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Microgels are soft colloidal particles constituted by cross-linked polymer networks with a high potential for applications. In particular, after adsorption at a fluid interface, interfacial tension provides two-dimensional (2D) confinement for microgel monolayers and drives the reconfiguration of the particles, enabling their deployment in foam and emulsion stabilization and in surface patterning for lithography, sensing and optical materials. However, most studies focus on systems of fluids with a high interfacial tension, e.g. alkanes/ or air/water interfaces, which imparts similar properties to the assembled monolayers. Here, instead, we compare two organic fluid phases, hexane and methyl tert-butyl ether, which have markedly different interfacial tension () values with water and thus tune the deformation of adsorbed microgels. We rationalize how controls the single-particle morphology, which consequently modulates the structural and mechanical response of the monolayers at varying interfacial compression. Specifically, when is low, the microgels are less deformed within the interface plane and their polymer networks can rearrange more easily upon lateral compression, leading to softer monolayers. Selecting interfaces with different surface energy offers an additional control to customize the 2D assembly of soft particles, from the fine-tuning of particle size and interparticle spacing to the tailoring of mechanical properties., Journal of Colloid and Interface Science, 608 (3), ISSN:0021-9797, ISSN:1095-7103

The development of permeable three dimensional (3D) macroporous carbon architectures loaded with active pseudocapacitive nanomaterials offers hybrid supercapacitor materials with higher energy density, shortened diffusion length for ions and higher charge/discharge rate capability, and thereby is highly relevant for electrochemical energy storage (EES). Herein, structurally complex and tailorable 3D pyrolytic carbon/Mn3O4 hybrid supercapacitor electrode materials are synthesized through self-assembly of MnO2 nanoflakes and nanoflowers onto the surface of stereolithography (SLA) 3D printed architectures via a facile wet chemical deposition route, followed by a single thermal treatment. The thermal annealing of the MnO2 nanostructures concurrent with carbonization of the polymer precursor leads to formation of a 3D hybrid supercapacitor electrode material with unique structural integrity and uniformity. The microstructural and chemical characterization of the hybrid electrode reveals the predominant formation of crystalline hausmannite-Mn3O4 after the pyrolysis/annealing process, which is a favourable pseudocapacitive material for EES. With the combination of the 3D free-standing carbon architecture with self-assembled binder-free Mn3O4 nanostructures, electrochemical capacitive charge storage with very good rate capability, gravimetric and areal capacitances (186 Fg-1 and 968 mFcm-2, respectively) and long lifespan (˃92% after 5000 cycles) is demonstrated. It is worth noting that the gravimetric capacitance value is obtained by considering the full mass of the electrode including the carbon current collector. When only the mass of the pseudocapacitive nanomaterial is considered, a capacitance value of 457 Fg-1 is achieved, which is comparable to state-of-the-art Mn3O4-based supercapacitor electrode materials.

Spiky/hollow metal nanoparticles have applications across a broad range of fields. However, current bottom-up methods to produce spiky/hollow metal nanoparticles rely heavily on the use of strongly adsorbing surfactant molecules, which is undesirable since these passivate the product particle surfaces. Here we report a high-yield surfactant-free synthesis of spiky hollow Au-Ag nanostars (SHAANs). Each SHAAN is composed of more than 50 spikes attached to a hollow ca. 150 nm diameter cubic core, which makes SHAANs highly plasmonically and catalytically active. Moreover, the surfaces of SHAANs are chemically exposed which gives them significantly enhanced functionality compared to their surfactant-capped counterparts, as demonstrated in surface-enhanced Raman spectroscopy (SERS) and catalysis. The chemical accessibility of the pristine SHAANs also allows the use of hydroxyethyl cellulose as a weakly-bound stabilizing agent. This produces colloidal SHAANs which remain stable for more than 1 month while retaining the functionalities of the pristine particles and allow even single-particle SERS to be realized., 10 pages, 6 figures, supplementary information

Hydrogels mimic the natural extracellular matrix in terms of their nanofibrous structure and large water content. However, the lack of a combination of properties including sufficient heterogeneity in the gel structure, intrinsic antimicrobial activity, and bioactivity limits the efficiency of hydrogels for tissue engineering applications. In this work, a hydrogel with a combination of these properties was fabricated by hybridizing silk fibroin with a low-molecular-weight peptide gelator. It was observed that silk fibroin and the peptide gelator assembled orthogonally in sequence. While the morphology of silk fibroin nanofibrils was not affected by the peptide gelator, silk fibroin promoted the formation of wider nanoribbons of the peptide gelator by modulating its nucleation and growth. Orthogonal assembly maintained the antimicrobial activity of the peptide gelator and the excellent biocompatibility of silk fibroin in the hybrid gel. The hybrid gel also demonstrated improved interactions with cells, an indicator of a higher bioactivity, possibly due to the heterogeneous double network structure.

A variety of nano-engineered photosensitizers have been developed for photodynamic therapy (PDT) of cancer diseases. However, traditional nano-engineering methods usually cannot avoid drug leakage and premature release, and have disadvantages such as low drug load and inaccurate release. The self-assembly strategy based on amphiphilic peptides has been considered to be more attractive nano-engineering method. Here we developed novel acid-activatable self-assembled nanophotosensitizers based on an amphiphilic peptide derivative. The peptide derivative was synthesized from a fluorescein molecule with thermally activated delayed fluorescence (TADF). The self-assembled nanophotosensitizers can specifically enter the tumor cells and disassemble inside lysosomes companied with “turn-on” fluorescence and photodynamic therapy effect. Such smart nanophotosensitizers will open new opportunities for cancer theranostics.

Photonic crystals film that possesses periodic dielectric structure have shown great prospect in developing environmentally friendly paper alternatives due to the unique properties of dye free and non-photobleaching, but their practical application is limited by the weak interaction between colloidal particles. Although some progress has been obtained, it is still a challenge to develop photonic paper with the desired mechanical and optical properties. Herein, multifunctional hard core/soft shell nanoparticles with controlled size are fabricated by semi-continuous seed emulsion polymerization method. Compared with convention colloidal particles, these core/shell nanoparticles can facile self-assemble into large-scale dense ordered structure film via dried at room temperature due to the relatively low glass transition temperature (Tg) of the shell layers. The facile fabrication route enables the continuous high-through put production of the photonic papers. The as-formed papers not only possess the capacity to solvent (water/ethanol) rewritable and multicolor painting, but also can rapidly reversible mechanochromic. Moreover, due to the good compatibility of core/shell interface, these photonic films possess excellent mechanical properties, demonstrating that this multifunctional film makes the fabrication of novel robust rewritable papers possible and enables visual monitoring of deformation degree.

