4-Ethylphenyl Sulfate Detection by an Electrochemical Sensor Based on a MoS2 Nanosheet-Modified Molecularly Imprinted Biopolymer.

One of the gut-derived uremic toxins 4-ethylphenyl sulfate (4-EPS) exhibits significantly elevated plasma levels in chronic kidney diseases and autism, and its early quantification in bodily fluids is important. Therefore, the development of rapid and sensitive technologies for 4-EPS detection is of significant importance for clinical diagnosis. In the current work, the synthesis of a molecularly imprinted biopolymer (MIBP) carrying 4-EPS specific cavities only using the biopolymer polydopamine (PDA) and molybdenum disulfide (MoS2) nanosheets has been reported. The fabricated electrode was prepared using screen-printed carbon electrodes on a polyvinyl chloride substrate. The synthesized material was characterized using several techniques, and electrochemical studies were performed using cyclic voltammetry (CV) and differential pulse voltammetry (DPV) techniques. The DPV technique for the electrochemical sensing of 4-EPS using the fabricated sensor (PDA@MoS2-MIBP) determined a sensitivity of 0.012 µA/ng mL/cm2 and a limit of detection of 30 ng/mL in a broad linear range of 1-2200 ng/mL. Also, the interferent study was performed to evaluate the selectivity of the fabricated sensor along with the control and stability study. Moreover, the performance of the sensor was evaluated in the spiked urine sample, and a comparison was made with the data obtained by ultraperformance liquid chromatography-tandem mass spectroscopy.

2D MoB MBene: An Efficient Co-Catalyst for Photocatalytic Hydrogen Production under Visible Light.

Highly active and low-cost co-catalysts have a positive effect on the enhancement of solar H2 production. Here, we employ two-dimensional (2D) MBene as a noble-metal-free co-catalyst to boost semiconductor for photocatalytic H2 production. MoB MBene is a 2D nanoboride, which is directly made from MoAlB by a facile hydrothermal etching and manual scraping off process. The as-synthesized MoB MBene with purity >95 wt % is treated by ultrasonic cell pulverization to obtain ultrathin 2D MoB MBene nanosheets (∼0.61 nm) and integrated with CdS via an electrostatic interaction strategy. The CdS/MoB composites exhibit an ultrahigh photocatalytic H2 production activity of 16,892 µmol g-1 h-1 under visible light, surpassing that of pure CdS by an exciting factor of ≈1135%. Theoretical calculations and various measurements account for the high performance in terms of Gibbs free energy, work functions, and photoelectrochemical properties. This work discovers the huge potential of these promising 2D MBene family materials as high-efficiency and low-cost co-catalysts for photocatalytic H2 production.

Recent Progress in Two-Dimensional Nanomaterials for Flame Retardance and Fire-Warning Applications.

Graphene-like 2D nanomaterials, such as graphene, MXene, molybdenum disulfide, and boron nitride, present a promising avenue for eco-friendly flame retardants. Their inherent characteristics, including metal-like conductivity, high specific surface area, electron transport capacity, and solution processability, make them highly suitable for applications in both structural fire protection and fire alarm systems. This review offers an up-to-date exploration of advancements in flame retardant composites, utilizing pristine graphene-like nanosheets, versatile graphene-like nanosheets with multiple functions, and collaborative systems based on these nanomaterials. Moreover, graphene-like 2D nanomaterials exhibit considerable potential in the development of early fire alarm systems, enabling timely warnings. This review provides an overview of flame-retarding and fire-warning mechanisms, diverse multifunctional nanocomposites, and the evolving trends in the development of fire alarm systems anchored in graphene-like 2D nanomaterials and their derivatives. Ultimately, the existing challenges and prospective directions for the utilization of graphene-like 2D nanomaterials in flame retardant and fire-warning applications are put forward.

Harnessing two-dimensional nanomaterials for diagnosis and therapy in neurodegenerative diseases: Advances, challenges and prospects.

