Chiral nanoparticle assemblies are an interesting class of materials whose chiroptical properties make them attractive for a variety of applications. Here, C18-(PEPAuM-ox)2 (PEPAuM-ox = AYSSGAPPMoxPPF) is shown to direct the assembly of single-helical gold nanoparticle superstructures that exhibit exceptionally strong chiroptical activity at the plasmon frequency with absolute g-factor values up to 0.04. Transmission electron microscopy (TEM) and cryogenic electron tomography (cryo-ET) results indicate that the single helices have a periodic pitch of approximately 100 nm and consist of oblong gold nanoparticles. The morphology and assembled structure of C18-(PEPAuM-ox)2 are studied using TEM, atomic force microscopy (AFM), Fourier transform infrared (FTIR) spectroscopy, circular dichroism (CD) spectroscopy, X-ray diffraction (XRD), and solid-state nuclear magnetic resonance spectroscopy (ssNMR). TEM and AFM reveal that C18-(PEPAuM-ox)2 assembles into linear amyloid-like 1-D helical ribbons having structural parameters that correlate to those of the single-helical gold nanoparticle superstructures. FTIR, CD, XRD, and ssNMR indicate the presence of cross-β and polyproline II (PPII) secondary structure. A molecular assembly model is presented that takes into account all experimental observations and that supports the single-helical nanoparticle assembly architecture. This model provides the basis for the design of future nanoparticle assemblies having programmable structures and properties.
Crystalline 3-D materials bearing interlinked domains of differential porosity and functionality offer the potential for organizing and shuttling molecular and nanoscale matter to specific locations within 3-D space. Here, we present methods for creating prototype MOF materials that have such structural features. Specifically, the process of pore expansion via ligand exchange was studied for an isoreticular series of mesoporous MOFs based on bMOF-100. It was found that pore expansion occurs incrementally in small steps and that it proceeds gradually in an "outside→in" fashion within individual crystals. The ligand exchange reaction can be terminated prior to complete crystal conversion to yield intermediate product MOFs, denoted bMOF-100/102 and bMOF-102/106, which bear descending porosity gradients from the crystal periphery to the crystal core. As a proof of concept, size-sensitive incorporation of a gold-thiolate nanocluster, Au133(SR)52, selectively in the bMOF-102/106 crystal periphery region was accomplished via cation exchange. These new methods open up the possibility of controlling molecular organization and transport within porous MOF materials.
The properties of nanoparticle superstructures depend on many factors, including the structural metrics of the nanoparticle superstructure (particle diameter, interparticle distances, etc.). Here, we introduce a family of gold-binding peptide conjugate molecules that can direct nanoparticle assembly, and we describe how these molecules can be systematically modified to adjust the structural metrics of linear double-helical nanoparticle superstructures. Twelve new peptide conjugates are prepared via linking a gold-binding peptide, AYSSGAPPMPPF (PEP(Au)), to a hydrophobic aliphatic tail. The peptide conjugates have 1, 2, or 3 PEP(Au) headgroups and a C12, C14, C16, or C18 aliphatic tail. The soft assembly of these peptide conjugates was studied using transmission electron microscopy (TEM), atomic force microscopy (AFM), and infrared (IR) spectroscopy. Several peptide conjugates assemble into 1-D twisted fibers having measurable structural parameters such as fiber width, thickness, and pitch that can be systematically varied by adjusting the aliphatic tail length and number of peptide headgroups. The linear soft assemblies serve as structural scaffolds for arranging gold nanoparticles into double-helical superstructures, which are examined via TEM. The pitch and interparticle distances of the gold nanoparticle double helices correspond to the underlying metrics of the peptide conjugate soft assemblies, illustrating that designed peptide conjugate molecules can be used to not only direct the assembly of gold nanoparticles but also control the metrics of the assembled structure.
Systematically controlling the assembly architecture within a class of chiral nanoparticle superstructures is important for fine-tuning their chiroptical properties. Here, we report a family of chiral gold nanoparticle single helices, varying in helical pitch and nanoparticle dimensions, that is assembled using a series of peptide conjugate molecules C-(PEP) (PEP = AYSSGAPPMPPF; x = 16-22). We demonstrate that the aliphatic tail length (i) can be used as a handle to systematically tune the helical pitch from 80 to 130 nm; and (ii) influences the size, shape, and aspect ratio of the component nanoparticles. Certain members of this family of materials exhibit intense plasmonic chiroptical activity. These studies highlight the multiple levels of structural control that can be achieved within a class of chiral nanoparticle superstructures via careful design and selection of peptide conjugate precursor.
The successful integration of 2D nanomaterials into functional devices hinges on developing fabrication methods that afford hierarchicalcontrol across length scales of the entire assembly.W ed emonstrate structural control over ac lass of crystalline 2D nanosheets assembled from collagen triple helices.Bylengthening the triple helix unit through sequential additions of Pro-Hyp-Gly triads,w ea chieved sub-angstrom tuning over the 2D lattice.T hese subtle changes influence the overall nanosheet size, which can be adjusted across the mesoscale size regime.The internal structure was observed by cryo-TEM with direct electron detection, whichprovides realspace high-resolution images,inwhich individual triple helices comprising the lattice can be clearly discerned. These results establish ag eneral strategy for tuning the structural hierarchy of 2D nanomaterials that employr igid, cylindrical structural units.
scite is a Brooklyn-based organization that helps researchers better discover and understand research articles through Smart Citations–citations that display the context of the citation and describe whether the article provides supporting or contrasting evidence. scite is used by students and researchers from around the world and is funded in part by the National Science Foundation and the National Institute on Drug Abuse of the National Institutes of Health.
hi@scite.ai
10624 S. Eastern Ave., Ste. A-614
Henderson, NV 89052, USA
Copyright © 2024 scite LLC. All rights reserved.
Made with 💙 for researchers
Part of the Research Solutions Family.