An amphiphilic phosphodiester-linked azobenzene trimer has been exploited in the development of stimuli-responsive water-soluble supramolecular polymers. It can reversibly undergo thermal and photoisomerization between Z and E isomers in EtOH solution. Its self-assembly properties in aqueous medium have been investigated by spectroscopic and microscopic techniques, demonstrating that E - and Z -azobenzene trimers form supramolecular nanosheets and toroidal nanostructures, respectively. By virtue of the E /Z photoisomerization of azobenzene units of the trimer, these two different supramolecular morphologies can be switched upon photoirradiation. This finding paves the way towards stimuli-responsive water-soluble supramolecular polymers which hold great promise in the construction of smart functional materials and also in biological applications.

Potassium-ion batteries (PIBs) is increasingly studied because of their suitable redox potential and high natural abundance. However, potential anode materials with long-term cycling stability are still in high demand because of the large radius of K+. Herein, an MOF-derived hierarchical carbon structure and the self-assembly of CNTs on hollow carbon polyhedrons are used as carbon matrices to disperse and stabilize metal selenides(Co-Se@CNNCP). When the hybrid is utilized in PIBs, it displays a specific capacity of 410 mA h g−1 at 0.1 A g−1 after 80 cycles and 253 mA h g−1 at 0.5 A g−1 after 200 cycles with a capacity retention of 100%, while the metal selenides dispersed on hollow carbon polyhedrons without CNTs (Zn-Co-Se@NCP) lose 86% of their capacity after 200 cycles. The superior cycling stability of the hybrid is mainly attributed to the large amounts of CNTs suppressing the agglomeration of the metal selenide nanoparticles on the surface, and the hollow carbon polyhedrons cause a high structural integrity during the repreated K+ insertion and extraction process. This work offers a feasible route to design a hierarchical carbon matrix for use as the anode materials of PIBs with long-term cycling stability.

Functional dicyclophanes with various substituents (e.g., NO2, Br, OCH3 and OH) were synthesized via one-pot SN2 reaction. Dicyclophanes can form nanospheres via the head-to-tail self-assembly between the cavities and the TPE units to exhibit aggregation-induced emission (AIE) in aqueous solution. These AIE-active nanospheres with cationic feature exhibited selective recognition with fluorescence response for anionic ATP via electrostatic interactions and hydrophobic effects in water.

In this paper, we report the in situ growth of FF nanotubes examined via liquid-cell transmission electron microscopy (LCTEM). This direct, high spatial, and temporal resolution imaging approach allowed us to observe the growth of peptide-based nanofibrillar structures through directional elongation. Furthermore, the radial growth profile of FF nanotubes through the addition of monomers perpendicular to the tube axis has been observed in real-time with sufficient resolution to directly observe the increase in diameter. Our study demonstrates that the kinetics, dynamics, structure formation, and assembly mechanism of these supramolecular assemblies can be directly monitored using LCTEM. The performance of the peptides and the assemblies they form can be verified and evaluated using post-mortem techniques including time-of-flight secondary ion mass spectrometry (ToF-SIMS).

Hypothesis: Common amphiphilic drug molecules often have a more rigid nonpolar part than conventional surfactants. The rigidity is expected to influence the self-assembling properties and possibly give rise to aggregation patterns different from that of regular surfactants. Experiments: We have investigated self-assembling properties of the hydrochloride salts of adiphenine (ADP), pavatrine (PVT), and amitriptyline (AMT) at concentrations up to 50 wt% using small-angle x-ray scattering, dynamic light scattering, cryo-transmission electron microscopy, and surface tension measurements. Findings: All drugs form small micelles of oblate spheroidal shape at concentrations above the critical micelle concentrations (CMC). The micelles grow weakly in size up to about 20 wt%, where the aggregation number reaches a maximum followed by a slight decrease in size at higher drug concentrations. We observe a correlation between the decrease in micelle size at high concentrations and an increasing charge of the micelles, as the degree of ionization increases with increasing drug concentration and decreasing pH. In contrast to what has previously been reported, the aggregation behavior of all studied drugs resembles the closed association behavior of conventional surfactants with a short aliphatic chain as hydrophobic tail group i.e. the micelles are always small in size and lack a second CMC. CMC values were determined with surface tension measurements, including also lidocaine hydrochloride (LDC) and chlorpromazine hydrochloride (CHL).

Hydrophobic blocks of amphiphilic block copolymers often form glassy micellar cores at room temperature with a rigid structure that limits their applications as nanocapsules for targeted delivery. Nevertheless, we prepared and analyzed core/shell micelles with a soft core, formed by a self-assembled block copolymer consisting of a hydrophobic block and a polycation block, poly(lauryl acrylate)-block-poly(trimethyl-aminoethyl acrylate) (PLA-QPDMAEA), in aqueous solution. By light and small-angle neutron scattering, by transmission electron microscopy and by fluorescence spectroscopy, we showed that these core/shell micelles are spherical and cylindrical with a fluid-like PLA core and a positively charged outer shell and that they can encapsulate and release hydrophobic solutes. Moreover, after mixing these PLA-QPDMAEA core/shell micelles with another diblock copolymer, consisting of a hydrophilic block and a polyanion block, namely poly(ethylene oxide)-block-poly(methacrylic acid) (PEO-PMAA), we observed the formation of novel vesicle-like multicompartment structures containing both soft hydrophobic and interpolyelectrolyte (IPEC) layers. By combining small-angle neutron scattering with self-consistent field modeling, we confirmed the formation of these complex vesicle-like structures with a swollen PEO core, an IPEC inner layer, a PLA soft layer, an IPEC outer layer and a loose PEO corona. Thus, these multicompartment micelles with fluid and IPEC layers and a hydrophilic corona may be used as nanocapsules with several tunable properties, including the ability to control the thickness of each layer, the charge of the IPEC layers and the stability of the micelles, to deliver both hydrophobic and multivalent solutes.

