Theranostic 2D Tantalum Carbide (MXene)

The large‐dimensional and rigid ceramic bulks fabricated by high‐temperature solid‐phase reaction and sintering have never been considered for possibly entering and circulating within the blood vessels for biomedical applications, especially on combating cancer. Here, it is reported for the first time that MAX ceramic biomaterials exhibit unique functionalities for dual‐mode photoacoustic/computed tomography imaging and are highly effective for in vivo photothermal ablation of tumors upon being exfoliated into ultrathin nanosheets within atomic thickness (MXene). As a paradigm, 2D ultrathin tantalum carbide nanosheets (Ta₄C₃ MXenes) with nanosized lateral sizes are successfully synthesized based on a two‐step liquid exfoliation strategy of MAX phase Ta₄AlC₃ by combined hydrofluoric acid (HF) etching and probe sonication. The structural, electronic, and surface characteristics of the as‐exfoliated nanosheets are revealed by various characterizations combined with first‐principles calculations via density functional theory. Especially, the superior photothermal‐conversion performance (efficiency η of 44.7%) and in vitro/in vivo photothermal ablation of tumor by biocompatible soybean phospholipid‐modified Ta₄C₃ nanosheets are systematically revealed and demonstrated. Based on the large family members of MXenes, this work may offer a paradigm that MXenes can achieve the specific biomedical applications (here, theranostic) providing that their compositions and nanostructures are carefully tuned and optimized to meet the strict requirements of biomedicine.     

Synthesis of Crystalline Black Phosphorus Thin Film on Sapphire

Black phosphorus (BP) has recently attracted significant attention due to its exceptional physical properties. Currently, high‐quality few‐layer and thin‐film BP are produced primarily by mechanical exfoliation, limiting their potential in future applications. Here, the synthesis of highly crystalline thin‐film BP on 5 mm sapphire substrates by conversion from red to black phosphorus at 700 °C and 1.5 GPa is demonstrated. The synthesized ≈50 nm thick BP thin films are polycrystalline with a crystal domain size ranging from 40 to 70 µm long, as indicated by Raman mapping and infrared extinction spectroscopy. At room temperature, field‐effect mobility of the synthesized BP thin film is found to be around 160 cm² V^?1 s^?1 along armchair direction and reaches up to about 200 cm² V^?1 s^?1 at around 90 K. Moreover, red phosphorus (RP) covered by exfoliated hexagonal boron nitride (hBN) before conversion shows atomically sharp hBN/BP interface and perfectly layered BP after the conversion. This demonstration represents a critical step toward the future realization of large scale, high‐quality BP devices and circuits.     

Silver‐Laden Black Phosphorus Nanosheets for an Efficient In Vivo Antimicrobial Application

Nanobactericides represent one of the most efficient and promising strategies for eliminating bacterial infection considering the increasing resistance threats of conventional antibiotics. Black phosphorus (BP) is the most exciting postgraphene layered 2D nanomaterial with convincing physiochemical properties, yet the study of BP‐based antibiotics is still in its infancy. Here, a compact silver nanoparticle (AgNP)–doped black phosphorus nanosheet (BPN) is constructed to synergistically enhance solar disinfection through the promoted reactive oxygen species (ROS) photogeneration, which is attributed to the improved electron–hole separation and recombination of BPNs as revealed from the systematic experimental studies. An in‐depth density functional theory (DFT) calculation confirms that the integrated AgNPs provide a preferred site for facilitating the adsorption and activation of O₂, thus promoting the more efficient and robust ROS generation on BPN–AgNP nanohybrids. Besides the enhanced photoinduced ROS, the anchored AgNPs simultaneously lead to a dramatically increased affinity toward bacteria, which facilitates a synergetic pathogen inactivation. Significantly, the convincing antimicrobial BPN–AgNP contributes to the prominent wound healing and antimicrobial ability in vivo with minimized biological burden. This sophisticated design of new 2D nanohybrids opens a new avenue for further exploiting BP‐based nanohybrids in portable bandage and broad‐spectrum disinfection applications.     

