Modeling Interactions between Liposomes and Hydrophobic Nanosheets

2D nanomaterials could cause structural disruption and cytotoxic effects to cells, which greatly challenges their promising biomedical applications including biosensing, bioimaging, and drug delivery. Here, the physical and mechanical interaction between lipid liposomes and hydrophobic nanosheets is studied utilizing coarse‐grained (CG) molecular dynamics (MD) simulations. The simulations reveal a variety of characteristic interaction morphologies that depend on the size and the orientation of nanosheets. Dynamic and thermodynamic analyses on the morphologic evolution provide insights into molecular motions such as “nanosheet rotation,” “lipid extraction,” “lipid flip‐flop,” and “lipid spreading.” Driven by these molecular motions, hydrophobic nanosheets cause morphologic changes of liposomes. The lipid bilayer structure can be corrugated, and the overall liposome sphere can be split or collapsed by large nanosheets. In addition, nanosheets embedded into lipid bilayers greatly weaken the fluidity of lipids, and this effect can be cumulatively enhanced as nanosheets continuously intrude. These results could facilitate molecular‐level understanding on the cytotoxicity of nanomaterials, and help future nanotoxicology studies associating computational modeling with experiments.     

Morphology Tunable Hybrid Carbon Nanosheets with Solvatochromism

The tunable photoluminescence of carbon‐based nanomaterials has received much attention for a wide range of applications. Herein, a unique, broad‐solvatochromic hybrid carbon nanosheet (CNS) synthesized through the hydrothermal carbonization of molecular precursors exploiting graphene oxide as a template is reported, resulting in the formation of clusters of carbon nanorings on the surface of graphene‐oxide nanosheets. Under UV and visible‐light excitation, the hybrid CNS exhibits tunable emission spanning the wide range of colors in a series of solvents with different polarities. This interesting spectroscopic behavior is found to originate from hydrogen‐bonding interactions between CNS and solvents, which eventually induce the morphological transition of CNS from 2D sheets to 3D crumpled morphologies, affecting the lifetimes of emissive states. This novel soft carbon nanostructure may open up a new possibility in tailoring the photophysical properties of carbon nanomaterials.     

Fast Gelation of Ti3C2Tx MXene Initiated by Metal Ions

Gelation is an effective way to realize the self‐assembly of nanomaterials into different macrostructures, and in a typical use, the gelation of graphene oxide (GO) produces various graphene‐based carbon materials with different applications. However, the gelation of MXenes, another important type of 2D materials that have different surface chemistry from GO, is difficult to achieve. Here, the first gelation of MXenes in an aqueous dispersion that is initiated by divalent metal ions is reported, where the strong interaction between these ions and ? OH groups on the MXene surface plays a key role. Typically, Fe²⁺ ions are introduced in the MXene dispersion which destroys the electrostatic repulsion force between the MXene nanosheets in the dispersion and acts as linkers to bond the nanosheets together, forming a 3D MXene network. The obtained hydrogel effectively avoids the restacking of the MXene nanosheets and greatly improves their surface utilization, resulting in a high rate performance when used as a supercapacitor electrode (≈226 F g^?1 at 1 V s^?1). It is believed that the gelation of MXenes indicates a new way to build various tunable MXene‐based structures and develop different applications.     

2D Nanomaterials for Cancer Theranostic Applications

2D nanomaterials with unique nanosheet structures, large surface areas, and extraordinary physicochemical properties have attracted tremendous interest. In the area of nanomedicine, research on graphene and its derivatives for diverse biomedical applications began as early as 2008. Since then, many other types of 2D nanomaterials, including transition metal dichalcogenides, transition metal carbides, nitrides and carbonitrides, black phosphorus nanosheets, layered double hydroxides, and metal–organic framework nanosheets, have been explored in the area of nanomedicine over the past decade. In particular, a large surface area makes 2D nanomaterials highly efficient drug delivery nanoplatforms. The unique optical and/or X-ray attenuation properties of 2D nanomaterials can be harnessed for phototherapy or radiotherapy of cancer. Furthermore, by integrating 2D nanomaterials with other functional nanoparticles or utilizing their inherent physical properties, 2D nanomaterials may also be engineered as nanoprobes for multimodal imaging of tumors. 2D nanomaterials have shown substantial potential for cancer theranostics. Herein, the latest progress in the development of 2D nanomaterials for cancer theranostic applications is summarized. Current challenges and future perspectives of 2D nanomaterials applied in nanomedicine are also discussed.     