Neurodegenerative diseases (NDDs) are specific brain disorders characterized by the progressive deterioration of different motor activities as well as several cognitive functions. Current conventional therapeutic options for NDDs are limited in addressing underlying causes, delivering drugs to specific neuronal targets, and promoting tissue repair following brain injury. Due to the paucity of plausible theranostic options for NDDs, nanobiotechnology has emerged as a promising field, offering an interdisciplinary approach to create nanomaterials with high diagnostic and therapeutic efficacy for these diseases. Recently, two-dimensional nanomaterials (2D-NMs) have gained significant attention in biomedical and pharmaceutical applications due to their precise drug-loading capabilities, controlled release mechanisms, enhanced stability, improved biodegradability, and reduced cell toxicity. Although various studies have explored the diagnostic and therapeutic potential of different nanomaterials in NDDs, there is a lack of comprehensive review addressing the theranostic applications of 2D-NMs in these neuronal disorders. Therefore, this concise review aims to provide a state-of-the-art understanding of the need for these ultrathin 2D-NMs and their potential applications in biosensing and bioimaging, targeted drug delivery, tissue engineering, and regenerative medicine for NDDs.

Magnetoresistance properties in nickel-catalyzed, air-stable, uniform, and transfer-free graphene.

A transfer-free graphene with high magnetoresistance (MR) and air stability has been synthesized using nickel-catalyzed atmospheric pressure chemical vapor deposition. The Raman spectrum and Raman mapping reveal the monolayer structure of the transfer-free graphene, which has low defect density, high uniformity, and high coverage (>90%). The temperature-dependent (from 5 to 300 K) current-voltage (I-V) and resistance measurements are performed, showing the semiconductor properties of the transfer-free graphene. Moreover, the MR of the transfer-free graphene has been measured over a wide temperature range (5-300 K) under a magnetic field of 0 to 1 T. As a result of the Lorentz force dominating above 30 K, the transfer-free graphene exhibits positive MR values, reaching ∼8.7% at 300 K under a magnetic field (1 Tesla). On the other hand, MR values are negative below 30 K due to the predominance of the weak localization effect. Furthermore, the temperature-dependent MR values of transfer-free graphene are almost identical with and without a vacuum annealing process, indicating that there are low density of defects and impurities after graphene fabrication processes so as to apply in air-stable sensor applications. This study opens avenues to develop 2D nanomaterial-based sensors for commercial applications in future devices.

Interaction of 2D nanomaterial with cellular barrier: Membrane attachment and intracellular trafficking.

The cell membrane serves as a barrier against the free entry of foreign substances into the cell. Limited by factors such as solubility and targeting, it is difficult for some drugs to pass through the cell membrane barrier and exert the expected therapeutic effect. Two-dimensional nanomaterial (2D NM) has the advantages of high drug loading capacity, flexible modification, and multimodal combination therapy, making them a novel drug delivery vehicle for drug membrane attachment and intracellular transport. By modulating the surface properties of nanocarriers, it is capable of carrying drugs to break through the cell membrane barrier and achieve precise treatment. In this review, we review the classification of various common 2D NMs, the primary parameters affecting their adhesion to cell membranes, and the uptake mechanisms of intracellular transport. Furthermore, we discuss the therapeutic potential of 2D NMs for several major disorders. We anticipate this review will deepen researchers' understanding of the interaction of 2D NM drug carriers with cell membrane barriers, and provide insights for the subsequent development of novel intelligent nanomaterials capable of intracellular transport.

Synthesis and Prospects of Holey Two-dimensional Platinum-group Metals in Electrocatalysis.

Advanced electrocatalysts can enable the widespread implementation of clean energy technologies. This paper reviews an emerging class of electrocatalytic materials comprising holey two-dimensional free-standing Pt-group metal (h-2D-PGM) nanosheets, which are categorically challenging to synthesize but inherently rich in all the qualities necessary to counter the kinetic and thermodynamic challenges of an electrochemical conversion process with high catalytic efficiency and stability. Although the 2D anisotropic growth of typical nonlayered metal crystals has succeeded and partly improved their atom-utilization efficiency, regularly distributed in-planar porosity can further optimize three critical factors that govern efficient electrocatalysis process: mass diffusion, electron transfer, and surface reactivity. However, producing such advanced morphological features within h-2D-PGMs is difficult unless they are specially engineered using approaches such as templating or kinetic ramification during 2D growth or controlled etching of preformed 2D-PGM solids. Therefore, this review highlighting the successful fabrication of various porous PGM nanosheets and their electrocatalytic benefits involving smart nanoscale features could inspire next-generation scientific and technological innovations toward securing a sustainable energy future.