Recent Progress in the Preparation,Assembly, Transformation,and Applications of Layer‐Structured Nanodisks beyond Graphene

Layered nanodisks with confined thickness and lateral size have been emerging as a unique type of two‐dimensional (2D) nanomaterials in recent years. Inheriting some properties of 2D nanosheets and meanwhile possessing the size‐confinement effect, these layered nanodisks exhibit unique optical, electronic, and chemical properties, which endow them with great promise in a wide range of applications. Here, the recent progress of layered nanodisks is introduced. The synthetic strategies, assembly, structural/compositional transformation, and applications of layered nanodisks are systematically described and discussed, with emphasis on their new appealing structures and functions. Finally, some perspectives and future research directions of this promising field are given.     

Nanosheets of oxides and hydroxides: Ultimate 2D charge-bearing functional crystallites

A wide variety of cation-exchangeable layered transition metal oxides and their relatively rare counterparts, anion-exchangeable layered hydroxides, have been exfoliated into individual host layers, i.e., nanosheets. Exfoliation is generally achieved via a high degree of swelling, typically driven either by intercalation of bulky organic ions (quaternary ammonium cations, propylammonium cations, etc.) for the layered oxides or by solvation with organic solvents (formamide, butanol, etc.) for the hydroxides. Ultimate two-dimensional (2D) anisotropy for the nanosheets, with thickness of around one nanometer versus lateral size ranging from submicrometer to several tens of micrometers, allows them to serve either as an ideal quantum system for fundamental study or as a basic building block for functional assembly. The charge-bearing inorganic macromolecule-like nanosheets can be assembled or organized through various solution-based processing techniques (e.g., flocculation, electrostatic sequential deposition, or the Langmuir-Blodgett method) to produce a range of nanocomposites, multilayer nanofilms, and core-shell nanoarchitectures, which have great potential for electronic, magnetic, optical, photochemical, and catalytic applications.     

Liquid‐Phase Exfoliated Indium–Selenide Flakes and Their Application in Hydrogen Evolution Reaction

Single‐ and few‐layered InSe flakes are produced by the liquid‐phase exfoliation of β‐InSe single crystals in 2‐propanol, obtaining stable dispersions with a concentration as high as 0.11 g L⁻¹. Ultracentrifugation is used to tune the morphology, i.e., the lateral size and thickness of the as‐produced InSe flakes. It is demonstrated that the obtained InSe flakes have maximum lateral sizes ranging from 30 nm to a few micrometers, and thicknesses ranging from 1 to 20 nm, with a maximum population centered at ≈5 nm, corresponding to 4 Se–In–In–Se quaternary layers. It is also shown that no formation of further InSe‐based compounds (such as In₂Se₃) or oxides occurs during the exfoliation process. The potential of these exfoliated‐InSe few‐layer flakes as a catalyst for the hydrogen evolution reaction (HER) is tested in hybrid single‐walled carbon nanotubes/InSe heterostructures. The dependence of the InSe flakes' morphologies, i.e., surface area and thickness, on the HER performances is highlighted, achieving the best efficiencies with small flakes offering predominant edge effects. The theoretical model unveils the origin of the catalytic efficiency of InSe flakes, and correlates the catalytic activity to the Se vacancies at the edge of the flakes.     

