Self-assembly is a phenomenon that continuously occurs at the nanoscale, as atoms form predetermined building blocks such as molecules and clusters, which then themselves gather into structures of a larger scale. The interplay of competing forces is a decisive factor in the emergence of these organized systems, but the precise mechanism by which this self-assembly progresses is seldom known. Using a combination of physical cluster deposition and atomic force microscopy, we have investigated the spontaneous formation of μm-sized rings of SiO(x)-supported metal nanoclusters. With the help of molecular dynamics simulations, we show that the competition between short-range van der Waals attractions and long-range repulsive dipolar forces, induced by the ionic surface, plays a key role in the self-assembly of these structures.
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http://dx.doi.org/10.1088/0957-4484/24/3/035602 | DOI Listing |
J Am Chem Soc
January 2025
Department of Chemistry, Massachusetts Institute of Technology, Cambridge, Massachusetts 02139, United States.
Graft-through ring-opening metathesis polymerization (ROMP) of norbornene-terminated macromonomers (MMs) prepared using various polymerization methods has been extensively used for the synthesis of bottlebrush (co)polymers, yet the potential of ROMP for the synthesis of MMs that can subsequently be polymerized by graft-through ROMP to produce new bottlebrush compositions remains untapped. Here, we report an efficient "ROMP-of-ROMP" method that involves the synthesis of norbornene-terminated poly(norbornene imide) (PNI)-based MMs that, following ROMP, provide new families of bottlebrush (co)polymers and "brush-on-brush" hierarchical architectures. In the bulk state, the organization of the PNI pendants drives bottlebrush backbone extension to enable rapid assembly of asymmetric lamellar morphologies with large asymmetry factors.
View Article and Find Full Text PDFJ Am Chem Soc
January 2025
Department of Chemistry, Brandeis University, 415 South St., Waltham, Massachusetts 02454, United States.
Despite their critical role in context-dependent interactions for protein functions, intrinsically disordered regions (IDRs) are often overlooked for designing peptide assemblies. Here, we exploit IDRs to enable context-dependent heterotypic assemblies of intrinsically disordered peptides, where "context-dependent" refers to assembly behavior driven by interactions with other molecules. By attaching an aromatic segment to oppositely charged intrinsically disordered peptides, we achieve a nanofiber formation.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
January 2025
East China University of Science and Technology, School of Chemistry and Molecular Engineering, Meilong Road 130, 200237, Shanghai, CHINA.
Kinetically controlled self-assembly is garnering increasing interest in the field of supramolecular polymers and materials, yet examples involving dynamic covalent exchange remain relatively unexplored. Here we report an unexpected dynamic covalent polymeric system whose aqueous self-assembly pathway is strongly influenced by the kinetics of evaporation of water. The key design is to integrate dual dynamic covalent bonds-including disulfide bonds and boroxine/borate-into a dynamic equilibrium system of monomers, polymers, and materials.
View Article and Find Full Text PDFJ Phys Chem B
January 2025
Department of Engineering Mechanics, KTH Royal Institute of Technology, 100 44 Stockholm, Sweden.
We here explore confinement-induced assembly of whey protein nanofibrils (PNFs) into microscale fibers using microfocused synchrotron X-ray scattering. Solvent evaporation aligns the PNFs into anisotropic fibers, and the process is followed in situ by scattering experiments within a droplet of PNF dispersion. We find an optimal temperature at which the order parameter of the protein fiber is maximized, suggesting that the degree of order results from a balance between the time scales of the forced alignment and the rotational diffusion of the fibrils.
View Article and Find Full Text PDFSmall
January 2025
MOE International Joint Laboratory of Materials Microstructure, Institute for New Energy Materials and Low Carbon Technologies, School of Materials Science and Engineering, Tianjin University of Technology, Tianjin, 300384, China.
The photocatalytic activity of lead-free perovskite heterostructures currently suffers from low efficiency due to the lack of active sites and the inadequate photogenerated carrier separation, the latter of which is hindered by slow charge transfer at the heterostructure interfaces. Herein, a facile strategy is reported for the construction of lead-free halide-perovskite-based heterostructure with swift interfacial charge transfer, achieved through direct partial conversion of 2D antimony oxybromide SbOBr to generate CsSbBr/SbOBr heterostructure. Compared to the traditional electrostatic self-assembly method, this approach endows the CsSbBr/SbOBr heterostructure with a tightly interconnected interface through in situ partial conversion, significantly accelerating interfacial charge transfer and thereby enhancing the separation efficiency of photogenerated carriers.
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