierarchical nanographene shell exhibits elastic, sponge-like features that allow it to self-adaptively change its volume to accommodate the volume expansion of silicon. In addition, the porous, spongy framework containing randomly stacked graphene nanosheets presents low diffusion barriers and provides sufficiently free and short-haul channel segments to allow the fast migration of Li and electrolyte ions. The unique properties of the present silicon anode result in excellent electrochemical performances in terms of long-term cycling stability (95% capacity retention after 510 cycles), rate performance, and cycling behavior for high mass loadings at different current densities.
Gases that are widely used in research and industry have a significant effect on both the configuration of solid materials and the evolution of reactive systems. Traditional studies on gas–solid interactions have mostly been static and post-mortem and unsatisfactory for elucidating the real active states during the reactions. Recent developments of controlled-atmosphere transmission electron microscopy (TEM) have led to impressive progress towards the simulation of real-world reaction environments, allowing the atomic-scale recording of dynamic events. In this review, on the basis of the in situ research of our group, we outline the principles and features of the controlled-atmosphere TEM techniques and summarize the significant recent progress in the research activities on gas–solid interactions, including nanowire growth, catalysis, and metal failure. Additionally, the challenges and opportunities in the real-time observations on such platform are discussed.
Molybdenum disulfide (MoS2), a promising non-precious electrocatalyst for the hydrogen evolution reaction with two-dimensional layered structure, has received increasing attention in recent years. Its electrocatalytic performance has been limited by the low active site content and poor conductivity. Herein, we report a facile and general ultrafast laser ablation method to synthesize MoS2 quantum dots (MS-QDs) for electrocatalytic HER with fully exposed active sites and highly enhanced conductivity. The MS-QDs were prepared by ultrafast laser ablation of the corresponding bulk material in aqueous solution, during which they were partially oxidized and formed defective structures. The as-prepared MS-QDs demonstrated high activity and stability in the electrocatalytic HER, owing to their very large surface area, defective structure, abundance of active sites, and high conductivity. The present MS-QDs can also find application in optics, sensing, energy storage, and conversion technologies.
A micropump induces the flow of its surrounding fluids and is extremely promising in a variety of applications such as chemical sensing or mass transportation. However, it is still challenging to manipulate its pumping direction. In this study, we examine a binary micropump based on perovskite and poly[(2-methoxy-5-ethylhexyloxy)-1,4-phenylenevinylene] (MEHPPV). The micropump is operational under the influence of light. Light exhibits significant versatility in controlling the pumping phenomenon of the micropump. It governs the start and stop and also regulates the velocity and directions. The direction control signifies immense opportunities for the development of micropumps with unprecedented pumping behaviors and functions (such as heartbeat-like pumping, rectification, and amplification). This makes them potentially useful in various fields. Hence, it is expected that the micropump reported in the current study could act as a key step towards the further development of more sophisticated micropumps for diverse applications.
Flexible memristor devices based on plastic substrates have attracted considerable attention due to their applications in wearable computers and integrated circuits. However, most plastic-substrate memristors cannot function or be grown in high-temperature environments. In this study, scotch-tape-exfoliated mica was used as the flexible memristor substrate in order to resolve these high-temperature issues. Our TiN/ZHO/IGZO memristor, which was constructed using a thin (10 μm) mica substrate, has superior flexibility and thermostability. After bending it 103 times, the device continues to exhibit exceptional electrical characteristics. It can also be implemented for transitions between high and low resistance states, even in temperatures of up to 300 °C. More importantly, the biological synaptic characteristics of paired-pulse facilitation/depression (PPF/PPD) and spike-timing-dependent plasticity (STDP) were observed through applying different pulse measurement modes. This work demonstrates that flexible memristor devices on mica substrates may potentially allow for the realization of high-temperature memristor applications for biologically-inspired computing systems.
Colloidal Au-core/Ag-shell nanorods with an asymmetric transverse cross-section and a strong octupolar plasmon resonance are synthesized by the controlled growth of Ag shells on one side of the Au cores. A largely enhanced second harmonic generation (SHG) from these asymmetric core–shell nanorods is demonstrated for the first time by tuning the dipolar and the octupolar plasmon modes to make them resonant with the fundamental and harmonic frequencies, respectively. The SHG intensity of the Au–Ag nanorods with dual-frequency resonances is enhanced by 21 times compared to that of the bare Au nanorods. The co-existence of the dipolar, quadrupolar, and octupolar radiations in the SHG is revealed. Additionally, the cellular uptake of the Au–Ag nanorods is monitored and the evolution of the membrane bleb is successfully observed by the SHG imaging. Our observations provide a strategy for enhancing the SHG of the colloidal metal nanoparticles and can have applications in chemical process monitoring and biological sensing.
Hierarchical FeP nanoarray films composed of FeP nanopetals were successfully synthesized via a bio-inspired hydrothermal route followed by phosphorization. Glycerol, as a crystal growth modifier, plays a significant role in controlling the morphology and structure of the FeO(OH) precursor during the biomineralization process, while the following transfer and pseudomorphic transformation of the FeO(OH) film successfully give rise to the FeP array film. The as-prepared FeP film electrodes exhibit excellent hydrogen evolution reaction (HER) performance over a wide pH range. Theoretical calculations reveal that the mixed P/Fe termination in the FeP film is responsible for the high catalytic activity of the nanostructured electrodes. This new insight will promote further explorations of efficient metal phosphoride-based catalysts for the HER. More importantly, this study bridges the gap between biological and inorganic self-assembling nanosystems and may open up a new avenue for the preparation of functional nanostructures with application in energy devices.