Adhesion of an Ultrasmall Nanoparticle on a Bilayer Membrane is Still Size and Shape Dependent

It has been found recently that an ultrasmall nanoparticle whose size is smaller than the thickness of a cell membrane has unique roles in biomedical applications including the development of next generation of drugs or advanced nanoscale cargo carriers.However,the effect of physical properties of an ultrasmall nanoparticle on its adhesion to a bilayer membrane,which is a key step for Nano-Bio interaction as well as the biomedical applications,is still largely unknown.By using molecular dynamics,we find that both size and shape of an ultrasmall nanoparticle strongly affect its adhesion states on a bilayer membrane(e.g.,adhesion,separation or entwined by polymer chains).Interestingly,our simulations show that with decreasing particle size,the effect of particle shape becomes even more evident for the adhesion behavior.It is indicated that the competition between nanoparticle-polymer binding and polymer chain deformation,both of which are influenced by particle size and shape,determines the final adhesion states of an ultrasmall nanoparticle.Our results are helpful for the full understanding of interaction mechanism between nanoparticles and cell membranes and the practical applications of such ultrasmall nanoparticles.     

Charged Layered Boron Nitride‐Nanoflake Membranes for Efficient Ion Separation and Water Purification

2D layered nanomaterials have attracted considerable attention for their potential for highly efficient separations, among other applications. Here, a 2D lamellar membrane synthesized using hexagonal boron nitride nanoflakes (h‐BNF) for highly efficient ion separation is reported. The ion‐rejection performance and the water permeance of the membrane as a function of the ionic radius, ion valance, and solution pH are investigated. The nonfunctionalized h‐BNF membranes show excellent ion rejection for small sized salt ions as well as for anionic dyes (>97%) while maintaining a high water permeability, ≈1.0 × 10^?3 L m m^?2 h^?1 bar^?1). Experiments show that the ion‐rejection performance of the membrane can be tuned by changing the solution pH. The results also suggest that the rejection is influenced by the ionic size and the electrostatic repulsion between fixed negative charges on the BN surface and the mobile ions, and is consistent with the Donnan equilibrium model. These simple‐to‐fabricate h‐BNF membranes show a unique combination of excellent ion selectivity and high permeability compared to other 2D membranes.     

Near‐Infrared Switchable Fullerene‐Based Synergy Therapy for Alzheimer's Disease

C₆₀ has a special dual function; it can act as both a powerful reactive oxygen species (ROS) producer under UV or visible light and an ROS scavenger in the dark. However, ROS has double‐edged effects in living systems. It is still a great challenge for biomedical application to switch and adjust the two opposite properties of C₆₀ in one system. Herein, UCNP@C₆₀‐pep (UCNP: upconversion nanoparticle, pep: Aβ‐target peptide KLVFF) is designed as a near‐infrared‐switchable nanoplatform for synergy therapy of Alzheimer's disease (AD). Under near‐infrared (NIR) light, the Aβ‐targeting hybrid nanoparticles produce ROS and result in Aβ photooxygenation, which can hinder Aβ aggregation and mitigate the attendant cytotoxicity. In the dark, UCNP@C₆₀‐pep shows protective effects against the increased oxidative stress. The ROS‐generating and ROS‐quenching abilities of UCNP@C₆₀‐pep are both beneficial for decreasing Aβ‐induced neurotoxicity and extending the longevity of the commonly used transgenic AD model Caenorhabditis elegans CL2006. Moreover, UCNP@C60‐pep can also be used for upconversion luminescence (UCL) and magnetic resonance imaging (MRI), which has benefits for “image‐guided therapy.” This study may offer a new perspective for the biological applications of C₆₀.     

Optimizing hemocompatibility of surfactant-coated silver nanoparticles in human erythrocytes

Several recent biological science studies have been focused on nanotechnology and nanomaterials due to their potential use in biomedicine. Drug delivery systems are an example of biomedical applications utilizing nanoparticles. Silver nanoparticles (AgNPs) can be used for these drug delivery systems. However, the effects of cytotoxicity caused by AgNPs are not fully understood. Determining the optimal characteristics to facilitate the biocompatibility of AgNPs is an important subject for application. In the present study, human erythrocytes were used as an in vitro model to examine the size, dose, and coating surfactant-dependent cytotoxicity of AgNPs. Our results demonstrated that polyvinylpyrrolidone (PVP) was a more suitable surfactant than polyethylene glycol (PEG) for AgNPs capping. In addition, we determined the appropriate particular size and dosage of AgNPs to reduce human erythrocytes hemolysis. Membrane damages including hemolysis, potassium efflux, protein leakage, and alterations in cell shape and membrane fragility were minimized with 100-nm AgNP particles. This study provides novel insights into AgNPs cytotoxicity and a basis for utilizing AgNPs for diagnostic and therapeutic applications.     