Graphene has been widely used to improve the electrochemical performance in rate and cycling stability for SnO2. However, the mechanism of the synergistic effect and the interfacial interaction between SnO2 and graphene are still not fully understood. Herein, we put forward a novel, cost effective strategy to construct hierarchical SnO2 nanoclusters anchored on the graphene sponges for lithium storage by in situ self assembly. The result shows that the synergistic effect and interfacial interaction origin form the existence of strong oxygen bridges between SnO2 and graphene via the C O Sn linkage. It is demonstrated for the first time that the interfacial interaction by C O Sn bonding plays a crucial role in the rate and cycling stability both experimentally and theoretically. Thus, the SnO2@graphene sponges exhibit remarkable rate capability (a reversible capability of 1141, 997, 912, 831, 693, 536, and 302 mA h g−1 at 0.2 C, 0.5 C, 1 C, 2 C, 5 C, 10 C and 20 C, respectively) and cycling performance (after 625 cycles at 6 A g−1 with a capacity retention of 537 mA h g−1).

Summary Bottom-up block copolymer (BCP) self-assembly involving crystallization of the core-forming block can lead, via a multistep protocol, to a range of uniform structures. One normally works with polymers of narrow molecular weight distribution, at low concentrations, and several steps are necessary because one has to separate the nucleation and growth steps. Here, we show that BCPs with polydisperse corona chains enable one to obtain a broad range of uniform structures in a single pot via a single heating-cooling-aging process, in which the nature of the structures is determined by the solvents and the annealing temperature. Most of the sample dissolves upon heating, but a fraction of the components in the mixture with the smallest corona/core block ratio persists as crystallites and, upon cooling, nucleates the growth of the more soluble components. Remarkably, this one-pot self-assembly can be scaled up to a concentration of 12% w/w, opening the door to useful applications.

Nature designs chemotactic supramolecular structures that can selectively bind specific groups present on surfaces, autonomously scan them moving along density gradients, and react once a critical concentration is encountered. While such properties are key in many biological functions, these also offer inspirations for designing artificial systems capable of similar bioinspired autonomous behaviors. One approach is to use soft molecular units that self-assemble in aqueous solution generating nanoparticles (NPs) that display specific chemical groups on their surface, enabling for multivalent interactions with complementarily functionalized surfaces. However, a first challenge is to explore the behavior of these assemblies at sufficiently high-resolution to gain insights on the molecular factors controlling their behaviors. Here we show that, coupling coarse-grained molecular models and advanced simulation approaches, it is possible to study the (autonomous or driven) motion of self-assembled NPs on a receptor-grafted surface at submolecular resolution. As an example, we focus on self-assembled NPs composed of facially amphiphilic oligomers. We observe how tuning the multivalent interactions between the NP and the surface allows to control NP binding, its diffusion along chemical surface gradients, and ultimately, the NP reactivity at determined surface group densities. In silico experiments provide physical-chemical insights on key molecular features in the self-assembling units which determine the dynamic behavior and fate of the NPs on the surface: from adhesion, to diffusion, and disassembly. This offers a privileged point of view into the chemotactic properties of supramolecular assemblies, improving our knowledge on how to design new types of materials with bioinspired autonomous behaviors.

Self‐assembly processes guide disordered molecules or particles into long‐range organized structures due to specific supramolecular interactions among the building entities. Herein, we report a unique evaporation‐induced self‐assembly (EISA) strategy for four different silica nanoparticle systems obtained through peptide functionalization of the particle surface. First, covalent peptide‐silica coupling was investigated in detail, starting with the grafting of a single amino acid (L‐serine) and expanded to specific small peptides (up to four amino acids) and transferred to different particle types (MCM‐48‐type MSNs, solid nanoparticles, and newly developed virus‐like nanoparticles). These materials were investigated regarding their ability to undergo EISA, which was shown to be independent of particle type and amount of peptide anchored to their surface. This EISA‐based approach provides new possibilities for the design of future advanced drug delivery systems, engineered hierarchical sorbents, and nanocatalyst assemblies., Evaporation‐induced self‐assembly of a bioconjugate is reported. The formation of ring‐like structures was independent of different silica particle types and the amount of peptide conjugated to the material. This novel approach paves the way for further production of functional materials for separation, catalysis, and medical applications.

Summary DNA nanostructures are highly addressable and compatible with biological systems but often require hundreds of unique strands for their assembly. On the other hand, nature can assemble complex structures from identical building blocks by compartmentalizing the process: assembling molecules into sub-components and bringing these together across multiple length scales. Inspired by this process, we report DNA-polymer conjugates that assemble through a unique heat-driven hierarchical mechanism to form fibers displaying blocks of different DNA sequences along their axis of polymerization. These one-dimensional “thermoset” DNA fibers retain the compartmentalization programmed in the pre-assembled segments. Length control over fiber segments is also achieved through gel purification of pre-assembled cylindrical micelles. Importantly, we show that the stereochemical sequence of the hydrophobic core can be amplified into distinctive morphological traits in the DNA fibers. Molecular dynamics simulations are used to model the structure and elucidate how stereochemical sequence manifests itself in different fiber-fiber interactions.

Summary The design principle of supramolecular architectures through a bottom-up strategy has always been guided by polyhedra such as Platonic solids, Archimedean solids, and prisms (antiprisms) with high symmetry. Non-uniform convex polyhedra with regular faces, i.e., Johnson solids, are rarely constructed experimentally although their topologies have been predicted through mathematical theory. Herein, self-assembly of a giant triangular orthobicupola [Zn24612], one of 92 Johnson solids J27, has been achieved from the coordination between 24 Zn2+ and 12 tetrakis-terpyridine building blocks 6 in DMF (N,N-Dimethylformamide). Different from classical Oh or Td symmetric cuboctahedron, the structure of this triangular orthobicupola revealed D3 symmetry which has been unambiguously determined by synchrotron X-ray analysis, NMR, and mass spectrometry. Surprisingly, the self-assembly process has been found to be solvent dependent. The same Zn2+ and tetrakis-terpyridine ligand 6 assembled into another pentagonal prism with the composition of [Zn20610] when using methanol as the reaction solvent.

