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© 2021 The Authors. Ultrasound-assisted liquid phase exfoliation is a promising method for manufacturing of 2D materials in large scale and sustainable manner. A large number of studies using ex-situ nano/micro structural characterization techniques have been made to investigate the underlying mechanisms, aiming to understand the exfoliation dynamics. Due to the complex multiphysics and multi-length nature of the process, those ex-situ methods cannot provide the real-time and in-situ dynamic information for understanding how exactly layer exfoliation starts and grows under ultrasound. Here, we used the ultrafast synchrotron-X-ray phase-contrast imaging (a combined temporal resolution of 3.68 μs and a spatial resolution of 1.9 μm/pixel) to study the exfoliation dynamics in real time and operando condition. We revealed, for the first time, the fatigue exfoliation phenomenon at the graphite surface caused by the imploding ultrasonic bubbles occurring cyclically in line with the ultrasound frequency. A multiphysics numerical model was also developed to calculate the shock wave produced at bubble implosion and the resulting cyclic and impulsive tensile and shear stresses acting on the graphite surface. Our research reveals that the graphite layer exfoliation rate and efficiency are predominantly determined by the number of imploding bubbles inside the effective cavitation bubble zone. The findings are valuable for developing industrial upscaling strategies for ultrasound processing of 2D materials. UK Engineering and Physical Sciences Research Council (Grant Nos. EP/R031665/1; EP/R031401/1; EP/R031819/1; EP/R031975/1); Royal Society.

Achieving a sustainable production of pristine high-quality graphene and other layered materials at a low cost is one of the bottlenecks that needs to be overcome for reaching 2D material applications at a large scale. Liquid phase exfoliation in conjunction with N-methyl-2-pyrrolidone (NMP) is recognized as the most efficient method for both the exfoliation and dispersion of graphene. Unfortunately, NMP is neither sustainable nor suitable for up-scaling production due to its adverse impact on the environment. Here, we show the real potential of green solvents by revealing the independent contributions of their exfoliation efficiency and graphene dispersibility to the graphene yield. By experimentally separating these two factors, we demonstrate that the exfoliation efficiency of a given solvent is independent of its dispersibility. Our studies revealed that isopropanol can be used to exfoliate graphite as efficiently as NMP. Our finding is corroborated by the matching ratio between the polar and dispersive energies of graphite and that of the solvent surface tension. This direct evidence of exfoliation efficiency and dispersibility of solvents paves the way to developing a deeper understanding of the real potential of sustainable graphene manufacturing at a large scale. UK Engineering and Physical Sciences Research Council (EPSRC), within the project “Sustainable and industrially scalable ultrasonic liquid phase exfoliation technologies for manufacturing 2D advanced functional materials” (EcoUltra2D), with the grant nos. EP/R031665/1; EP/R031401/1; EP/R031819/1; and EP/R031975/1. We wish to acknowledge the support of the Henry Royce Institute for advanced materials for K.L.N. through the Student Equipment Access Scheme enabling access to the Kruss GmbH K100C Surface Tensiometer facilities at the University of Manchester; EPSRC grant number EP/R00661X/1. N.G. thanks the Royal Society for financial support.

Heteroatomic nanotubes consisting of graphitic carbon (g-C) and hexagonal boron nitride (h-BN) were first synthesised over two decades ago, representing the earliest example of a carbon nanotube (CNT) covalently doped with h-BN. This opened up a exiting new field of study into BxCyNz heteronanotubes that exhibit tunable electronic properties based on stoichiometry. Increased research focus on such heteronanotubes has also led to the development of novel configurations of g-C and h-BN in van der Waals type hybrids. In particular, heteronanotubes consisting of a core CNT sheathed with h-BN, coaxial shell layers (CNT@BN), have recently witnessed advances in their synthesis and exploitation. CNT@BNs exhibit superior thermal stability, chemical inertness and mechanical robustness in comparison to CNTs, whilst the h-BN also adds the rare duo of thermal conduction pathways and electrical insulation. The various synthesis methods yield a range of different structure, crystallinity and composition profiles in CNT@BN. Here, we review the current methods of CNT@BN production and characterisation and highlight the prospect for application of these heteronanotubes in high temperature composites, nano-mechanical components, nano-electronics, field emitters and thermal management materials, and propose future avenues of research.