Two-dimensional dielectric nanosheets: novel nanoelectronics from nanocrystal building blocks

Two-dimensional (2D) nanosheets, which possess atomic or molecular thickness and infinite planar lengths, are regarded as the thinnest functional nanomaterials. The recent development of methods for manipulating graphene (carbon nanosheet) has provided new possibilities and applications for 2D systems; many amazing functionalities such as high electron mobility and quantum Hall effects have been discovered. However, graphene is a conductor, and electronic technology also requires insulators, which are essential for many devices such as memories, capacitors, and gate dielectrics. Along with graphene, inorganic nanosheets have thus increasingly attracted fundamental research interest because they have the potential to be used as dielectric alternatives in next-generation nanoelectronics. Here, we review the progress made in the properties of dielectric nanosheets, highlighting emerging functionalities in electronic applications. We also present a perspective on the advantages offered by this class of materials for future nanoelectronics.     

Effect of graphene oxide nanosheets on the physico-mechanical properties of chitosan/bacterial cellulose nanofibrous composites

In this work, novel chitosan/bacterial cellulose (CS/BC) nanofibrous composites reinforced with graphene oxide (GO) nanosheets are introduced. As cell attachment and permeability of nanofibrous membranes highly depend on their fiber diameter, the working window for successful electrospinning to attain sound nanofibrous composites with a minimum fiber diameter was determined by using the response surface methodology. It is shown that the addition of GO nanosheets to CS/BC significantly reduces the average size of the polymeric fibers. Their mechanical properties are also influenced and can be tailored by the concentration of GO. Fourier transform infrared spectroscopy reveals hydrogen bonding between the GO nanosheets and the polymer matrix. A decrease in the hydrophilicity of the electrospun nanofibers and their water vapor permeability with the addition of GO are also reported. The prepared nanofibrous composites are potentially suitable candidates for biomedical applications such as skin tissue engineering and wound dressing.     

Surface Coating‐Dependent Cytotoxicity and Degradation of Graphene Derivatives: Towards the Design of Non‐Toxic,Degradable Nano‐Graphene

With the increasing interests of using graphene and its derivatives in the area of biomedicine, the systematic evaluation of their potential risks and impacts to biological systems is becoming critically important. In this work, we carefully study how surface coatings affect the cytotoxicity and extracellular biodegradation behaviors of graphene oxide (GO) and its derivatives. Although naked GO could induce significant toxicity to macrophages, coating those two‐dimensional nanomaterials with biocompatible macromolecules such as polyethylene glycol (PEG) or bovine serum albumin (BSA) could greatly attenuate their toxicity, as independently evidenced by several different assay approaches. On the other hand, although GO can be gradually degraded through enzyme induced oxidization by horseradish peroxidase (HRP), both PEG and BSA coated GO or reduced GO (RGO) are rather resistant to HRP‐induced biodegradation. In order to obtain biocompatible functionalized GO that can still undergo enzymatic degradation, we conjugate PEG to GO via a cleavable disulfide bond, obtaining GO‐SS‐PEG with negligible toxicity and considerable degradability, promising for further biomedical applications.     

An Increase in Membrane Cholesterol by Graphene Oxide Disrupts Calcium Homeostasis in Primary Astrocytes

The use of graphene nanomaterials (GNMs) for biomedical applications targeted to the central nervous system is exponentially increasing, although precise information on their effects on brain cells is lacking. In this work, the molecular changes induced in cortical astrocytes by few‐layer graphene (FLG) and graphene oxide (GO) flakes are addressed. The results show that exposure to FLG/GO does not affect cell viability or proliferation. However, proteomic and lipidomic analyses unveil alterations in several cellular processes, including intracellular Ca²⁺ ([Ca²⁺]_i) homeostasis and cholesterol metabolism, which are particularly intense in cells exposed to GO. Indeed, GO exposure impairs spontaneous and evoked astrocyte [Ca²⁺]_i signals and induces a marked increase in membrane cholesterol levels. Importantly, cholesterol depletion fully rescues [Ca²⁺]_i dynamics in GO‐treated cells, indicating a causal relationship between these GO‐mediated effects. The results indicate that exposure to GNMs alters intracellular signaling in astrocytes and may impact astrocyte–neuron interactions.     

