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Currently, hybrid noble metal nanostructures have garnered significant interest due to their exceptional properties and diverse applications in fields such as catalysis, energy conversion, plasmonic sensing, and surface-enhanced Raman scattering (SERS). In this work, we report the highly site-specific growth of a single Ag island on both the concave face and the sharp tip of concave Au nanocube (c-AuNC) seeds, resulting in different c-AuNC-Ag Janus heterostructures. This site specificity was achieved by combining the surface curvature effect of the c-AuNCs with strong ligand-mediated interfacial energy control. Further integration of interfacial energy and growth kinetic control led to the formation of c-AuNC-(Ag)n core–satellite structures with varying numbers of Ag satellites. Benefiting from the continuous tunability of the interfacial energy and growth kinetics, the structural evolution of the c-AuNC-Ag hybrid structures continuously occurred, enabling precise control of the Au–Ag bimetallic structures. Notably, the resulting c-AuNC-Ag structures showed tunable intense localized surface plasmon resonance (LSPR) absorptions within the 400–1000 nm wavelength along with strong SERS signals. The broad spectral absorption and strong SERS made the c-AuNC-Ag structures promising candidates for SERS and LSPR-based applications, including sensing, imaging, light energy harvesting, and conversion. Moreover, the effective synthetic control demonstrated in this work could facilitate the development of advanced hybrid metal nanomaterials with valuable properties, further broadening their application potential across various fields. [ABSTRACT FROM AUTHOR]

Gold nanostars (AuNSs) are nanoparticles with intricate three-dimensional structures and shape-dependent optoelectronic properties. For example, AuNSs uniquely display three distinct surface curvatures, i.e. neutral, positive, and negative, which provide different environments to adsorbed ligands. Hence, these curvatures are used to introduce different surface chemistries in nanoparticles. This review summarizes and discusses the role of surface curvature in AuNS properties and its impact on biomedical and chemical applications, including surface-enhanced Raman spectroscopy, contrast agent performance, and catalysis. We examine the main synthetic approaches to generate AuNSs, control their morphology, and discuss their benefits and drawbacks. We also describe the optical characteristics of AuNSs and discuss how these depend on nanoparticle morphology. Finally, we analyze how AuNS surface curvature endows them with properties distinctly different from those of other nanoparticles, such as strong electromagnetic fields at the tips and increased hydrophilic environments at the indentations, together making AuNSs uniquely useful for biosensing, imaging, and local chemical manipulation.

Organic ligands are critical in determining the physiochemical properties of inorganic nanocrystals. However, precise nanocrystal surface modification is extremely difficult to achieve. Most research focuses on finding ligands that fully passivate the nanocrystal surface, with an emphasis on the supramolecular structure generated by the ligand shell. Inspired by molecular metal-coordination complexes, we devised an approach based on ligand anchoring groups that are flanked by encumbering organic substituents and are chemoselective for binding to nanocrystal corner, edge, and facet sites. Through experiment and theory, we affirmed that the surface-ligand steric pressures generated by these organic substituents are significant enough to impede binding to regions of low nanocurvature, such as nanocrystal facets, and to promote binding to regions of high curvature such as nanocrystal edges.

The design of scaffolds for tissue engineering has to consider two trade-off properties: mechanical and mass-transport properties. This is particularly true for additively manufactured scaffolds with the structures of minimal surfaces, and notably, the influence of the surface curvature of the structure on the mechanical and mass-transport properties remains unclear. This work presents our study on the scaffolds designed with the structure of triply periodic minimal surfaces (TPMS), with a focus on discovering the influence of surface curvature on the mechanical response and the mass-transport property or permeability of the scaffolds. Based on the entropy weight fuzzy comprehensive evaluation method, a model representative of both mechanical and permeable properties of scaffolds was developed; scanning electron microscopy (SEM) and finite element analysis (FEA) were also used to reveal the influence mechanism of curvature on structural fracture and deformation behavior. AlSi10Mg samples of scaffolds designed with different surface curvatures were manufactured using selective laser melting (SLM), and their mechanical and permeable properties were examined and characterized by both experiments and simulations. Our results illustrate that at the same porosity, the more concentrated the curvature distribution of the same type of unit, the better trade-off mechanical and mass-transport properties the scaffolds have. Particularly, at the porosity of 55%, the compressive elastic modulus and permeability of the Dte structure are increased by 2.03 times and 1.95 times compared with the Diamond unit, respectively. The fusion structure can greatly improve permeability performance at the cost of mechanical properties. Our results also show that porosity has the greatest influence on mechanical and permeable properties, followed by the surface curvature. The study illustrates that the surface curvature has a significant influence on the mechanical and permeable properties of scaffolds, and that the developed scaffold performance evaluation scheme is an effective means for the optimization and evaluation of scaffold performance.

