their potential for applications in bioimaging, therapy, sensing, and catalysis. [4,5] For instance, ultrathin 2D noble metal nanomaterials have attracted increasing attention due to their ultrathin nature and 2D morphology. The ultrathin nature leads to high surface area-to-volume ratio and abundant exposed catalytically-active sites. [6][7][8] The 2D morphology confers a large interfacial area in contact with the substrate compared with either 1D or 3D nanostructures (e.g., nanowire or nanoparticles), which can enhance the interactions between reactants and the surface of catalysts, contributing to high activity. [8] In view of the fascinating attributes and numerous potential applications of ultrathin 2D metal nanomaterials associated with their unique structural features, it is essential to develop feasible facile and reliable synthesis routes. [2] However, the production of ultrathin 2D metal nanomaterials, free of a solid substrate, represents a significant challenge, due to the tendency of metal atoms to form a highly isotropic 3D close-packed crystal lattice. [9] This natural tendency toward 3D growth can be suppressed by the introduction of confinement to induce anisotropic growth. [4] To date, a range of synthesis strategies have been utilized to prohibit the free 2D metal nanomaterials offer exciting prospects in terms of their properties and functions. However, the ambient aqueous synthesis of atomicallythin, 2D metallic nanomaterials represents a significant challenge. Herein, freestanding and atomically-thin gold nanosheets with a thickness of only 0.47 nm (two atomic layers thick) are synthesized via a one-step aqueous approach at 20 °C, using methyl orange as a confining agent. Owing to the high surface-area-to-volume ratio, abundance of unsaturated atoms exposed on the surface and large interfacial areas arising from their ultrathin 2D nature, the as-prepared Au nanosheets demonstrate excellent catalysis performance in the model reaction of 4-nitrophenol reduction, and remarkable peroxidase-mimicking activity, which enables a highly sensitive colorimetric sensing of H 2 O 2 with a detection limit of 0.11 × 10 −6 m. This work represents the first fabrication of freestanding 2D gold with a sub-nanometer thickness, opens up an innovative pathway toward atomically-thin metal nanomaterials that can serve as model systems for inspiring fundamental advances in materials science, and holds potential across a wide region of applications. Sub-Nanometer Thick Gold Nanosheets
Rising concerns over multidrug-resistant bacteria have necessitated an expansion to the current antimicrobial arsenal and forced the development of novel delivery strategies that enhance the efficacy of existing treatments. Antimicrobial peptides (AMPs) are a promising antibiotic alternative that physically disrupts the membrane of bacteria, resulting in rapid bactericidal activity; however, clinical translation of AMPs has been hindered by their susceptibility to protease degradation. Through the co-loading of liposomes encapsulating model AMP, IRIKIRIK-CONH2 (IK8), and gold nanorods (AuNRs) into a poly(ethylene glycol) (PEG) hydrogel, we have demonstrated the ability to protect encapsulated materials from proteolysis and provide the first instance of the triggered AMP release. Laser irradiation at 860 nm, at 2.1 W cm–2, for 10 min led to the photothermal triggered release of IK8, resulting in bactericidal activity against Gram-negative Pseudonomas aeruginosa and Gram-positive Staphylococcus aureus. Furthermore, by increasing the laser intensity to 2.4 W cm–2, we have shown the thermal enhancement of AMP activity. The photothermal triggered release, and enhancement of AMP efficacy, was demonstrated to treat two rounds of fresh S. aureus, indicating that the therapeutic gel has the potential for multiple rounds of treatment. Taken together, this novel therapeutic hydrogel system demonstrates the stimuli-responsive release of AMPs with photothermal enhanced antimicrobial efficacy to treat pathogenic bacteria.
High purity gold nanorods (AuNRs) with tunable morphology have been synthesized through a binary-surfactant seedless method, which enables the formation of monocrystalline AuNRs with diameters between 7 and 35 nm. The protocol has high shape yield and monodispersity, demonstrating good reproducibility and scalability allowing synthesis of batches 0.5 l in volume. Morphological control has been achieved through the adjustment of the molar concentrations of cetyltrimethylammonium bromide and sodium oleate in the growth solution, providing fine tuning of the optical scattering and absorbance properties of the AuNRs across the visible and NIR spectrum. Sodium oleate was found to provide greatest control over the aspect ratio (and hence optical properties) with concentration changes between 10 and 23 mM leading to variation in the aspect ratio between 2.8 and 4.8. Changes in the geometry of the end-caps were also observed as a result of manipulating the two surfactant concentrations.
The ability to synthesize plasmonic nanomaterials with well-defined structures and tailorable size is crucial for exploring their potential applications. Gold nanoplates (AuNPLs) exhibit appealing structural and optical properties, yet their applications are limited by difficulties in thickness control. Other challenges include a narrow range of tunability in size and surface plasmon resonance, combined with a synthesis conventionally involving cytotoxic cetyltrimethylammonium (CTA) halide surfactant. Here, a one-step, high-yield synthesis of single-crystalline AuNPLs is developed, based on the combined use of two structure-directing agents, methyl orange and FeBr 3 , which undergo preferential adsorption onto different crystalline facets of gold. The obtained AuNPLs feature high shape homogeneity that enables mesoscopic self-assembly, broad-range tunability of dimensions (controlled thickness from ≈7 to ≈20 nm, accompanied by modulation of the edge length from ≈150 nm to ≈2 µm) and plasmonic properties. These merits, coupled with a preparation free of CTA-halide surfactants, have facilitated the exploration of various uses, especially in bio-related areas. For example, they are demonstrated as biocompatible photothermal agents for cell ablation in NIR I and NIR II windows. This work paves the way to the innovative fabrication of anisotropic plasmonic nanomaterials with desired attributes for wide-ranging practical applications.
Biomineralisation peptides that facilitate the one-pot synthesis of gold nanoparticles (AuNPs) with selected optical properties, were screened using a coherent peptide-spotted array consisting of a AuNP binding peptide library.
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