Simple photoreduction of graphene oxide nanosheet under mild conditions

Graphene oxide (GO) nanosheets were reduced by UV irradiation in H2 or N2 under mild conditions (at room temperature) without a photocatalyst. Photoreduction proceeded even in an aqueous suspension of nanosheets. The GO nanosheets reduced by this method were analyzed by X-ray photoelectron spectroscopy and Raman spectroscopy. It was found that epoxy groups attached to the interiors of aromatic domains of the GO nanosheet were destroyed during UV irradiation to form relatively large sp2 islands resulting in a high conductivity. I-V curves were measured by conductive atomic force microscopy (AFM; perpendicular to a single nanosheet) and a two-electrode system (parallel to the nanosheet). They revealed that photoreduced GO nanosheets have high conductivities, whereas nonreduced GO nanosheets are nearly insulating. Ag+ adsorbed on GO nanosheets promoted the photoreduction. This photoreduction method was very useful for photopatterning a conducting section of micrometer size on insulating GO. The developed photoreduction process based on a photoreaction will extend the applications of GO to many fields because it can be performed in mild conditions without a photocatalyst.     

多维度纳米增强水泥基复合材料的研究进展

纳米材料领域的飞速发展为水泥基复合材料的增强改性提供了宝贵的机会。工程纳米材料存在3种主要形状,即0维纳米颗粒、1维纳米纤维和2维纳米片层。有大量文献已经报道了0维纳米颗粒和1维纳米纤维(如纳米二氧化硅和碳纳米管)在水泥基中的应用,而2维纳米片层状的氧化石墨烯(GO)的发现为水泥基复合材料提供了又一种维度的增强方式,目前已经受到了越来越广泛的关注。综述了近期各种维度纳米改性水泥基复合材料的研究进展,并总结了纳米材料与水泥基复合材料复合后的工作性、水化反应、力学性能及微观结构。     

Minimizing oxidation and stable nanoscale dispersion improves the biocompatibility of graphene in the lung

To facilitate the proposed use of graphene and its derivative graphene oxide (GO) in widespread applications, we explored strategies that improve the biocompatibility of graphene nanomaterials in the lung. In particular, solutions of aggregated graphene, Pluronic dispersed graphene, and GO were administered directly into the lungs of mice. The introduction of GO resulted in severe and persistent lung injury. Furthermore, in cells GO increased the rate of mitochondrial respiration and the generation of reactive oxygen species, activating inflammatory and apoptotic pathways. In contrast, this toxicity was significantly reduced in the case of pristine graphene after liquid phase exfoliation and was further minimized when the unoxidized graphene was well-dispersed with the block copolymer Pluronic. Our results demonstrate that the covalent oxidation of graphene is a major contributor to its pulmonary toxicity and suggest that dispersion of pristine graphene in Pluronic provides a pathway for the safe handling and potential biomedical application of two-dimensional carbon nanomaterials.     

Silicene: Wet‐Chemical Exfoliation Synthesis and Biodegradable Tumor Nanomedicine

Silicon‐based biomaterials play an indispensable role in biomedical engineering; however, due to the lack of intrinsic functionalities of silicon, the applications of silicon‐based nanomaterials are largely limited to only serving as carriers for drug delivery systems. Meanwhile, the intrinsically poor biodegradation nature for silicon‐based biomaterials as typical inorganic materials also impedes their further in vivo biomedical use and clinical translation. Herein, by the rational design and wet chemical exfoliation synthesis of the 2D silicene nanosheets, traditional 0D nanoparticulate nanosystems are transformed into 2D material systems, silicene nanosheets (SNSs), which feature an intriguing physiochemical nature for photo‐triggered therapeutics and diagnostic imaging and greatly favorable biological effects of biocompatibility and biodegradation. In combination with DFT‐based molecular dynamics (MD) calculations, the underlying mechanism of silicene interactions with bio‐milieu and its degradation behavior are probed under specific simulated physiological conditions. This work introduces a new form of silicon‐based biomaterials with 2D structure featuring biodegradability, biocompatibility, and multifunctionality for theranostic nanomedicine, which is expected to promise high clinical potentials.     