Low Temperature Chemoresistive Oxygen Sensors Based on Titanium-Containing Ti2CTx and Ti3C2Tx MXenes.

The chemoresistive properties of multilayer titanium-containing Ti2CTx and Ti3C2Tx MXenes, synthesized by etching the corresponding MAX phases with NaF solution in hydrochloric acid, and the composites based on them, obtained by partial oxidation directly in a sensor cell in an air flow at 150 °C, were studied. Significant differences were observed for the initial MXenes, both in microstructure and in the composition of surface functional groups, as well as in gas sensitivity. For single Ti2CTx and Ti3C2Tx MXenes, significant responses to oxygen and ammonia were observed. For their partial oxidation at a moderate temperature of 150 °C, a high humidity sensitivity (T, RH = 55%) is observed for Ti2CTx and a high and selective response to oxygen for Ti3C2Tx at 125 °C (RH = 0%). Overall, these titanium-containing MXenes and composites based on them are considered promising as receptor materials for low temperature oxygen sensors.

Nanobio Interface Between Proteins and 2D Nanomaterials.

Two-dimensional (2D) nanomaterials have significantly contributed to recent advances in material sciences and nanotechnology, owing to their layered structure. Despite their potential as multifunctional theranostic agents, the biomedical translation of these materials is limited due to a lack of knowledge and control over their interaction with complex biological systems. In a biological microenvironment, the high surface energy of nanomaterials leads to diverse interactions with biological moieties such as proteins, which play a crucial role in unique physiological processes. These interactions can alter the size, surface charge, shape, and interfacial composition of the nanomaterial, ultimately affecting its biological activity and identity. This review critically discusses the possible interactions between proteins and 2D nanomaterials, along with a wide spectrum of analytical techniques that can be used to study and characterize such interplay. A better understanding of these interactions would help circumvent potential risks and provide guidance toward the safer design of 2D nanomaterials as a platform technology for various biomedical applications.

Ultrastrong yet Ductile 2D Titanium Nanomaterial for On-Skin Conformal Triboelectric Sensing.

Conventional titanium (e.g., bulk or thin films) is well-known for its relatively high mechanical strength, excellent corrosion resistance, and superior biocompatibility, which are suitable for biomedical engineering and wearable devices. However, the strength of conventional titanium often trades off its ductility, and their use in wearable devices has not been explored yet. In this work, we fabricated a series of large-sized 2D titanium nanomaterials with the method of polymer surface buckling enabled exfoliation (PSBEE), which possess a unique heterogeneous nanostructure containing nanosized titanium, titanium oxide, and MXene-like phases. As a result, these 2D titaniums exhibit both superb mechanical strength (6-13 GPa) and remarkable ductility (25-35%) at room temperature, outperforming all other titanium-based materials reported so far. More interestingly, we demonstrate that the 2D titanium nanomaterials also showed good performance in triboelectric sensing and can be used to fabricate self-powered, on-skin conformal triboelectric sensors with good mechanical reliability.

Layered Double Hydroxides: A Novel Promising 2D Nanomaterial for Bone Diseases Treatment.

Bone diseases including bone defects, bone infections, osteoarthritis, and bone tumors seriously affect life quality of the patient and bring serious economic burdens to social health management, for which the current clinical treatments bear dissatisfactory therapeutic effects. Biomaterial-based strategies have been widely applied in the treatment of orthopedic diseases but are still plagued by deficient bioreactivity. With the development of nanotechnology, layered double hydroxides (LDHs) with adjustable metal ion composition and alterable interlayer structure possessing charming physicochemical characteristics, versatile bioactive properties, and excellent drug loading and delivery capabilities arise widespread attention and have achieved considerable achievements for bone disease treatment in the last decade. However, to the authors' best knowledge, no review has comprehensively summarized the advances of LDHs in treating bone disease so far. Herein, the advantages of LDHs for orthopedic disorders treatment are outlined and the corresponding state-of-the-art achievements are summarized for the first time. The potential of LDHs-based nanocomposites for extended therapeutics for bone diseases is highlighted and perspectives for LDHs-based scaffold design are proposed for facilitated clinical translation.

