Supramolecular assemblies from single-chain hydrocarbon fluorocarbon hybrid bolaamphiphiles

Three types of single-chain hydrocarbon fluorocarbon hybrid bolaamphiphiles were synthesized.They readily formed different kinds of organized supramolecular assemblies,including vesicles,tapes,and micellar fibers,in aqueous solution.The aggregates morphology was characterized by transmission electron microscopy (TEM) after negative staining.The superstructures of these aggregates seemed to be determined by the geometry and the head group's properties of the corresponding amphiphiles.     

Tuning the Electronic Properties of Platinum in Hybrid-Nanoparticle Assemblies for use in Hydrogen Evolution Reaction

Platinum is the best electrocatalyst for the hydrogen evolution reaction (HER). Here, we demonstrate that by contact electrification of Pt nanoparticle satellites on a gold or silver core, the Fermi level of Pt can be tuned. The electronic properties of Pt in such hybrid nanocatalysts were experimentally characterized by X-ray photoelectron spectroscopy (XPS) and surface-enhanced Raman scattering (SERS) with the probe molecule 2,6-dimethyl phenyl isocyanide (2,6-DMPI). Our experimental findings are corroborated by a hybridization model and density functional theory (DFT) calculations. Finally, we demonstrate that tuning of the Fermi level of Pt results in reduced or increased overpotentials in water splitting.     

Dynamic Reconfigurable DNA Nanostructures,Networks and Materials

DNA nanotechnology relies on the structural and functional information encoded in nucleic acids. Specifically, the sequence-guided reconfiguration of nucleic acids by auxiliary triggers provides a means to develop DNA switches, machines and stimuli-responsive materials. The present Review addresses recent advances in the construction and applications of dynamic reconfigurable DNA nanostructures, networks and materials. Dynamic transformations proceeding within engineered origami frames or between origami tiles, and the triggered dynamic reconfiguration of scaled supramolecular origami structures are addressed. The use of origami frameworks to assemble dynamic chiroplasmonic optical devices and to operate switchable chemical processes are discussed. Also, the dynamic operation of DNA networks is addressed, and the design of “smart” stimuli-responsive all-DNA materials and their applications are introduced. Future perspectives and applications of dynamic reconfigurable DNA nanostructures are presented.     

Charge-Segregated Stacking Structure with Anisotropic Electric Conductivity in NIR-Absorbing and Emitting Positively Charged π-Electronic Systems

Squarylium-based π-electronic cation with an augmented dipole was synthesized by methylation of zwitterionic squarylium. The cation formed various ion pairs in combination with anions, and the ion pairs exhibited distinct photophysical properties in the dispersed state, ascribed to the formation of J- and H-aggregates. The ion pairs provided solid-state assemblies based on cation stacking. It is noteworthy that complete segregation of cations and anions was observed in a pseudo-polymorph of the ion pair with pentacyanocyclopentadienide as a π-electronic anion. In the crystalline state, the ion pairs exhibited photophysical properties and electric conductivity derived from cation stacking. In particular, the charge-segregated ion-pairing assembly induces an electric conductive pathway along the stacking axis. The charge-segregated mode and fascinating properties were derived from the reduced electrostatic repulsion between adjacent π-electronic cations via dipole–dipole interactions.     

Stabilizing Liquids Using Interfacial Supramolecular Assemblies

Stabilizing liquids based on supramolecular assembly (non-covalent intermolecular interactions) has attracted significant interest, due to the increasing demand for soft, liquid-based devices where the shape of the liquid is far from the equilibrium spherical shape. The components comprising these interfacial assemblies must have sufficient binding energies to the interface to prevent their ejection from the interface when the assemblies are compressed. Here, we highlight recent advances in structuring liquids based on non-covalent intermolecular interactions. We describe some of the progress made that reveals structure–property relationships. In addition to treating advances, we discuss some of the limitations and provide a perspective on future directions to inspire further studies on structured liquids based on supramolecular assembly.     

Controlled Construction of Heteroleptic [Pd2(LA)2(LB)(LC)]4+ Cages: A Facile Approach for Site-Selective endo-Functionalization of Supramolecular Cavities

Construction of supramolecular structures with internal functionalities is a promising approach to build enzyme-like cavities. The endo-functionalized [Pd₁₂L₂₄] and [Pd₂L₄] coordination cages represent the most successful systems in this regard. However, these systems mainly contain one type of endo-moiety. We herein provide a solution for the controlled endo-functionalization of [Pd₂L₄] cages. Site-selective introduction of the endo-functional group was achieved through the formation of heteroleptic [Pd₂( L^A )₂( L^B )( L^C )] cages. Using two orthogonal steric control elements is the key for the selective formation of the hetero-assemblies. We demonstrated the construction of two hetero-cages with a single internal functional group as well as a hetero-cage with two distinct endohedral functionalities. The endo-functionalized hetero-cages bound sulfonate guests with fast-exchange dynamics. This strategy provides a new solution for the controlled endo-functionalization of supramolecular cavities.     

Highly Stable Triangular Single-Layer 2D Assemblies: Synthesis and Their Stimuli-Responsive Elastic and Anisotropic Curling

Synthesis of highly stable two-dimensional single-layer assemblies (SLAs) is a key challenge in supramolecular science, especially those with long-range molecular order and well-defined morphology. Here, thin (thickness <2 nm) triangular Au^I-thiolate SLAs with high thermo-, solvato- and mechano- stability have been synthesized via a double-ligand co-assembly strategy. Furthermore, the SLAs show assembly-level elastic and anisotropic deformation responses to external stimuli as a result of the long-range anisotropic molecular packing, which provides SLAs with new application potentials in bio-mimic nanomechanics.     

Polymer-Protein Assemblies with Tunable Vesicular and Hierarchical Nanostructures

The construction of variable structured multi-protein nano-assemblies is of great interest for the development of protein-based therapeutic systems. This study showcases the synthesis of polymer-protein assemblies with tunable structure like single- and multi-layer polymer-crosslinked protein vesicles, Janus protein vesicles and other hierarchical-structured assemblies by utilizing a dynamic template-assistant intermittent-assembly approach. The generalization of the methodology helps the protein assemblies to gain notable functional complexity. And we demonstrate compelling evidence highlighting the substantial impact of the topological morphology of protein nanoaggregates on their cellular uptake capacity.     

Asymptotic modeling of assemblies of thin linearly elastic plates

We derive various models of assemblies of thin linearly elastic plates by abutting or superposition through an asymptotic analysis taking into account small parameters associated with the size and the stiffness of the adhesive. They correspond to the linkage of two Kirchhoff–Love plates by a mechanical constraint which strongly depends on the magnitudes of the previous parameters. To cite this article: C. Licht, C. R. Mecanique 335 (2007).