Supramolecular soft-templating approaches to mesoporous materials have revolutionized the generation of regular nanoarchitectures exhibiting unique features such as uniform pore structure with tunable dimensions, large surface area, and high pore volume, variability of composition, and/or ease of functionalization with a wide range of organo-functional groups or good hosts for the in situ synthesis of nano-objects. One appealing concept in this field is the development of ordered mesoporous thin films as such a configuration has proven to be essential for various applications including separation, sensing, catalysis (electro and photo), energy conversion and storage, photonics, solar cells, photo- and electrochromism, and low-k dielectric coatings for microelectronics, bio and nanobio devices, or biomimetic surfaces. Supported or free-standing mesoporous films are mostly prepared by evaporation induced self-assembly methods, thanks to their good processing capability and flexibility to manufacture mesostructured oxides and organic-inorganic hybrids films with periodically organized porosity.One important challenge is the control of pore orientation, especially in one-dimensional nanostructures, which is not straightforward from the above evaporation induced self-assembly methods. Accessibility of the pores represents another critical issue, which can be basically ensured in the event of effective interconnections between the pores, but the vertical alignment of mesopore channels will definitely offer the best configuration to secure the most efficient transfer processes through the mesoporous membranes. The orthogonal growth of mesochannels is however not thermodynamically favored, requiring the development of methods enabling self-organization through nonequilibrium states. We found that electrochemistry afforded a real boon to tackle this problem via the electrochemically assisted self-assembly (EASA) method, which not only provides a fast and versatile way to generate highly ordered and hexagonally packed mesopore channels but also constitutes a real platform for the development of functionalized oriented films carrying a wide range of organo-functional groups of adjustable composition and properties.This Account introduces the EASA concept and discusses its development along with the significant progress made from its discovery, notably in view of recent advances on the functionalization of oriented mesoporous silica films, which expand their fields of application. EASA is based on the in situ combination of electrochemically triggered pH-induced polycondensation of silica precursors with electrochemical interfacial surfactant templating, leading to the very fast (a few seconds) growth of vertically aligned silica walls through self-assembly around surfactant hemimicelles transiently formed onto the underlying support. This method benefits from the possibility to deposit uniform thin films onto surfaces of different natures and complex morphologies including at the microscale. From this discovery, our research expanded to cover domains beyond the simple production of bare silica films, turning to the challenge of incorporation and exploitation of organo-functional groups or nanofilaments. So far, the great majority of methods developed for the functionalization of mesoporous silica is based on postsynthesis grafting or co-condensation approaches, which suffer from serious limitations with oriented films (pore blocking, lack of ordering). We demonstrated the uniqueness of EASA combined with click chemistry to afford a versatile and universal route to oriented mesoporous films bearing organo-functional groups of multiple composition. This opened perspectives for future developments and applications, some of which (sensing, permselective coatings, energy storage, electrocatalysis, electrochromism) are also considered in this Account.

The self-assembly and structure of nanoparticles containing curved polycyclic aromatic hydrocarbon molecules (cPAHs) are investigated using molecular modelling. These polar fullerene-like molecules are receiving increased attention recently due to the steric and electronic properties caused by the inclusion of five-membered ring(s) within their hexagonal lattice. In this work, the curPAHIP potential is extended to describe the interactions between large cPAHs. It is then used within molecular dynamics simulations to produce nanoparticles containing cPAHs. Structural and energetic metrics, including diameter, density, intermolecular spacing, coordination number, alignment angle, radial distance, and energy value, are used to analyse systems containing cPAHs of different sizes and ratios, and containing flat PAHs or ions. Homogeneous cPAH particles are more tightly packed than their flat PAH counterparts, with large cPAHs displaying stacked columnar configurations absent in nanoparticles containing small cPAHs. Mixing cPAHs of different sizes disrupts the ordered mesophase and forms a core-shell structure in which the larger molecules make up the core and the smaller molecules comprise the shell, although this partitioning is less distinct compared to flat PAHs. In addition, the presence of flat PAHs and ions within cPAH nanoparticles promotes distinct arrangements dominated by weak dispersive interactions and strong electrostatic interactions, respectively.

There is an increased interest in the use of natural surfactant as replacements for synthetic surfactants due to their biosustainable and biocompatible properties. A category of natural surfactants which are attracting much current interest is the triterpenoid saponins; surface active components found extensively in a wide range of plant species. A wide range of different saponin structures exist, depending upon the plant species they are extracted from; but regardless of the variation in structural details they are all highly surface active glycosides. Greater exploitation and application requires a characterisation and understanding of their basic adsorption and self-assembly properties.HypothesisGlycyrrhizic acid, extracted from Licorice root, is a monodesmosidic triterpenoid saponin. It is widely used in cosmetic and pharmaceutical applications due to its anti-inflammatory properties, and is an ingredient in foods as a sweetener additive. It has an additional attraction due to its gel forming properties at relatively low concentrations. Although it has attracted much recent attention, many of its basic surface active characteristics, adsorption and self-assembly, remain relatively unexplored. How the structure of the Glycyrrhizic acid saponin affects its surface active properties and the impact of gelation on these properties are important considerations, and to investigate these are the focus of the study.ExperimentsIn this paper the adsorption properties at the air-water interface and the self-assembly in solution have been investigated using by neutron reflectivity and small angle neutron scattering; in non-gelling and gelling conditions.FindingsThe adsorption isotherm is determined in water and in the presence of gelling additives, and compared with the adsorption behaviour of other saponins. Gelation has minimal impact on the adsorption; apart from producing a rougher surface with a surface texture on a macroscopic length scale. Globular micelles are formed in aqueous solution with modest anisotropy, and are compared with the structure of other saponin micelles. The addition of gelling agents results in only minimal micelle growth, and the solutions remain isotropic under applied shear flow.

A triple dynamic complex system has been designed, implementing a dynamic covalent process coupled to two supramolecular self-assembly steps. To this end, two dynamic covalent libraries (DCLs), DCL-1 and DCL-2, have been established on the basis of dynamic covalent C═C/C═N organo-metathesis between two Knoevenagel derivatives and two imines. Each DCL contains a barbituric acid-based Knoevenagel constituent that may undergo a sequential double self-organization process involving first the formation of hydrogen-bonded hexameric supramolecular macrocycles that subsequently undergo stacking to generate a supramolecular polymer SP yielding a viscous gel state. Both DCLs display selective self-organization-driven amplification of the constituent that leads to the SP. Dissociation of the SP on heating causes reversible randomization of the constituent distributions of the DCLs as a function of temperature. Furthermore, diverse distribution patterns of DCL-2 were induced by modulation of temperature and solvent composition. The present dynamic systems display remarkable self-organization-driven constitutional adaption and tunable composition by coupling between dynamic covalent component selection and two-stage supramolecular organization. In more general terms, they reveal dynamic adaptation by component selection in low Reynolds number conditions of living systems where frictional effects dominate inertial behavior.