Harmonious Heterointerfaces Formed on 2D-Pt Nanodendrites by Facet-Respective Stepwise Metal Deposition for Enhanced Hydrogen Evolution Reaction.

The performance of nanocrystal (NC) catalysts could be maximized by introducing rationally designed heterointerfaces formed by the facet- and spatio-specific modification with other materials of desired size and thickness. However, such heterointerfaces are limited in scope and synthetically challenging. Herein, we applied a wet chemistry method to tunably deposit Pd and Ni on the available surfaces of porous 2D-Pt nanodendrites (NDs). Using 2D silica nanoreactors to house the 2D-PtND, an 0.5-nm-thick epitaxial Pd or Ni layer (e-Pd or e-Ni) was exclusively formed on the flat {110} surface of 2D-Pt, while a non-epitaxial Pd or Ni layer (n-Pd or n-Ni) was typically deposited at the {111/100} edge in absence of nanoreactor. Notably, these differently located Pd/Pt and Ni/Pt heterointerfaces experienced distinct electronic effect to influence unequally in electrocatalytic synergy for hydrogen evolution reaction (HER). For instance, an enhanced H2 generation on the Pt{110} facet with 2D-2D interfaced e-Pd deposition and faster water dissociation on the edge-located n-Ni overpowered their facet-located counterparts in respective HER catalysis. Therefore, a feasible assembling of the valuable heterointerfaces in the optimal 2D n-Ni/e-Pd/Pt catalyst overcame the sluggish alkaline HER kinetics, with a catalytic activity 7.9 times higher than that of commercial Pt/C.

Development of Two-Dimensional Functional Nanomaterials for Biosensor Applications: Opportunities, Challenges, and Future Prospects.

New possibilities for the development of biosensors that are ready to be implemented in the field have emerged thanks to the recent progress of functional nanomaterials and the careful engineering of nanostructures. Two-dimensional (2D) nanomaterials have exceptional physical, chemical, highly anisotropic, chemically active, and mechanical capabilities due to their ultra-thin structures. The diversity of the high surface area, layered topologies, and porosity found in 2D nanomaterials makes them amenable to being engineered with surface characteristics that make it possible for targeted identification. By integrating the distinctive features of several varieties of nanostructures and employing them as scaffolds for bimolecular assemblies, biosensing platforms with improved reliability, selectivity, and sensitivity for the identification of a plethora of analytes can be developed. In this review, we compile a number of approaches to using 2D nanomaterials for biomolecule detection. Subsequently, we summarize the advantages and disadvantages of using 2D nanomaterials in biosensing. Finally, both the opportunities and the challenges that exist within this potentially fruitful subject are discussed. This review will assist readers in understanding the synthesis of 2D nanomaterials, their alteration by enzymes and composite materials, and the implementation of 2D material-based biosensors for efficient bioanalysis and disease diagnosis.

Effects of industrially produced 2-dimensional molybdenum disulfide materials in primary human basophils.

MoS2 has been increasingly used in place of graphene as a flexible and multifunctional 2D material in many biomedical applications such as cancer detection and drug delivery, which makes it crucial to evaluate downstream compatibility in human immune cells. Molybdenum is a component of stainless-steel stent implants and has previously been implicated in stent hypersensitivity. In view of this, it is important to ascertain the effect of MoS2 on allergy-relevant cells. Basophils are a less commonly used immune cell type. Unlike mast cells, basophils can be easily derived from primary human blood and can act as a sentinel for allergy. However, merely testing any one type of MoS2 in basophils could result in different biological results. We thus decided to compare 2D MoS2 from the two companies BeDimensional© (BD) and Biograph Solutions (BS), manufactured with two different but commonly exploited methods (BD, deoxycholate surfactant in a high-pressure liquid exfoliation, and BS using glycine in ball-milling exfoliation) to elucidate immunological end-points common to both MoS2 and to demonstrate the need for biological verification for end-users who may require a change of supplier. We report higher histamine production in human basophils with MoS2. No effects on either surface basophil activation markers CD63 and CD203c or reactive oxygen species (ROS) production and cell viability were observed. However, different cytokine production patterns were evidenced. IL-6 and IL-1ß but not TNF and GM-CSF were increased for both MoS2. BS-MoS2 increased IL-4, while BD-MoS2 decreased IL-4 and increased IL-13. Molybdate ion itself only increased IL-1ß and IL-4. Deoxycholate surfactant decreased viability at 18 h and increased ROS upon basophil activation. Therefore, these results demonstrate the safety of MoS2 in human basophils in general and highlight the importance of considering manufacturer additives and variability when selecting and investigating 2D materials such as MoS2.