Tuning the Optical and Electrical Properties of Few‐Layer Black Phosphorus via Physisorption of Small Solvent Molecules

Black phosphorus (BP) is recently becoming more and more popular among semiconducting 2D materials for (opto)electronic applications. The controlled physisorption of molecules on the BP surface is a viable approach to modulate its optical and electronic properties. Solvents consisting of small molecules are often used for washing 2D materials or as liquid media for their chemical functionalization with larger molecules, disregarding their ability to change the opto‐electronic properties of BP. Herein, it is shown that the opto‐electronic properties of mechanically exfoliated few‐layer BP are altered when physically interacting with common solvents. Significantly, charge transport analysis in field‐effect transistors reveals that physisorbed solvent molecules induce a modulation of the charge carrier density which can be as high as 10¹² cm^?2 in BP, i.e., comparable to common dopants such as F₄‐TCNQ and MoO₃. By combining experimental evidences with density functional theory calculations, it is confirmed that BP doping by solvent molecules not only depends on charge transfer, but is also influenced by molecular dipole. The results clearly demonstrate how an exquisite tuning of the opto‐electronic properties of few‐layer BP can be achieved through physisorption of small solvent molecules. Such findings are of interest both for fundamental studies and more technological applications in opto‐electronics.     

Biomedical Applications of Layer‐by‐Layer Assembly: From Biomimetics to Tissue Engineering

The design of advanced, nanostructured materials at the molecular level is of tremendous interest for the scientific and engineering communities because of the broad application of these materials in the biomedical field. Among the available techniques, the layer‐by‐layer assembly method introduced by Decher and co‐workers in 1992 has attracted extensive attention because it possesses extraordinary advantages for biomedical applications: ease of preparation, versatility, capability of incorporating high loadings of different types of biomolecules in the films, fine control over the materials' structure, and robustness of the products under ambient and physiological conditions. In this context, a systematic review of current research on biomedical applications of layer‐by‐layer assembly is presented. The structure and bioactivity of biomolecules in thin films fabricated by layer‐by‐layer assembly are introduced. The applications of layer‐by‐layer assembly in biomimetics, biosensors, drug delivery, protein and cell adhesion, mediation of cellular functions, and implantable materials are addressed. Future developments in the field of biomedical applications of layer‐by‐layer assembly are also discussed.     

Few‐Layered Black Phosphorus: From Fabrication and Customization to Biomedical Applications

As a new kind of 2D material, black phosphorus has gained increased attention in the past three years. Although few‐layered black phosphorus nanosheets (BPs) degrade quickly under ambient conditions to phosphate anions, which greatly hampers their optical and electronic applications, this property also makes BPs highly biocompatible and biodegradable, and is regarded as an advantage for various biomedical applications. This Concept summarizes the state‐of‐art progresses of BPs, from fabrication and surface modification to biomedical applications. It is expected that BPs with such fascinating properties will encourage more scientists to engage in expanding its biomedical applications by tackling the scientific challenges involved in their development.     