© 2021 The Author(s). Ultrasound-aided liquid phase exfoliation (ULPE) of graphene in pure water is environment-friendly. Two limiting factors of ULPE are the non-uniform thickness of few-layer graphene (FLG) and a relatively low graphene yield. Here we describe ULPE in water that enables us to produce FLG flakes with a thickness of 3 layers and the flake sizes exceeding 1 μm2 in just 2 h. This process is based on using a combination of two ultrasound sources of high and low frequencies: 1174 kHz and 20 kHz. Two different frequencies generate a wider population and size distribution of cavitation bubbles that act through a number of mechanisms towards the exfoliation of graphene. For the first time ULPE was characterized by acoustic measurements. Results show that a high graphene yield (10%) can be achieved. This study demonstrates that the use of a dual frequency ultrasonic source and control of acoustic pressure is critical in optimizing the quality and yield of the cavitation assisted LPE of graphene in pure water. It is suggested that the width of the acoustic pressure peak reflecting shock-wave emissions can be used as an indicator of ULPE completeness, opening for the first time a way of in-situ monitoring of the process. Engineering and Physical Sciences Research Council (grant nos. EP/R031665/1; EP/R031401/1; EP/R031819/1; EP/R031975/1).

It is already known that cells respond strongly to topography and chemistry of 2D surfaces. In this work we study cell-material interactions; in particular, we investigated the attachment and alignment of SH-SY5Y cells of neuronal origin on grooved-patterns made from Silicon (Si) and Gold (Au). The Au-Si groove-pattern stimulated 93% of SH-SY5Y cells to differentiate into neuroblast-like type (N-type) in 2 days and outgrown neurites exhibited strong anisotropy along the grooves with 90% of cells having one or two neurites. In comparison, random distribution of morphology type, neurite number, and alignment were observed on control flat surfaces (Si and Au). We further show that designed Au-Si groove-patterns can be used to form reversed groove patterns on polycarolactone surface via soft lithography approach. Sixty-nine percentage of SH-SY5Y cells aligned along the obtained reversed groove patterns of the same dimensional characteristics to Si-Au grooves. In particular, this work demonstrated that the Au-Si grooves pattern stimulates neurite polarity, elongation, and morphological differentiation of neuroblastoma cells without any exogenous supply of growth factors or stimulants in just 2 days, which can lead to selective procedure of obtaining homologous population of neuron-like cells for future nerve regeneration therapies.

A novel approach using a zwitterionic sulfobetaine-based surfactant for the synthesis of spherical copper oxide nanoparticles (Cu

Liquid Phase Exfoliation (LPE) is an efficient method for graphene flake exfoliation and considered to be compatible with industrial production requirements. However, most of available LPE methods require the uses of harmful and expensive solvents for chemical exfoliation prior to mechanical dispersion of the flakes, and therefore an additional step is needed to remove the contamination caused by the added chemicals, making the process complex, costly, unsafe and detrimental to the environment. By studying the effects of key ultrasonic LPE parameters, our study demonstrates the possibility to control the production and quality of few-layer graphene flakes in pure water in a relatively short period of time. The driving frequency of an ultrasonic source, a higher acoustic cavitation intensity and uniform distribution of the cavitation events in the sonicated volume are the key parameters for controlling the thickness, surface area and production yield of few-layer graphene flakes. The results are discussed in the context of mechanical exfoliation. This opens a direction for developing LPE into a cost effective, clean, environmentally friendly, and scalable manufacturing process for the next generation of two-dimensional nanomaterials for industrial-scale applications. UK Engineering and Physical Sciences Research Council (EPSRC) “Sustainable and industrially scalable ultrasonic liquid phase exfoliation technologies for manufacturing 2D advanced functional materials” (EcoUltra2D) (grant nos. EP/R031665/1; EP/R031401/1; EP/R031819/1; EP/R031975/1); Royal Society.