Abnormal aggregation of alpha-synuclein (α-syn), an intrinsically disordered neuronal protein, is strongly implicated in the development of Parkinson's disease. Efforts to better understand α-syn's native function and its pathogenic role in neurodegeneration have revealed that the protein interacts with anionic lipid vesicles via adoption of an amphipathic α-helical structure; however, the ability of α-syn to remodel lipid membranes has made it difficult to decipher the role of vesicle surface curvature in protein binding behavior. In this study, sodium dodecyl sulfate (SDS)-coated gold nanoparticles (AuNPs), which mimic bilayer vesicle architecture, were synthesized in order to conduct a systematic investigation into the binding interaction of α-syn and two of its mutants (A30P and E46K) with rigid lipid vesicle mimics of defined surface curvature. By incorporating a rigid AuNP core (∼10-100 nm), the ability of α-syn to remodel the vesicle mimics was removed and their surface curvature could be fixed. Proteomics studies showed that, upon binding of free α-syn to the surface of SDS-AuNPs, the N-terminus of α-syn became less solvent accessible, whereas its C-terminus became more accessible. Interestingly, α-syn's non-amyloid-β component (NAC) region also exhibited increased solvent accessibility, suggesting that α-syn bound to rigid vesicle-like structures could possess heightened aggregation propensity and therefore pathogenicity. Additionally, both the A30P and E46K mutations were found to adopt distinct binding modes on the mimics' surface. In contrast with previous reports, similar binding affinities were observed for WT, A30P, and E46K α-syn toward SDS-AuNPs of all sizes, indicating the potential importance of vesicle deformability in determining α-syn binding behavior.

This Letter describes how the endosomal organization of immunostimulatory nanoconstructs can tune the in vitro activation of macrophages. Nanoconstructs composed of gold nanoparticles conjugated with unmethylated cytosine-phosphate-guanine (CpG) oligonucleotides have distinct endosomal distributions depending on the surface curvature. Mixed-curvature constructs produce a relatively high percentage of hollow endosomes, where constructs accumulated primarily along the interior edges. These constructs achieved a higher level of toll-like receptor (TLR) 9 activation along with the enhanced secretion of proinflammatory cytokines and chemokines compared to constant-curvature constructs that aggregated mostly in the center of the endosomes. Our results underscore the importance of intraendosomal interactions in regulating immune responses and targeted delivery.

Chemically and topographically patterned nanoparticles (NPs) with dimensions on the order of tens of nanometers have a diverse range of applications and are a valuable system for fundamental research. Recently, thermodynamically controlled segregation of a smooth layer of polymer ligands into pinned micelles (patches) offered an approach to nanopatterning of polymer-functionalized NPs. Control of the patch number, size, and spatial distribution on the surface of spherical NPs has been achieved, however, the role of NP shape remained elusive. In the present work, we report the role of NP shape, namely, the effect of the local surface curvature, on polymer segregation into surface patches. For polymer-functionalized metal nanocubes, we show experimentally and theoretically that the patches form preferentially on the high-curvature regions such as vertices and edges. An in situ transformation of the nanocubes into nanospheres leads to the change in the number and distribution of patches; a process that is dominated by the balance between the surface energy and the stretching energy of the polymer ligands. The experimental and theoretical results presented in this work are applicable to surface patterning of polymer-capped NPs with different shapes, thus enabling the exploration of patch-directed self-assembly, as colloidal surfactants, and as templates for the synthesis of hybrid nanomaterials.