Highly Luminescent–Paramagnetic Nanophosphor Probes for In Vitro High‐Contrast Imaging of Human Breast Cancer Cells

Highly luminescent–paramagnetic nanophosphors have a seminal role in biotechnology and biomedical research due to their potential applications in biolabeling, bioimaging, and drug delivery. Herein, the synthesis of high‐quality, ultrafine, europium‐doped yttrium oxide nanophosphors (Y_1.9O₃:Eu_0.1³⁺) using a modified sol–gel technique is reported and in vitro fluorescence imaging studies are demonstrated in human breast cancer cells. These highly luminescent nanophosphors with an average particle size of ≈6 nm provide high‐contrast optical imaging and decreased light scattering. In vitro cellular uptake is shown by fluorescence microscopy, which visualizes the characteristic intense hypersensitive red emission of Eu³⁺ peaking at 610 nm (⁵D₀–⁷F₂) upon 246 nm UV light excitation. No apparent cytotoxicity is observed. Subsequently, time‐resolved emission spectroscopy and SQUID magnetometry measurements demonstrate a photoluminescence decay time in milliseconds and paramagnetic behavior, which assure applications of the nanophosphors in biomedical studies.     

Synthesis of Ultrathin Metallic MTe2 (M = V,Nb, Ta) Single‐Crystalline Nanoplates

Two‐dimensional materials with intrinsic magnetism have recently drawn intense interest for both the fundamental studies and potential technological applications. However, the studies to date have been largely limited to mechanically exfoliated materials. Herein, an atmospheric pressure chemical vapor deposition route to ultrathin group VB metal telluride MTe₂ (M = V, Nb, Ta) nanoplates with thickness as thin as 3 nm is reported. It is shown that the resulting nanoplates can be systematically evolved from mostly thicker hexagonal domains to thinner triangular domains with an increasing flow rate of the carrier gas. X‐ray diffraction and transmission electron microscopy studies reveal MTe₂ (M = V, Nb, Ta) nanoplates are high‐quality single crystals. High‐resolution scanning transmission electron microscope imaging reveals the VTe₂ and NbTe₂ nanoplates adopt the hexagonal 1T phase and the TaTe₂ nanoplates show a monoclinic distorted 1T phase. Electronic transport studies show that MTe₂ single crystals exhibit metallic behavior. Magnetic measurements show that VTe₂ and NbTe₂ exhibit ferromagnetism and TaTe₂ shows paramagnetic behavior. The preparation of ultrathin few‐layered MTe₂ nanoplates will open up exciting opportunities for the burgeoning field of spintronics, sensors, and magneto‐optoelectronics.     

A Poly(lactide) Stereocomplex Structure with Modified Magnesium Oxide and Its Effects in Enhancing the Mechanical Properties and Suppressing Inflammation

Biodegradable polymers such as poly(l ‐lactide) (PLLA) have been widely utilized as materials for biomedical applications. However, the relatively poor mechanical properties of PLLA and its acid‐induced cell inflammation brought about by the acidic byproducts during biodegradation pose severe problems. In this study, these drawbacks of PLLA are addressed using a stereocomplex structure, where oligo‐d ‐lactide‐grafted magnesium hydroxide (MgO‐ODLA) is synthesized by grafting d ‐lactide onto the surface of magnesium hydroxide, which is then blended with a PLLA film. The structure, morphology, pH change, thermal and mechanical properties, in‐vitro cytotoxicity, and inflammation effect of the MgO‐ODLAs and their PLLA composites are evaluated through various analyses. The PLLA/MgO70‐ODLA30 (0–20 wt%) composite with a stereocomplex structure shows a 20% increase in its tensile strength and an improvement in the modulus compared to its oligo‐l ‐lactide (PLLA/MgO70‐OLLA30) counterpart. The interfacial interaction parameter of PLLA/MgO70‐ODLA30 (5.459) has superior properties to those of PLLA/MgO70‐OLLA30 (4.013) and PLLA/Mg(OH)₂ (1.774). The cell cytotoxicity and acid‐induced inflammatory response are suppressed by the neutralizing effect of the MgO‐ODLAs. In addition, the inflammatory problem caused by the rapid acidification of the stereocomplex structure is also addressed. As a result, the stereocomplex structure of the MgO‐ODLA/PLLA composite can be used to overcome the problems associated with the biomedical applications of PLLA films.     