Recent Advances in Synthesis and Biomedical Applications of Two‐Dimensional Transition Metal Dichalcogenide Nanosheets

During recent decades, a giant leap in the development of nanotechnology has been witnessed. Numerous nanomaterials with different dimensions and unprecedented features have been developed and provided unimaginably wide scope to solve the challenging problems in biomedicine, such as cancer diagnosis and therapy. Recently, two‐dimensional (2D) transition metal dichalcogenide (TMDC) nanosheets (NSs), including MoS₂, WS₂, and etc., have emerged as novel inorganic graphene analogues and attracted tremendous attention due to their unique structures and distinctive properties, and opened up great opportunities for biomedical applications, including ultrasensitive biosensing, biological imaging, drug delivery, cancer therapy, and antibacterial treatment. A comprehensive overview of different synthetic methods of ultrathin 2D TMDC NSs and their state‐of‐the‐art biomedical applications, especially those that have appeared in the past few years, is presented. At the end of this review, the future opportunities and challenges for 2D TMDC NSs in biomedicine are also discussed.     

Molecular Hemocompatibility of Graphene Oxide and Its Implication for Antithrombotic Applications

Surface‐induced blood clotting is one of the major problems associated with the long‐term use of blood‐contacting biomedical devices. Central to this obstructive blood clotting is the adsorption of plasma proteins following the interactions between blood and material surface. Of all proteins circulating in the blood plasma, albumin and fibrinogen are the two important proteins regulating the blood–material interaction. As such, the adsorption of plasma proteins has been used as an indicator for the assessment of the blood compatibility of the biomedical devices. Numerous nanomaterials have been developed for antithrombotic surface coating applications, including the 2D graphene and its derivatives. Here, the antithrombotic property of albumin‐functionalized graphene oxide (albumin‐GO) and its potential for antithrombotic coating application under flow are investigated. The loading capacities, conformational changes, and adsorptions of albumin and fibrinogen on GO are probed. It is observed that GO possesses a high loading capacity for both proteins and simultaneously, it does not disrupt the overall secondary structure and conformational stability of albumin. Both albumin and fibrinogen adsorb well on the surface of GO. Subsequently, it is demonstrated that the albumin‐functionalized GO possesses enhanced antithrombotic effect and may potentially be used as an antithrombotic coating material of blood‐contacting devices under dynamic flow.     

Nanocomposite nanofibers of poly(d, l-lactic-co-glycolic acid) and graphene oxide nanosheets

Significant improvements in the thermomechanical and surface chemical properties of nanocomposite nanofibers of poly(d, l-lactic-co-glycolic acid) (PLGA) were achieved by adding 2-dimensional nanoscale fillers of graphene oxide (GO) nanosheets to PLGA nanofibers. The significant enhancement of storage and loss moduli of the PLGA/GO (2 wt.%.) nanocomposite nanofibers were presumably caused by enhanced chemical bonding between the oxygenated functional groups of the highly dispersible GO nanosheets and the hydroxyl groups of the polymer chains in the PLGA matrix, resulting in strong interfacial interactions between the nanofiller and polymer matrix. Enhanced hydrophilicity of nanocomposite nanofibers caused by embedded GO nanosheets also allowed for good biocompatibility of neuronal cells, resulting in enhanced cell proliferation and viability. Our findings indicate that nanocomposite biopolymer nanofibers embedded with GO nanosheets are attractive candidates for use in biomedical applications such as scaffolds.     

Controllable Bipolar Doping of Graphene with 2D Molecular Dopants

The fine control of graphene doping levels over a wide energy range remains a challenging issue for the electronic applications of graphene. Here, the controllable doping of chemical vapor deposited graphene, which provides a wide range of energy levels (shifts up to ± 0.5 eV), is demonstrated through physical contact with chemically versatile graphene oxide (GO) sheets, a 2D dopant that can be solution‐processed. GO sheets are a p‐type dopant due to their abundance of electron‐withdrawing functional groups. To expand the energy window of GO‐doped graphene, the GO surface is chemically modified with electron‐donating ethylene diamine molecules. The amine‐functionalized GO sheets exhibit strong n‐type doping behaviors. In addition, the particular physicochemical characteristics of the GO sheets, namely their sheet sizes, number of layers, and degree of oxidation and amine functionality, are systematically varied to finely tune their energy levels. Finally, the tailor‐made GO sheet dopants are applied into graphene‐based electronic devices, which are found to exhibit improved device performances. These results demonstrate the potential of GO sheet dopants in many graphene‐based electronics applications.     

