Counterfeits in the supply chain of high-value advanced materials such as graphene and their derivatives have become a concerning problem with a potential negative impact on this growing and emerging industry. Recent studies have revealed alarming facts that a large percentage of manufactured graphene materials on market are not graphene, raising considerable concerns for the end users. The common and recommended methods for the characterization of graphene materials, such as transmission electron microscopy (TEM), atomic force microscopy (AFM), and Raman spectroscopy based on spot analysis and probing properties of individual graphene particles, are limited to provide the determination of the properties of "bulk" graphene powders at a large scale and the identification of non-graphene components or purposely included additives. These limitations are creating counterfeit opportunities by adding low-cost black carbonaceous materials into manufactured graphene powders. To address this problem, it is critical to have reliable characterization methods, which can probe the specific properties of graphene powders at bulk scale, confirm their typical graphene signature, and detect the presence of unwanted additional compounds, where the thermogravimetric analysis (TGA) method is one of the most promising methods to perform this challenging task. This paper presents the evaluation of the TGA method and its ability to detect low-cost carbon additives such as graphite, carbon black, biochar, and activated carbon as potential counterfeiting materials to graphene materials and their derivatives such as graphene oxide (GO) and reduced GO. The superior performance of the TGA method is demonstrated here, showing its excellent capability to successfully detect these additives when mixed with graphene materials, which is not possible by two other comparative methods (Raman spectroscopy and powder X-ray diffraction (XRD)), which are used as the common characterization methods for graphene materials.
Understanding the upconversion pathways of a rare‐earth dopant is crucial to furthering the use of that material, either toward applications in imaging or elsewhere. This work outlines a new analysis approach that consists of using two synchronized widely‐tunable laser sources to explore the properties of upconverting materials. By examining sensitizer‐free rare‐earth nanoparticles based on a matrix of hexagonal sodium yttrium tetrafluoride (β‐NaYF4) doped with praseodymium but no ytterbium sensitizer, a “non‐degenerate” two‐color upconversion fluorescence at a combined excitation of 1020–850 nm is shown. This insight demonstrates the ability of this technique to locate and interrogate novel upconversion pathways. The dopant level of the nanoparticles could be modified without altering other factors, such as the particle's shape or size, that would also change optical properties and this allows investigation of the dopant‐level dependency of the optical properties. The approach also allows exploration of the time delay domain between the arrival times of the two non‐degenerate excitation pulses, which allows modulation of the brightness from the visible light emissions. This work opens up the parameter space for the systematic synthesis and characterization of new materials with non‐degenerate upconversion emission.
Antibacterial treatment strategies using functional nanomaterials, such as photodynamic therapy, are urgently required to combat persistent Staphylococcus aureus small colony variant (SCV) bacteria. Using a stepwise approach involving thermolysis to form β-NaYF 4 :Yb/Tm upconversion nanoparticles (UCNPs) and surface ligand exchange with cetyltrimethylammonium bromide (CTAB), followed by zeolite imidazolate framework-8 (ZIF-8) coating and conversion to zinc oxide (ZnO), β-NaYF 4 :Yb/Tm@ ZnO nanoparticles were synthesized. The direct synthesis of β-NaYF 4 :Yb/Tm@ZIF-8 UCNPs proved problematic due to the hydrophobic nature of the as-synthesized material, which was shown by zeta potential measurements using dynamic light scattering (DLS). To facilitate deposition of a ZnO coating, the zeta potentials of (i) as-synthesized UCNPs, (ii) calcined UCNPs, (iii) polyvinylpyrrolidone (PVP), and (iv) CTAB-coated UCNPs were measured, which revealed the CTAB-coated UCNPs to be the most hydrophilic and the better-dispersed form in water. β-NaYF 4 :Yb/Tm@ZIF-8 composites formed using the CTAB-coated UCNPs were then converted into β-NaYF 4 :Yb/Tm@ZnO nanoparticles by calcination under carefully controlled conditions. Photoluminescence analysis confirmed the upconversion process for the UCNP core, which allows the β-NaYF 4 :Yb/Tm@ZnO nanoparticles to photogenerate reactive oxygen species (ROS) when activated by near-infrared (NIR) radiation. The NIR-activated UCNPs@ZnO nanoparticles demonstrated potent efficacy against both Staphylococcus aureus (WCH-SK2) and its associated SCV form (0.67 and 0.76 log colony forming unit (CFU) reduction, respectively), which was attributed to ROS generated from the NIR activated β-NaYF 4 :Yb/Tm@ZnO nanoparticles.
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