This review presents the latest innovations and trends in the field of surface functionalization of various nanomaterials. The most recent protocols of smart materials fabrication as well as the main challenges which should be overcome in order to improve their final performance are discussed here. Particular attention has been paid to the properties improvement of polymer, silica, inorganic and hybrid nanomaterials and their potential for application in many fields, from industry, materials science, environmental protection to advanced biomedicine.

Photoluminescence properties of red-emitting Pr3+-doped Bi2ZnOB2O6 microcrystalline powder and PMMA-based composite materials were reported. Bi2ZnOB2O6:Pr3+ powders were synthesized by means of the modified Pechini method. The morphology and crystallographic structure of Bi2ZnOB2O6:Pr3+ microcrystals were investigated by XRD and HRTEM. The PMMA-based composite materials were prepared by embedding of Bi2ZnOB2O6:Pr3+ powder in the PMMA matrix. The vibrational properties of the powder and composite systems were investigated by μ-Raman spectroscopy. Emission spectra of the samples were measured under blue (451.6 nm) and UV (320 nm) excitation. Both, the powder and composite samples show enhancement of red emission (1D2 → 3H4) and quenching of greenish-blue luminescence from 3P0 level of Pr3+ ions after excitation in UV and VIS caused by the 3P0 ∼ 1D2 non-radiative relaxation of Pr3+ ion by low-lying charge transfer state and non-radiative de-excitation through Pr3+–Bi3+ energy transfer. The response of the powder and composite samples to pulsed excitation at 451.6 nm was measured by monitoring emission from the 1D2 level (595 nm/3P0 → 3H6 transition). The determined lifetimes τ1 and τ2 of the red emission at 595 nm (1D2 → 3H4 transition) of the composite are significantly longer in comparison to powder samples. Moreover, because of the good nonlinear optical properties of the Bi2ZnOB2O6 crystals and effective luminescence of the Pr3+-doped Bi2ZnOB2O6 powders and composites, they can be very useful as bi-functional materials in the new generation of optoelectronic devices.

In this study we examine multiwall carbon nanotube (MWCNT) based nanosystems i.e. aligned MWCNT matrices, as potential scaffolds for cell growth and tissue engineering. We present the effect of samples purification and surface modification on the viability, adhesiveness and morphology of human normal gingival fibroblasts (HGF-1) and human osteosarcoma (U2OS) cell lines. We employ spectroscopic and analytical techniques (Scanning Electron Microscopy, Thermal Gravimetric Analysis, Atomic Force Microscopy, Raman and Fourier Transform Infrared Absorption Spectroscopy and Confocal Microscopy) in order to characterize the obtained structures. Furthermore, we analyze the expression level of selected cell adhesion-related genes by the quantitative real-time (qRT-PCR) method and the cell viability for MWCNT powders. We show that the surface structure of MWCNTs carpets contributes to the adhesion of cells. Additionally, we report the increased expression level of integrin, talin and fibronectin, proteins which are involved in cell attachment. We speculate that carbon nanotube based materials can be consider as potential candidates for biomedical purposes and as a biocompatible scaffold for cell growth.