Discrete and structurally diverse foldamer sequences are constructed in both natural and abiotic systems primarily using inert connectivity with irreversible organic covalent bonds, serving to preserve the identity of the sequence. The formation of sequences under thermodynamic control using labile coordination bonds would be attractive for synthetic ease and modular capability, but this presents issues regarding sequence preservation. Here is presented an approach integrating palladium(II) metal ions into the sequence itself, with fidelity maintained through use of complementary pairings of ligand arrangements at the metal centre. This is accomplished using sites of different denticity and/or hydrogen bonding capability. In this fashion, discrete and ordered metallo-sequences are formed as thermodynamic products in a single step, and these then fold into defined conformations due to π-π interactions between electron-rich and -poor aromatic regions of the combined componentry.

Summary The synthesis of multi-walled nanostructures represents a formidable challenge owing to the limitations imposed by existing synthetic strategies. Herein, we report a strategy involving molecular-strain engineering (MSE) for constructing double-walled polyhedra from strained bow-shaped macrocycles called molecular bows (MBs). As a proof of concept, four double-walled tetrahedra have been assembled from L-shaped dual-panels subtending ∼70.5° and producing MBs, which incorporate porphyrin and o-xylylene units, forming strained shape-persistent conformations. The head-to-tail closed-loop stacking of these units, driven by complementary non-covalent bonding interactions, leads to a large porphyrin-lined tetrahedron encapsulating a small o-xylylene-lined tetrahedron. The synergistic aromatic shielding effects emanating from the porphyrin tetrahedron result in the largest upfield chemical shifts of −7.7 ppm for protons and −8.8 ppm for carbons from those for the free dual panels. This demonstration, which features the launching of MSE for constructing sophisticated supramolecular nanostructures, could herald a fresh approach to the fabrication of multi-porphyrin photocatalytic systems.

Herein, a solution-free dry strategy for the growth of self-assembled ordered tricopper phosphide (Cu3P) nanorod arrays is developed and the product is employed as a high-energy, stable positive electrode for a solid-state hybrid supercapacitor (HSC). The ordered Cu3P nanorod arrays grown on the copper foam deliver an excellent specific capacity of 664 mA h/g with an energy efficiency of 88% at 6 A/g and an ultra-long cycling stability over 15,000 continuous charge–discharge cycles. These electrochemical features are attributed to the ordered growth of the Cu3P nanorod arrays, which offers a large number of accessible electroactive sites, a reduced number of ion transfer paths, and reversible redox activity. The potential of the Cu3P nanorod arrays is further explored by engineering solid-state HSCs in which the nanorods are paired with an activated carbon-based negative electrode. The constructed cell is shown to convey a specific energy of 76.85 Wh/kg at a specific power of 1,125 W/kg and an 88% capacitance retention over 15,000 cycles. Moreover, the superior energy storing and delivery capacity of the cell is demonstrated by an energy efficiency of around 65%. The versatile solution-free dry strategies developed here pave the way towards engineering a range of electrode materials for next-generation energy storage systems.

Embargado hasta 09/04/2023 Polymersomes and related self-assembled nanostructures displaying Aggregation-Induced Emission (AIE) are highly relevant for plenty of applications in imaging, biology and functional devices. Experimentally simple, scalable and universal strategies for on-demand self-assembly of polymers rendering well-defined nanostructures are highly desirable. A purposefully designed combination of amphiphilic block copolymers including tunable lengths of hydrophilic polyethylene glycol (PEGm) and hydrophobic AIE polymer poly(tetraphenylethylene-trimethylenecarbonate) (P(TPE-TMC)n) has been studied at the air/liquid interface. The unique 2D assembly properties have been analyzed by thermodynamic measurements, UV-vis reflection spectroscopy and photoluminescence in combination with molecular dynamics simulations. The (PEG)m-b-P(TPE-TMC)n monolayers formed tunable 2D nanostructures self-assembled on demand by adjusting the available surface area. Tuning of the PEG length allows to modification of the area per polymer molecule at the air/liquid interface. Molecular detail on the arrangement of the polymer molecules and relevant molecular interactions has been convincingly described. AIE fluorescence at the air/liquid interface has been successfully achieved by the (PEG)m-b-P(TPE-TMC)n nanostructures. An experimentally simple 2D to 3D transition allowed to obtain 3D polymersomes in solution. This work suggests that engineered amphiphilic polymers for AIE may be suitable for selective 2D and 3D self-assembly for imaging and technological applications.

Biomolecular assemblies composed of proteins and oligonucleotides play a central role in biological processes. While in nature, oligonucleotides and proteins usually assemble via non‐covalent interactions, synthetic conjugates have been developed which covalently link both modalities. The resulting peptide‐oligonucleotide conjugates have facilitated novel biological applications as well as the design of functional supramolecular systems and materials. However, despite the importance of concerted protein/oligonucleotide recognition in nature, conjugation approaches have barely utilized the synergistic recognition abilities of such complexes. Herein, the structure‐based design of peptide‐DNA conjugates that bind RNA through Watson‐Crick base pairing combined with peptide‐mediated major groove recognition is reported. Two distinct conjugate families with tunable binding characteristics have been designed to adjacently bind a particular RNA sequence. In the resulting ternary complex, their peptide elements are located in proximity, a feature that was used to enable an RNA‐templated click reaction. The introduced structure‐based design approach opens the door to novel functional biomolecular assemblies., DNA, Protein, RNA: The structure‐based design of biomolecular conjugates composed of protein and DNA fragments that synergistically bind RNA via Watson‐Crick base pairing and peptide‐mediated major groove recognition is reported. Two distinct conjugate families with tunable binding characteristics were designed whereby two conjugates can simultaneously assemble on a single RNA scaffold. Through ternary complex formation, the peptide elements of each conjugate are drawn into close proximity, and this feature was exploited to enable an RNA‐templated, double click reaction.

We carried out steady-state and stopped-flow photophysical measurements to determine the kinetics of a discrete disassembly driven turn-on fluorescent system. On and off rates for both DimerDye1 assembly and nicotine binding were determined. Relative rates for these competing processes provide insight on how this system can be optimized for sensing applications. Kinetics studies in artificial saliva showed that moving to more complex media has minimal effects on the sensing ability of the system.