Molecular mechanisms of integrin αvß8 activation regulated by graphene, boron nitride and black phosphorus nanosheets.

Integrin αvß8 is a heterodimeric transmembrane protein on macrophages. Nanosheets can activate the integrin and elicit immune responses, exhibiting adverse immunotoxicity. Understanding the mechanism of integrin activation regulated by nanosheets is crucial for safe and effective use of nanosheets in biomedical applications. Herein, we performed all-atom molecular dynamics simulations to clarify the interactions between integrin αvß8 in the cell membrane and three types of nanosheets, graphene (GRA), hexagonal boron nitride (BN), and black phosphorus (BP). We observed that BP could adsorb the intracellular end of αv monomer and thus break the inner membrane clasp, an important hydrophobic cluster for maintaining the inactive state of integrin. The association between αv and ß8 subunit is weakened, promoting the integrin activation. By contrast, GRA and BN exert little influence on the association state of the integrin. Interestingly, the puckered structure of BP affects the integrin activation, where BP with the armchair direction perpendicular to the membrane plane cannot unpack the integrin. Moreover, the perturbation effect of nanosheets on the membrane was also evaluated. BP shows a milder effect on membrane structures and lipid properties than GRA and BN. This work unravels the molecular basis on the activation of integrin mediated by three nanosheets, and suggests the toxicity and therapeutic effect of well-established nanomaterials in the immune system.

Size-dependent molecular interaction of nontraditional 2D antibiotics withStaphylococcus aureus.

The application of nanomaterials for their antibacterial properties is the subject of many studies due to antibiotic resistance of pathogen bacteria and the necessity of omitting them from food and water resources. Graphene oxide (GO) is one of the most popular candidates for antibacterial application. However, the optimum condition for such an effect is not yet clear for practical purposes. To shed light on how GO and bacteria interaction depends on size, a wide range of GO flake sizes from hundreds of µm2going down to nano-scale as low as 10 N m2was produced. In anin-vitrosystematic study to inhibitStaphylococcus aureusgrowth, the correlation between GO flake size, thickness, functional group density, and antibacterial activity was investigated. The GO suspension with the average size of 0.05 µm2, in the order of the size of the bacteria itself, had the best bacteriostatic effect onS. aureuswith the minimum inhibitory concentration value of 8 µg ml-1, well within the acceptable range for practical use. The bacteriostatic effect was measured to be a 76.2% reduction of the colony count over 2 h of incubation and the mechanism of action was the wrapping and isolation of cells from the growth environment. Furthermore,in-vivoanimal studies revealed that 16 µg ml-1of the optimum GO has efficient antibacterial performance against the methicillin-resistant strains of the bacteria with an enhanced wound healing rate and tensiometrial parameters which is important for realized targets.

Nanocrystal Conversion Chemistry within Slit-like 2D Nanogap for High-Rate Cyclic Stability of Lithium-Ion Battery Anodes.