Many bacteria become progressively more resistant to antibiotics and it remains a challenging task to control their overall levels. Polymers combined with active biomolecules come to the forefront for the design of antibacterial materials that can address this encounter. In this work, we investigated the photo-crosslinking approach of UV-sensitive benzophenone molecule (BP) with polyvinylpyrrolidone (PVP) polymer within electrospun fibres. The BP and PVP solutions allowed fabricating polymer mats that were subsequently functionalised with antibacterial lysozyme. The physical properties of the crosslinked electrospun fibres were investigated by scanning electron microscopy and atomic force microscopy. The average diameter of the obtained fibres decreased from 290 ± 50 nm to 270 ± 70 nm upon the addition of the crosslinking molecules and then to 240 ± 80 nm and 180 ± 90 nm after subsequent crosslinking reaction at an increasing time: 3 and 5 h, respectively. The peak force quantitative nanomechanical mapping (PF-QNM) indicated the increase of DMT modulus of obtained cross-linked fibres from 4.1 ± 0.8 GPa to 7.2 ± 0.5 GPa. Furthermore, the successful crosslinking reaction of PVP and BP solution into hydrogels was investigated in terms of examining photo-crosslinking mechanism and was confirmed by rheology, Raman, Fourier transform infrared and nuclear magnetic resonance. Finally, lysozyme was successfully encapsulated within cross-linked PVP-BP hydrogels and these were successfully electrospun into mats which were found to be as effective antibacterial agents as pure lysozyme molecules. The dissolution rate of photo cross-linked PVP mats was observed to increase in comparison to pure PVP electrospun mats which opened a potential route for their use as antibacterial, on-demand, dissolvable coatings for various biomedical applications., Graphical Abstract

This study examines the use of oxidized multi-walled carbon nanotube/iron (O-MWCNT/Fe) nanohybrids modified with polyethylene glycol (PEG) as multifunctional cellular imaging agents for magnetic resonance imaging (MRI) and fluorescence microscopy. The PEGylated MWCNTs with embedded iron particles were investigated as T2-weighted contrast agents for MRI. The number of PEG molecules attached to the MWCNT surface was calculated. The PEG–MWCNT/Fe complex was characterized by transmission electron microscopy, scanning electron microscopy, Fourier transform infrared and Raman spectroscopies. Covalent surface modification of the MWCNTs improves their solubility and enables the attachment of further biomolecules to their surface. The PEGylated nanostructures were labeled with the MDC organic dye and internalized inside HeLa cells for cellular imaging. Additionally, the minimal cytotoxic effect of PEGylated complexes in comparison to non-PEGylated samples was measured using the WST-1 test and an In Cell Analyzer. A confocal microscopy study of the organelle morphology also confirmed that the HeLa cell morphology was unchanged after treatment with PEGylated MWCNTs.

In this work, functionalized Multiwall Carbon Nanotubes of specified length and containing well-defined iron particles (O-MWCNT/Fe) were prepared. A significant enhancement in contrast in Magnetic Resonance Imaging was found for the investigated composites. The magnetic characterization revealed the ferromagnetic nature of iron particles embedded within O-MWCNTs. The enhancement of the 1 H spin–spin relaxation time of MRI scans using hydrophilic O-MWCNT/Fe as potential contrast agents was estimated for selected dispersive media. Moreover, the cytotoxicity of the hybrids was studied in two cell lines, i.e. cancer cells (HeLa) and fibroblasts (GM07492). The intracellular impact of O-MWCNT/Fes in HeLa cells was observed after staining of selected organelles (nuclei and mitochondria). Significant changes in cell morphology were found for water soluble MWCNT/Fes with diameters above 30 nm.

Composite coatings provide a promising way of in vitro cell behavior screening. Previous efforts included fabrication of single-walled carbon nanotubes (SWCNTs)-polymer materials, however in this work, for the first time we combined two polymers of different hydrophobic character: poly(maleic-alt-1-octadecene) and polyvinylpyrrolidone with multi-walled carbon nanotubes (MWCNTs) to produce composite coatings with varied hydrophobicity. Prior to their incorporation, MWCNTs were characterized using Raman spectroscopy during ball-milling procedure at different times to establish ideal fabrication conditions for their best quality. Electrostatic force microscopy was then used to look at the distribution and MWCNTs networks formation in the composite coatings. Atomic force and scanning electron microscopies were used to establish the topographical features and thicknesses of produced coatings, which varied with the content of MWCNTs. All composites as well as control pure polymer coatings proved to be biocompatible and exhibited a viability of >80% on two human cell lines: cancerous osteosarcoma (U2OS) and fibroblast (MSU-1.1) that varied by their tumorigenicity, irrespectively of the hydrophobicity of the coating. Both cell lines were further shown by scanning electron microscopy to remain in the typical morphological state with high proliferation and attachment to all formed composites. These results show the potential of formation of MWCNTs-polymer composites by facile preparation way (spin-coating) and their potential as coatings for 2D in vitro cell culture platforms.