A label-free fluorescence assay for hyaluronidase (HAase) activity based on self-assembly of quantum dots is developed. A cationic polymer (polycation) can induce aggregation of the negatively charged quantum dots through electrostatic interactions and the fluorescence of the quantum dots is quenched. When the polycation is mixed with hyaluronic acid (HA), intense binding of HA to the polycation makes the quantum dots free and recovery of the fluorescence of the quantum dots is observed. However, in the presence of HAase, HA is hydrolyzed into small fragments and the polycation induces reaggregation of the quantum dots. A simple and rapid fluorescence sensor with high sensitivity and selectivity for HAase activity detection is therefore successfully established with a detection limit of 0.01 U/mL. Moreover, we have demonstrated an assay that can be applied to detect HAase activity in a complex mixture sample including 1% human serum.

The structuring of liquid-liquid and liquid-air interfaces may play an important role in novel microfabrication platforms and biotechnologies, from the spontaneous formation of microfilaments from liquid droplets and the 3D printing of liquids, to the culture of stem cells on emulsions. Understanding the mechanical anisotropy of associated liquid interfaces is essential for the development of such systems. Models of AFM indentation at liquid interfaces, based on the Young-Laplace model, currently do not allow the quantification of interfacial mechanical properties of associated molecular films. This report presents such a model and compares its predictions to interfacial mechanical properties characterised via interfacial shear rheology. An extreme reversal of mechanical anisotropy of liquid-liquid interfaces is observed, upon self-assembly of protein nanosheets, by 5 orders of magnitude. Results indicate that, although interfacial rheology is more sensitive than AFM indentation to the mechanics of molecular films in the low range of interfacial mechanics, AFM indentation allows the quantification of mechanical properties of stiffer molecular films, and remains better adapted to the characterisation of small samples and enables the characterisation of local heterogeneity.

Self-assembly of colloidal nanoparticles (NPs) into well-defined superstructures has been recognized as one of the most promising ways to fabricate rationally-designed functional materials for a variety of applications. Introducing hierarchical mesoporosity into NP superstructures will facilitate mass transport while simultaneously enhancing the accessibility of constituent NPs, which is of critical importance for widening their applications in catalysis and energy-related fields. Herein, we develop a colloidal co-assembly strategy to construct mesostructured, carbon-coated Co0.5Fe2.5O4 NP superstructures (M-C@CFOSs), which show great promise as highly efficient electrocatalysts for the oxygen evolution reaction (OER). Specifically, organically-stabilized SiO2 NPs are employed as both building blocks and sacrificial template, which co-assemble with Co0.5Fe2.5O4 NPs to afford binary NP superstructures through a solvent drying process. M-C@CFOSs are obtainable after in situ ligand carbonization followed by the selective removal of SiO2 NPs. The hierarchical mesoporous structure of M-C@CFOSs, combined with the conformal graphitic carbon coating derived from the native organic ligands, significantly improves their electrocatalytic performance as OER electrocatalysts when compared with nonporous Co0.5Fe2.5O4 NP superstructures. This work establishes a new and facile approach for designing NP superstructures with hierarchical mesoporosity, which may find wide applications in energy storage and conversion.

Chondroitin sulfate-mediated albumin corona nanoparticles were readily prepared without any chemical reaction, and their active tumor targeting and therapeutic effects were examined. Negatively charged chondroitin sulfate (CS) and positively charged doxorubicin (DOX) self-assembled into nanoparticles (CS-DOX-NPs) via electrostatic interactions. Bovine serum albumin (BSA) was then adsorbed on the surface of CS-DOX-NPs to form albumin corona nanoparticles (BC-DOX-NPs) protected from endogenous proteins. Due to the dual effect of BSA and CS, BC-DOX-NPs interacted with the gp60, SPARC and CD44 receptors on tumor cells, facilitating their rapid and efficient transcytosis and improving their accumulation and uptake within tumor tissues. The simultaneous presence of BSA and CS also allowed BC-DOX-NPs to target CD44 efficiently, leading to greater cellular uptake and cytotoxicity against 4T1 cells than CS-DOX-NPs or free DOX. Intravenous injection of BC-DOX-NPs into orthotopic 4T1 tumor-bearing mice led to greater drug accumulation at the tumor site than with CS-DOX-NPs or free DOX, resulting in significant inhibition of tumor growth and lower exposure of major organs to the drug., Graphical abstract Albumin corona can enhance the anti-tumor effect of chondroitin sulfate-mediated nanoparticles through BSA-gp60-SPARC pathway, which helps nanoparticles pass through the vascular endothelial barrier faster and accumulate more in tumor tissues.Image, graphical abstract

Janus particles exhibit a strong tendency to directionally assemble and segregate to interfaces and thus offer advantages as colloidal analogues of molecular surfactants to improve the stability of multiphasic mixtures. Investigation and application of the unique adsorption properties require synthetic procedures that enable careful design and reliable control over the particles’ asymmetric chemistry and wettability profiles with high morphological uniformity across a sample. Herein, we report on a novel one-step synthetic approach for the generation of amphiphilic polymer Janus particles with highly uniform and tunable wettability contrasts, which is based on using reconfigurable bi-phasic Janus emulsions as versatile particle scaffolds. Two phase-separated acrylate oils were used as the constituent droplet phases and transformed into their solidified Janus particle replicas via UV-induced radical polymerization. Using Janus emulsions as particle precursors offers the advantage that their internal droplet geometry can be fine-tuned by changing the force balance of surface tensions acting at the individual interfaces via surfactants or the volume ratio of the constituent phases. In addition, preassembled functional surfactants at the droplet interfaces can be locked in position upon polymerization, which enables both access toward postfunctionalization reaction schemes and the generation of highly uniform Janus particles with adjustable wettability profiles. Depending on the particle morphology and wettability, their interfacial position can be adjusted, which allows us to stabilize either air bubbles-in-water or water droplets-in-air (liquid marbles). Motivated by the interfacial activity of the particles and particularly the longevity of the resulting particle-stabilized air-in-water bubbles, we explored their ability to promote the delivery of oxygen inside a liquid-phase reaction medium, namely, for the heterogeneous Au-NP-mediated catalytic oxidation of d-glucose. We observed a 2.2-fold increase in the reaction rate attributed to the increase of the local concentration of oxygen around catalysts, thus showcasing a new strategy to overcome the limited solubility of gases in aqueous reaction media.