Finite-sized graphene sheets, such as graphene nanoislands (GNIs), are promising candidates for practical applications in graphene-based nanoelectronics. GNIs with well-defined zigzag edges are predicted to have spin-polarized edge-states similar to those of zigzag-edged graphene nanoribbons, which can achieve graphene spintronics. However, it has been reported that GNIs on metal substrates have no edge states because of interactions with the substrate.We used a combination of scanning tunneling microscopy, spectroscopy, and density functional theory calculations to demonstrate that the edge states of GNIs on an Ir substrate can be recovered by intercalating a layer of Si atoms between the GNIs and the substrate. We also found that the edge states gradually shift to the Fermi level with increasing island size. This work provides a method to investigate spin-polarized edge states in high-quality graphene nanostructures on a metal substrate.
Two-dimensional (2D) nanomaterials have gained tremendous attention in the field of biomedicine because of their high specific surface areas and fascinating physicochemical properties. Herein, 2D monolayered double hydroxide (MLDH) nanosheets were employed to localize doxorubicin (DOX), an anticancer drug, with a loading capacity of as high as 3.6 mg·mg–1 (w/w). Structural characterizations and theoretical calculations indicate that the DOX molecule is uniformly arranged and oriented at the surface of the MLDHs with a binding energy of 15.90 eV, showing significant electrostatic interaction. With the assistance of the targeting agent folic acid (FA), DOX-FA/MLDHs demonstrate targeted cellular uptake and superior anticancer behavior based on in vitro tests performed with cancer cells. In addition, this composite material exhibits a selective release toward cancer cells and good biocompatibility with normal cells, which would guarantee its practical applications in cancer therapy.
In this study, a potentially universal new strategy is reported for the large-scale, low-cost fabrication of visible-light-active highly ordered heteronanostructures based on the spontaneous photoelectric-field-enhancement effect inherent in pyramidal morphology. The hierarchical vertically oriented arrayed structures comprise an active molecular co-catalyst at the apex of a visible-light-active large band gap semiconductor for low-cost solar water splitting in a neutral aqueous medium without the use of a sacrificial agent.
The development of an electrocatalyst based on abundant elements for the oxygen evolution reaction (OER) is important for water splitting associated with renewable energy sources. In this study, we develop an interconnected Ni(Fe)OxHy nanosheet array on a stainless steel mesh (SSNNi) as an integrated OER electrode, without using any polymer binder. Benefiting from the well-defined three-dimensional (3D) architecture with highly exposed surface area, intimate contact between the active species and conductive substrate improved electron and mass transport capacity, facilitated electrolyte penetration, and improved mechanical stability. The SSNNi electrode also has excellent OER performance, including low overpotential, a small Tafel slope, and long-term durability in the alkaline electrolyte, making it one of the most promising OER electrodes developed.
Electronic properties of stanene, the Sn counterpart of graphene are theoretically studied using first-principles simulations. The topological to trivial insulating phase transition induced by an out-of-plane electric field or by quantum confinement effects is predicted. The results highlight the potential to use stanene nanoribbons in gate-voltage controlled dissipationless spin-based devices and are used to set the minimal nanoribbon width for such devices, which is typically approximately 5 nm.
A thermal emitter composed of a frequency-selective surface metamaterial layer and a hexagonal boron nitride-encapsulated graphene filament is demonstrated. The broadband thermal emission of the metamaterial (consisting of ring resonators) was tailored into two discrete bands, and the measured reflection and emission spectra agreed well with the simulation results. The high modulation frequencies that can be obtained in these devices, coupled with their operation in air, confirm their feasibility for use in applications such as gas sensing.
Graphene oxide (GO) is a graphene derivative bearing various oxygen-containing functional groups attached to the basal plane and to the edges of the graphene lattice and hence has a unique structure in which numerous hydrophobic sp2 clusters are isolated within the hydrophilic sp3 C–O matrix. In this study, the hydrophilic nature and water-transporting properties of GO were exploited to promote germination and growth of plants. It was found that a low dose of GO significantly promoted the germination of spinach and chive in soil. The oxygen-containing functional groups of GO collected water, and the hydrophobic sp2 domains transported water to the seeds to accelerate the germination of plants. The strong interaction between GO and the surfaces of soil grains stabilized GO in the soil and prevented dissipation of GO. In addition, no GO was detected either on the surface or inside the cells of plants; this finding confirmed that GO was not phytotoxic. Therefore, GO may serve as a promising nontoxic additive to increase a plant yield.
The emergence and establishment of new techniques for material fabrication are of fundamental importance in the development of materials science. Thus, we herein report a general synthetic strategy for the preparation of monolayer graphene. This novel synthetic method is based on the direct solid-state pyrolytic conversion of a sodium carboxylate, such as sodium gluconate or sodium citrate, into monolayer graphene in the presence of Na2CO3. In addition, gram-scale quantities of the graphene product can be readily prepared in several minutes. Analysis using Raman spectroscopy and atomic force microscopy clearly demonstrates that the pyrolytic graphene is composed of a monolayer with an average thickness of ～0.50 nm. Thus, the present pyrolytic conversion can overcome the issue of the low monolayer contents (i.e., 1 wt.%–12 wt.%) obtained using exfoliation methods in addition to the low yields of chemical vapor deposition methods. We expect that this novel technique may be suitable for application in the preparation of monolayer graphene materials for batteries, supercapacitors, catalysts, and sensors.