Purpose The study discusses the value of electrospun cilostazol-loaded (CIL) polymer structures for potential vascular implant applications. Methods Biodegradable polycaprolactone (PCL) fibers were produced by electrospinning on a rotating drum collector. Three different concentrations of CIL: 6.25%, 12.50% and 18.75% based on the amount of polymer, were incorporated into the fibers. The fibers were characterized by their size, shape and orientation. Materials characterization was carried out by Fourier Transformed Infrared spectroscopy (FTIR), Raman spectroscopy, differential scanning calorimetry (DSC) and X-ray diffraction (XRD). In vitro drug release study was conducted using flow-through cell apparatus (USP 4). Results Three-dimensional structures characterized by fibers diameter ranging from 0.81 to 2.48 μm were in the range required for cardiovascular application. DSC and XRD confirmed the presence of CIL in the electrospun fibers. FTIR and Raman spectra confirmed CIL polymorphic form. Elastic modulus values for PCL and the CIL-loaded PCL fibers were in the range from 0.6 to 1.1 GPa. The in vitro release studies were conducted and revealed drug dissolution in combination with diffusion and polymer relaxation as mechanisms for CIL release from the polymer matrix. Conclusions The release profile of CIL and nanomechanical properties of all formulations of PCL fibers demonstrate that the cilostazol loaded PCL fibers are an efficient delivery system for vascular implant application. Electronic supplementary material The online version of this article (10.1007/s11095-017-2314-0) contains supplementary material, which is available to authorized users.

In this study, the oxidation of multiwalled carbon nanotubes (MWCNTs) sonicated and/or refluxed in acids (H2SO4/HNO3) was investigated using a combination of high-resolution transmission electron microscopy, Raman spectroscopy, Fourier transform infrared spectroscopy, and ab initio computational methods. Sonication of the sample has the strongest effect, leading to the highest concentration of defects and carboxyl groups on the walls. Substantial correlations between treatment protocols, CNT size, and the types of chemical moieties are observed. Finally, based on experimental and computational results, we suggest the mechanism of the oxidation process for attaching the functional groups on the sidewalls.

For electromagnetic absorbing and shielding applications, carbon nanotubes (CNT) are widely used due to their excellent electrical and physical properties. Fabrication of microwave absorbing materials involves the use of compounds capable of generating dielectric and/or magnetic losses when impinged by an electromagnetic wave. The presence of lattice defects e.g. vacancies and dislocations contributes to the loss and attenuation in the electromagnetic waves, which in turn remarkably enhance the absorption ability of the material. With the CVD technique which is known to produce several lattice defects in the final product, aligned MWCNTs were successfully synthesized by pyrolizing toluene and ferrocene in an inert argon environment. The morphology analysis of the aligned MWCNTs was conducted via FESEM and TEM analysis, to reveal the average length of approximately 295 μm, with diameters in the range of 60-200 nm. EDS analysis indicates the high yield of CNTs, with more than 90% in weight composition, with less than 5 % Fe impurities presence. Textural properties of MWCNTs were studied by measuring pore size and BET surface area. To understand the response of CNTs to an electromagnetic field, permeability and permittivity measurement were conducted in the frequency range of 100 Hz to 110 MHz. In conclusion, the presence of defects in MWCNTs is desirable for enhanced electromagnetic absorption ability.