Controlling the structural order of nanoparticles (NPs), morphology, and composition is of paramount significance in tailoring the physical properties of nanoassembly. However, the commonly reported symmetrical nanocomposites often suffer an interference or sacrifice of the photophysical properties of the original components. To address this challenge, we developed a novel type of organic-inorganic Janus nanocomposite (JNCP) with an asymmetric architecture, offering unique features such as the precisely controlled localization of components, combined modular optical properties, and independent stimuli. As a proof of concept, JNCPs were prepared by incorporating two photoacoustic (PA) imaging agents, namely an organic semiconducting dye and responsive gold nanoparticles (AuNP) assembly in separate compartments of JNCP. Theoretical simulation results confirmed that the formation mechanism of JNCPs arises from the entropy equilibrium in the system. The AuNP assembly generated a PA images with the variation of pH, while the semiconducting molecule served as an internal PA standard agent, leading to ratiometric PA imaging of pH. JNCP based probe holds great potential for real-time and accurate detection of diverse biological targets in living systems.

Hypothesis Controlled particle assembly from a dilute suspension droplet is challenging yet important for many lab-on-a-chip and biosensing applications. The formation of hot spots on the localized surface plasmonic resonance (LSPR) substrates induced by laser excitation can generate microbubbles. These microbubbles, upon the laser removal, shrink and collapse due to electron energy dissipation, leading to guided particle assembly on the LSPR substrate. Experiments After depositing dilute silica particles dispersions on both nanoisland (AuNI) and planar gold (Au) plasmonic substrates (referred to as LSPR and SPR substrates respectively), microbubbles were formed when a laser beam was applied. Particle dispersion concentration, laser power, and the radius of circular laser sequence were varied to produce different sizes of particle clusters on the LSPR substrate after bubble shrinkage upon the laser removal. To stabilize the assembled structures over time, sodium chloride (NaCl) was ad ded to the dispersions. Findings Even though thermo-plasmonic flow and microbubbles can be produced with SPR substrates, particle assembly is only possible on LSPR substrates because of electron energy dissipation via nanoscale air gaps trapped in the LSPR substrate. By tuning the laser power, the radius of the circular laser sequence, and the particle dispersion concentration, the number of particles in the assembled structure can be controlled. The addition of NaCl to the dispersion can screen the electrostatic charges among the particles and between the particles and substrate, favoring hydrogen bonding and stabilizing the assembled structures for hours. These findings establish a new framework for utilizing nanophotonic chips where particle assembly can be achieved by a single source of light.

Here we report the formation of an unexpected and unique family of chiral helicates. Crystal structures show that these triple-stranded ZnII2 L3 complexes are held together by subcomponent assembly of axially chiral diamine-functionalized 1,1'-biphenol ditopic with 2-formylpyridine and ZnII . Specifically, the molecular helicity of the complexes can be controlled by the absolute configurations of the bimetallic vertices, which has been shown to be homoconfiguration (ΔΔ) or mesomeric configuration (ΔΛ), depending critically on the bulky groups and length of the spacers. Fascinatingly, in this system we can engineer the space-restricted chiral microenvironments with varied polar and apolar moieties, which profoundly influence the binding affinities and chiral discrimination properties of the helicates, leading to highly enantio- and helix-sense-selective recognition for chiral amino alcohols (up to 9.35). This work reveals the transformation of single-molecule chirality to global supramolecular chirality within well-defined helicates and demonstrates that their chiral discrimination are highly dependent on the superior microenvironments.

N-Heterocyclic carbenes (NHCs) are promising modifiers and anchors for surface functionalization and offer some advantages over thiol-based systems. Because of their strong binding affinity and high electron donation, NHCs can dramatically change the properties of the surfaces to which they are bonded. Highly ordered NHC monolayers have so far been limited to metal surfaces. Silicon, however, remains the element of choice in semiconductor devices and its modification is therefore of utmost importance for electronic industries. Here, a comprehensive study on the adsorption of NHCs on silicon is presented. We find covalently bound NHC molecules in an upright adsorption geometry and demonstrate the formation of highly ordered monolayers exhibiting good thermal stability and strong work function reductions. The structure and ordering of the monolayers is controlled by the substrate geometry and reactivity and in particular by the NHC side groups. These findings pave the way towards a tailor-made organic functionalization of silicon surfaces and, thanks to the high modularity of NHCs, new electronic and optoelectronic applications. Although monolayers of N-heterocyclic carbenes (NHCs) readily form on metals, surface reactivity usually hinders their self-assembly on semiconductors. Now, it has been shown that thermally stable, well-ordered monolayers of NHCs can be formed on silicon surfaces. A large reduction in work function is observed and steric effects enable sufficient diffusivity of the NHCs.

Long-range electrostatic interactions beyond biomolecular interaction interfaces have not been extensively studied due to the limitation in engineering electric double layers in physiological fluids. Here we find that long-range electrostatic interactions play an essential role in kinetic modulation of DNA hybridizations. Protein and gold nanoparticles with different charges are encapsulated in tetrahedral frameworks to exert diverse electrostatic effects on site-specifically tethered single DNA strands. Using this strategy, we have successfully modulated the hybridization kinetics in both bulk solution and single molecule level. Experimental and theoretical studies reveal that long-range Coulomb interactions are the key factor for hybridization rates. This work validates the important role of long-range electrostatic forces in nucleic acid-biomacromolecule complexes, which may encourage new strategies of gene regulation, antisense therapy, and nucleic acid detection.

The development of robust and thin CO2 separation membranes that allow fast and selective permeation of CO2 will be crucial for rebalancing the global carbon cycle. Hydrogels are attractive membrane materials because of their tunable chemical properties and exceptionally high diffusion coefficients for solutes. However, their fragility prevents the fabrication of thin defect-free membranes suitable for gas separation. Here, we report the assembly of defect-free hydrogel nanomembranes for CO2 separation. Such membranes can be prepared by coating an aqueous suspension of colloidal hydrogel microparticles (microgels) onto a flat, rough, or micropatterned porous support as long as the pores are hydrophilic and the pore size is smaller than the diameter of the microgels. The deformability of the microgel particles enables the autonomous assembly of defect-free 30-50 nm-thick membrane layers from deformed ∼15 nm-thick discoidal particles. Microscopic analysis established that the penetration of water into the pores driven by capillary force assists the assembly of a defect-free dense hydrogel layer on the pores. Although the dried films did not show significant CO2 permeance even in the presence of amine groups, the permeance dramatically increased when the membranes are adequately hydrated to form a hydrogel. This result indicated the importance of free water in the membranes to achieve fast diffusion of bicarbonate ions. The hydrogel nanomembranes consisting of amine-containing microgel particles show selective CO2 permeation (850 GPU, αCO2/N2 = 25) against post-combustion gases. Acid-containing microgel membranes doped with amines show highly selective CO2 permeation against post-combustion gases (1010 GPU, αCO2/N2 = 216) and direct air capture (1270 GPU, αCO2/N2 = 2380). The membrane formation mechanism reported in this paper will provide insights into the self-assembly of soft matters. Furthermore, the versatile strategy of fabricating hydrogel nanomembranes by the autonomous assembly of deformable microgels will enable the large-scale manufacturing of high-performance separation membranes, allowing low-cost carbon capture from post-combustion gases and atmospheric air.