Chemical Preparation of Graphene‐Based Nanomaterials and Their Applications in Chemical and Biological Sensors

Graphene is a flat monolayer of carbon atoms packed tightly into a 2D honeycomb lattice that shows many intriguing properties meeting the key requirements for the implementation of highly excellent sensors, and all kinds of proof‐of‐concept sensors have been devised. To realize the potential sensor applications, the key is to synthesize graphene in a controlled way to achieve enhanced solution‐processing capabilities, and at the same time to maintain or even improve the intrinsic properties of graphene. Several production techniques for graphene‐based nanomaterials have been developed, ranging from the mechanical cleavage and chemical exfoliation of high‐quality graphene to direct growth onto different substrates and the chemical routes using graphite oxide as a precusor to the newly developed bottom‐up approach at the molecular level. The current review critically explores the recent progress on the chemical preparation of graphene‐based nanomaterials and their applications in sensors.     

氧化石墨烯纳米片/环氧树脂复合材料的制备与性能

氧化石墨烯(GO)是石墨烯重要的衍生物之一,通过氧化和超声波分散制备了GO纳米片/环氧树脂复合材料。采用XRD、拉曼光谱、FTIR和TEM表征了GO纳米片的结构与形貌,研究了GO纳米片用量对GO纳米片/环氧树脂复合材料热稳定性、力学性能及介电性能的影响。结果表明:GO纳米片的加入提高了GO纳米片/环氧树脂复合材料失热稳定性;随着GO纳米片填充量的增加,GO纳米片/环氧树脂复合材料的冲击强度和抗弯性能先提高后降低,其介电常数和介电损耗则先减小后增加。GO纳米片填充量为0.3wt%的GO纳米片/环氧树脂复合材料的失重5%时的热分解温度由纯环氧树脂的400.2℃提高到424.5℃,而冲击强度和弯曲强度分别在GO纳米片填充量为0.2wt%和0.3wt%时达到最大,冲击强度由纯环氧树脂的10.5kJ/m2提高到19.7kJ/m2,弯曲强度由80.5 MPa提高到104.0 MPa。     

Determination of the Lateral Dimension of Graphene Oxide Nanosheets Using Analytical Ultracentrifugation

In this paper, a method to determine the lateral dimensions of 2D nanosheets directly in suspension by analytical ultracentrifugation (AUC) is shown. The basis for this study is a well‐characterized and stable dispersion of graphene oxide (GO) monolayers in water. A methodology is developed to correlate the sedimentation coefficient distribution measured by AUC with the lateral size distribution of the 2D GO nanosheets obtained from atomic force microscopy (AFM). A very high accuracy can be obtained by virtue of counting several thousand sheets, thereby minimizing any coating effects or statistical uncertainties. The AFM statistics are further used to fit the lateral size distribution obtained from the AUC to determine the unknown hydrodynamic sheet thickness or density. It is found that AUC can derive nanosheet diameter distributions with a relative error of the mean sheet diameter of just 0.25% as compared to the AFM analysis for 90 mass% of the particles in the distribution. The standard deviation of the size‐dependent error for the total distribution is found to be 3.25%. Based on these considerations, an expression is given to calculate the cut size of 2D nanosheets in preparative centrifugation experiments.     

Fabrication of high-pore volume carbon nanosheets with uniform arrangement of mesopores

Carbon nanosheets with a tunable mesopore size,large pore volume,and good electronic conductivity are synthesized via a solution-chemistry approach.In this synthesis,diaminohexane and graphene oxide (GO) are used as the structural directing agents,and a silica colloid is used as a mesopores template.Diaminohexane plays a crucial role in bridging silica colloid particles and GO,as well as initiating the polymerization of benzoxazine on the surfaces of both the GO and silica,resulting in the formation of a hybrid nanosheet polymer.The carbon nanosheets have graphene embedded in them and have several spherical mesopores with a pore volume up to 3.5 cm3·g-1 on their surfaces.These nuerous accessible mesopores in the carbon layers can act as reservoirs to host a high loading of active charge-storage materials with good dispersion and a uniform particle size.Compared with active materials with wide particle-size distributions,the unique proposed configuration with confined and uniform particles exhibits superior electrochemical performance during lithiation and delithiation,especially during long cycles and at high rates.