Self-assembled Supramolecular Structures Research Articles

Lattice Symmetry-Guided Charge Transport and Recombination in Supramolecular Assemblies

Synthetic soft materials mimicking biological structures are promising for many applications in fields such as photovoltaics and photocatalysis. For these applications, a deep understanding of the charge- and energy-transfer mechanisms is required to build more efficient devices. In this work, we investigate self-assembled 2D supramolecular structures using angle-resolved photoluminescence (PL) imaging techniques and decompose the optical transition dipoles in the supramolecular structures. Combining these optical studies with Monte Carlo simulations, we reveal the important role played by lattice symmetry in charge dissociation, transport, and recombination, as well as the exciton spin states. These mechanistic findings have important implications for engineering soft materials towards efficient energy conversion and photocatalytic applications.

Controlling the function of bioactive worm micelles by enzyme-cleavable non-covalent inter-assembly cross-linking

Drugs that form self-assembled supramolecular structures to be most-active is a promising way of creating new highly specific and active pharmaceuticals. Controlling the activity of bioactive supramolecular structures such as drug-loaded micelles is possible by both core/shell and inter-assembly cross-linking. However, if the flexibility of the assembly is mandatory for the activity cross-linking is not feasible. Thus, such structures cannot be manipulated in their activity.The present study demonstrates a novel concept to control the activity of not drug-releasing, non-cross-linked bioactive superstructures. This is achieved by formation of nanostructured nanoparticles derived by non-covalent inter-assembly cross-linking of the superstructures. This is shown on the example of amphiphilic diblock-copolymers conjugated with the antibiotic ciprofloxacin (CIP). These polymer-antibiotic conjugates form worm micelles, which greatly activate the conjugated antibiotic without releasing it. Non-covalent inter-assembly cross-linking of these CIP-worm-micelles with amphiphilic triblock copolymers terminated with lipase-cleavable esters leads to nanostructured nanoparticles that resemble cross-linked worm micelles and show an up to 135-fold lower activity than the free worm micelles. The activity of the worm-micelles can be fully recovered by cleaving the end groups of the polymeric cross-linker with lipase.

Red-light-controlled supramolecular assemblies of indigo amphiphiles at multiple length scales

Amphiphilic molecules functionalized with photoresponsive motifs have attractive prospects for applications in smart functional bio-material ranging from cell-material interfaces to drug delivery systems owing to the precisely controllable functionality of self-assembled hierarchical supramolecular structures in aqueous media by a non-invasive light stimulation with high temporal- and spatial-resolution. However, most of reported photoresponsive amphiphiles are triggered by bio-damaging UV-light, which greatly limits the potential in bio-related applications. Herein, we present newly designed red-light controlled N,N’-diaryl-substituted indigo amphiphiles (IA), exhibiting excellent photoswitchablity and photostability with dual red-/green-light in organic media. Meanwhile, aqueous solutions of IA assembled into supramolecular structures in both microscopic and macroscopic length-scale, though the photoresponsiveness of IA is slightly compromised in aqueous media. At macroscopic length-scale, morphological changes of IA macroscopic scaffold prepared by a shear-flow method can be fine adjusted upon red-light irradiation. Moreover, the preferential attachment of live h-MSCs to IA macroscopic scaffold surface also indicates a good biocompatibility of IA macroscopic scaffold. These results provide the potential for developing the next generation of red-light controlled soft functional materials with good biocompatibility.

Noncovalent Dualism in Perylene-Diimide-Based Keggin Anion Complexes: Theoretical and Experimental studies.