Nanolattices exhibit attractive mechanical, energy conversion and optical properties, but it is challenging to fabricate large nanolattices while maintaining the dense regular nanometre features that enable their properties. Here we report a crack-free self-assembly approach for fabricating centimetre-scale nickel nanolattices with much larger crack-free areas than prior self-assembled nanolattices and many more unit cells than three-dimensionally printed nanolattices. These nickel nanolattices have a feature size of 100 nm, a grain size of 30 nm and a tensile strength of 260 MPa, which approaches the theoretical strength limit for porous nickel. The self-assembly method and porous metal mechanics reported in this work may advance the fabrication and applications of high-strength multifunctional porous materials.

A range of morphologically distinct metallosupramolecular Cu(II) and Pd(II) complexes has been constructed, based on the tritopic ligand 1,1',1″-(benzene-1,3,5-triyl)tris(4,4-dimethylpentane-1,3-dione) (H). By control of the reaction conditions, it is possible to generate distinct coordination assemblies possessing either macrocyclic or polymeric structures and more importantly distinct activity in catalysis of the Suzuki-Miyaura cross-coupling.

Controlling enzyme orientation and location on surfaces is a critical step for their successful deployment in diverse applications from biosensors to lab-on-a-chip devices. Functional activity of the enzymes on the surface will largely depend on the spatial arrangement and orientation. Solid binding peptides have been proven to offer versatility for immobilization of biomolecules on inorganic materials including metals, oxides, and minerals. Previously, we demonstrated the utility of a gold binding peptide genetically incorporated into the enzyme putrescine oxidase (PutOx-AuBP), enabling self-enzyme assembly on gold substrates. PutOx is an attractive biocatalyst among flavin oxidases, using molecular oxygen as an electron acceptor without requiring a dissociable coenzyme. Here, we explore the selective self-assembly of this enzyme on a range of surfaces using atomic force microscopy (AFM) along with the assessment of functional activity. This work probes the differences in surface coverage, distribution, size, shape, and activity of PutOx-AuBP in comparison to those of native putrescine oxidase (PutOx) on multiple surfaces to provide insight for material-selective enzymatic assembly. Surfaces investigated include metal (templated-stripped gold (TSG)), oxide (native SiO2 on Si(111)), minerals (mica and graphite), and self-assembled monolayers (SAMs) with a range of hydrophobicity and charge. Supported by both the coverage and the dimensions of immobilized enzymes, our results indicate that of the surfaces investigated, material-selective binding takes place with orientation control only for PutOx-AuBP onto the TSG substrate. These differences are consistent with the measurements of surface-bound enzymatic activities. Substrate-dependent differences observed indicate significant variations in enzyme-surface interactions ranging from peptide-directed self-assembly to enzyme aggregation. The implications of this study provide insight for the fabrication of enzymatic patterns directed by self-assembling peptide tags onto localized surface regions. Enabling functional enzyme-based nanoscale materials offers a fascinating path for utilization of sustainable biocatalysts integrated into multiscale devices.

Self-assembly of block copolymers (BCPs) is an alternative patterning technique that promises high resolution and density multiplication with lower costs. The defectivity of the resulting nanopatterns remains too high for many applications in microelectronics and is exacerbated by small variations of processing parameters, such as film thickness, and fluctuations of solvent vapor pressure and temperature, among others. In this work, a solvent vapor annealing (SVA) flow-controlled system is combined with design of experiments (DOE) and machine learning (ML) approaches. The SVA flow-controlled system enables precise optimization of the conditions of self-assembly of the high Flory-Huggins interaction parameter (χ) hexagonal dot-array forming BCP, poly(styrene-b-dimethylsiloxane) (PS-b-PDMS). The defects within the resulting patterns at various length scales are then characterized and quantified. The results show that the defectivity of the resulting nanopatterned surfaces is highly dependent upon very small variations of the initial film thicknesses of the BCP, as well as the degree of swelling under the SVA conditions. These parameters also significantly contribute to the quality of the resulting pattern with respect to grain coarsening, as well as the formation of different macroscale phases (single and double layers and wetting layers). The results of qualitative and quantitative defect analyses are then compiled into a single figure of merit (FOM) and are mapped across the experimental parameter space using ML approaches, which enable the identification of the narrow region of optimum conditions for SVA for a given BCP. The result of these analyses is a faster and less resource intensive route toward the production of low-defectivity BCP dot arrays via rational determination of the ideal combination of processing factors. The DOE and machine learning-enabled approach is generalizable to the scale-up of self-assembly-based nanopatterning for applications in electronic microfabrication.

Nature segregates fundamental tasks such as information storage/transmission and catalysis between two different compound classes (e.g. polynucleotides for replication and folded polyamides for catalysis). This division of labor is likely a product of evolution, raising the question of how simpler systems in which replicators and folded macromolecules co‐exist may emerge in the transition from chemistry to biology. In synthetic systems, achieving co‐existence of replicators and foldamers in a single molecular network remains an unsolved problem. Previous work on dynamic molecular networks has given rise to either self‐replicating fibers or well‐defined foldamer structures (or completely un‐sorted complex systems). We report a system in which two cross‐reactive dithiol (nucleobase‐ and peptide‐based) building blocks self‐sort into a replicator fiber and foldamer that both emerge spontaneously and co‐exist. The self‐sorting behavior remains prevalent across different building block ratios as two phases of emergence occur: replicator growth followed by foldamer formation. This is attributed to the autocatalytic formation of the replicator fiber, followed by enrichment of the system in the remaining building block, which is subsequently incorporated into a foldamer., Two different dithiol building blocks interconvert through reversible covalent bonds to initially form a dynamic combinatorial library of macrocycles of various size. The self‐sorting process starts by the amplification of a single library member to form self‐replicating fibers. This step is followed by enrichment of the system in the remaining building block, which forms a large macrocyclic foldamer.