Characterizing the Lateral Friction of Nanoparticles on On‐Chip Integrated Black Lipid Membranes

The use of nanoparticles (NPs) in biomedical applications creates a need for appropriate model systems to systematically investigate NP–membrane interactions under well‐defined conditions. Black lipid membranes (BLMs) are free‐floating membranes with defined composition that are ideally suited for characterizing NP–membrane interactions free of any potential perturbation through a supporting substrate. Herein, arrays of microfabricated BLMs are integrated into a chip‐based platform that is compatible with high‐speed optical NP tracking. This system is used to investigate the lateral diffusion of 40 nm gold spheres tethered to biotinylated lipids through antibody‐functionalized ligands (single‐stranded DNA or polyethylene glycol). Although the NPs show an almost free and ergodic diffusion, their lateral motion is subject to substantial drag at the membrane surface, which leads to systematically smaller diffusion coefficients than those obtained for lipids in the membrane through fluorescence recovery after photobleaching. The lateral mobility of the NPs is influenced by the chemical composition and salt concentration at the NP‐membrane interface, but is independent of the ligand density in the membrane. Together with the observation that nanoprisms, which have a larger relative contact area with the membrane than spherical NPs, show an even slower diffusion, these findings indicate that the lateral mobility of NPs tethered in close vicinity to a membrane is significantly reduced by the friction at the NP‐membrane interface.     

Polysaccharide Nanofiber-Stabilized Pickering Emulsion Microparticles Induce Pyroptotic Cell Death in Hepatocytes and Kupffer Cells

The intracellular uptake and interaction behavior of emulsion microparticles in liver cells critical to host defense and inflammation is significant to understanding their potential cytotoxicity and biomedical applications. In this study, the cell death responses of fibroblastic, hepatocyte, and Kupffer cells (KCs) induced by four types of emulsion particles that are stabilized by polysaccharide nanofibers (cellulose or chitin), an inorganic nanoparticle (β-tricalcium phosphate), or surfactants are compared. Pickering emulsion (PE) microparticles stabilized by polysaccharide nanofibers or inorganic nanoparticles have a droplet size of 1–3 µm, while the surfactant-stabilized emulsion has a diameter of ≈190 nm. Polysaccharide nanofiber-stabilized PEs (PPEs) markedly induce lactate dehydrogenase release in all cell types. Additionally, characteristic pyroptotic cell death, which is accompanied by cell swelling, membrane blebbing, and caspase-1 activation, occurs in hepatocytes and KCs. These PE microparticles are co-cultured with lipopolysaccharide-primed KCs associated with cytokine interleukin-1β release, and the PPEs demonstrate biological activity as a mediator of the inflammation response. Well-designed PPE microparticles induce pyroptosis of liver cells, which may provide new insight into regulating inflammation-related diseases for designing potent anticancer drugs and vaccine adjuvants.     

Invasion and Defense Interactions between Enzyme‐Active Liquid Coacervate Protocells and Living Cells

The design and construction of mutual interaction models between artificial microsystems and living cells have the potential to open a wide range of novel applications in biomedical and biomimetic technologies. In this study, an artificial form of invasion‐defense mutual interactions is established in a community of glucose oxidase (GOx)‐containing liquid coacervate microdroplets and living cells, which interact via enzyme‐mediated reactive oxygen species (ROS) damage. The enzyme‐containing coacervate microdroplets, formed via liquid–liquid phase separation, act as invader protocells to electrostatically bind with the host HepG2 cell, resulting in assimilation. Subsequently, the glucose oxidation in the liquid coacervates initiates the generation of H₂O₂, which serves as an ROS resource to block cell proliferation. As a defense strategy, introduction of catalase (CAT) into the host cells is exploited to resist the ROS damage. CAT‐mediated decomposition of H₂O₂ leads to the ROS scavenging and results in the recovery of cell viability. The results obtained in the current study highlight the remarkable opportunities for the development of mutual interacting communities on the interface of artificial protocells/living cells. They also provide a new approach for engineering cellular behaviors through exploiting artificial nonliving microsystems.