Nanoscale optimization of late transition-metal oxides for fixing the reversible lithiation/delithiation mechanism with an in-depth mechanistic understanding of nanocrystal (NC) conversion chemistry is important for furthering next-generation Li-ion battery (LIB) technologies. Herein, 1 nm-thin Ni3CoOx (1 nm-NCO) nanosheets synthesized through isomorphic transformation of NiCo layered double hydroxides within a two-dimensional (2D)-SiO2 envelope are chosen. The interconversion of metal/metal-oxide NCs under redox-switching thermal treatment, while retaining reversibility, inspired the accomplishment of identical consequences under the harsh operational conditions of LIB redox cycles by application of the thin-NCO-defined 2D nanospace. During charge/discharge cycles, 1 nm-NCO covered with an in situ formed solid-electrolyte-interphase layer enables fully reversible interconversion between the reactive NC redox pairs, as evidenced by detailed morphological and electrochemical analyses, thus providing high-rate capability with a specific capacity of 61.2% at 5.0 C relative to 0.2 C, outstanding cycle stability delivering a reversible capacity of 1169 mAh g-1, and 913 mAh g-1 with high average Coulombic efficiency (>99.2%) at 3.0 and 5.0 C for 1000 cycles, respectively, which has not been achieved with other transition-metal oxides. Such a nanospace-confinement effect on sustainability of reactive NCs to follow-up a highly reversible conversion reaction at fast charging in LIBs is operative within a slit-like ultrathin 2D nanogap from 1 nm-NCO only, as a relatively thicker 7 nm-NCO anode, with accompanying larger space available, has evidenced poor reversibility of NCs and inadequate cyclic stability under potential high-power density LIB application.

MXene as a novel cartridge for N-glycan enrichment.

In this study, we applied MXene as column cartridge for N-glycan enrichment from human samples with a focus on the analysis of sialic acid linkages using a derivatisation protocol followed by glycan analysis via Matrix Assisted Laser Desorption Ionisation-Time Of Flight Mass Spectrometry (MALDI-TOF-MS). The MXene-based cartridge enriches a higher number of glycans (i.e., sialylated and bisecting N-glycans) when compared to the commercial HILIC columns. We demonstrate the strong potential of MXene as a stationary phase in MS glycomic analysis.

2D Nano-Mica Sheets Assembled Membranes for High-Efficiency Oil/Water Separation.

Oil-polluted water has become one of the most important environmental concerns nowadays due to the increasing industrial oily wastewater and frequent oil spill accidents. Herein, a novel two-dimensional (2D) nano-mica sheets assembled composite membrane with underwater super-oleophobic properties was developed for effective oil/water separation. A 2D nano-mica sheet was synthesized by a facile solvent-assisted ultrasonic exfoliation and then the obtained 2D nano-mica sheets were co-deposited with dopamine on polyvinylidene fluoride substrate to prepare nano-mica composite membranes (NCM). The NCM is hydrophilic in air and super-oleophobic underwater (the water contact angle in the air is 37.6°, and the oil contact angle in water is 151.4°). Furthermore, the prepared NCM provided outstanding stability in different acid-base environments (pH = 1-11). Noteworthily, the oil removal rate is higher than 99.5% as the sodium dodecyl sulfate SDS-stabilized oil (soya-bean oil, mineral oil and pump oil) -in-water emulsions. Meanwhile, the NCM showed excellent reusability, as the oil removal efficiency kept at 99.0% after ten soya-bean oil-in-water or mineral oil-in-water emulsion filtration cycles. The present work paved a new way for developing a low-cost and environmentally friendly strategy for oily wastewater treatment and developed a high-increment utilization application field for natural minerals.

Using Green, Economical, Efficient Two-Dimensional (2D) Talc Nanosheets as Lubricant Additives under Harsh Conditions.

Two-dimensional (2D) nanomaterials have attracted much attention for lubrication enhancement of grease. It is difficult to disperse nanosheets in viscous grease and the lubrication performances of grease under harsh conditions urgently need to be improved. In this study, the 2D talc nanosheets are modified by a silane coupling agent with the assistance of high-energy ball milling, which can stably disperse in grease. The thickness and size of the talc nanosheet are about 20 nm and 2 µm. The silane coupling agent is successfully grafted on the surface of talc. Using the modified-talc nanosheet, the coefficient of friction and wear depth can be reduced by 40% and 66% under high temperature (150 °C) and high load (3.5 GPa), respectively. The enhancement of the lubrication and anti-wear performance is attributed to the boundary adsorbed tribofilm of talc achieving a repairing effect of the friction interfaces, the repairing effect of talc on the friction interfaces. This work provides green, economical guidance for developing natural lubricant additives and has great potential in sustainable lubrication.