We report the synthesis and comprehensive characterization of organic-inorganic hybrid salts formed by bis-cationic N,N'-bis(2-(trimethylammonium)ethylene)perylene-3,4,9,10-tetracarboxylic acid bisimide (PTCD2+) and Keggin-type [XW12O40]n- (X = Si, n = 4; X = P, n = 3) polyoxometalates. (PTCD)3[PW12O40]2·3DMSO·2H2O (2) and (PTCD)2[SiW12O40]·DMSO·2H2O (3) were structurally characterized by single crystal X-ray diffraction. The cations in both structures exhibited infinite chainlike arrangements through π-π interactions, contrasting with the previously reported cation-anion stacking observed in naphthalene diimide derivatives. A detailed theoretical study employing topological analysis of the electron density distribution within the quantum theory of atoms in molecules approach provided further insights into this structural dualism. Atomic force microscopy analyses revealed the formation of self-assembled supramolecular structures on graphite from molecular monolayers (3 nm of thick) to submicrometer aggregates for 2. Hyperspectral Raman spectroscopy imaging revealed that such heterostructures are likely formed by an enhanced π-π interactions. Both complexes demonstrated interesting electrochemical behavior, photoluminescence and X-ray-induced luminescence. Electron spin resonance analysis confirmed charge separation in both compounds, with enhanced efficiency observed in compound 2. Our findings of these perylene-based organic-inorganic hybrid salts offer the potential for their application in optoelectronic devices and functional materials.

Manipulating Molecular Self-Assembly Process at the Solid-Liquid Interface Probed by Scanning Tunneling Microscopy.

The phenomenon of ordered self-assembly on solid substrates is a topic of interest in both fundamental surface science research and its applications in nanotechnology. The regulation and control of two-dimensional (2D) self-assembled supra-molecular structures on surfaces have been realized through applying external stimuli. By utilizing scanning tunneling microscopy (STM), researchers can investigate the detailed phase transition process of self-assembled monolayers (SAMs), providing insight into the interplay between intermolecular weak interactions and substrate-molecule interactions, which govern the formation of molecular self-assembly. This review will discuss the structural transition of self-assembly probed by STM in response to external stimuli and provide state-of-the-art methods such as tip-induced confinement for the alignment of SAM domains and selective chirality. Finally, we discuss the challenges and opportunities in the field of self-assembly and STM.

Virus-like particles nanoreactors: from catalysis towards bio-applications.

Virus-like particles (VLPs) are self-assembled supramolecular structures found in nature, often used for compartmentalization. Exploiting their inherent properties, including precise nanoscale structures, monodispersity, and high stability, these architectures have been widely used as nanocarriers to protect or enrich catalysts, facilitating catalytic reactions and avoiding interference from the bulk solutions. In this review, we summarize the current progress of virus-like particles (VLPs)-based nanoreactors. First, we briefly introduce the physicochemical properties of the most commonly used virus particles to understand their roles in catalytic reactions beyond the confined space. Next, we summarize the self-assembly of nanoreactors forming higher-order hierarchical structures, highlighting the emerging field of nanoreactors as artificial organelles and their potential biomedical applications. Finally, we discuss the current findings and future perspectives of VLPs-based nanoreactors.

Deciphering pressure-induced nanoarchitectonics in a monolayer of heterocoronene-based discotics at air-water and air-solid interfaces.

Understanding and control of molecular alignment at the nanoscale in self-assembled supramolecular structures is a prerequisite for the subsequent exploitation of molecules in functional devices. Here, we have clarified the surface-pressure induced molecular nanoarchitectures in a monolayer of a heterocoronene-based discotic liquid crystal (DLC) at air-water and air-solid interfaces using surface manometry, real-time Brewster angle microscopy, and real-space atomic force microscopy (AFM). Chloroform-spread DLCs at a concentration of ∼108 μM exhibit floating domains at the air-water interface comprising small aggregates of edge-on stacked molecules interacting via peripheral alkyl chains. Detailed analysis of surface manometry and relaxation measurements reveal that, upon compression, these domains coalesce to form a coherent monolayer which then undergoes irreversible structural transformations via mechanisms such as monolayer loss due to desorption and localized nucleation of defects. AFM images of the films transferred on a hydrophilic substrate reveal that with increasing surface-pressure, the nanoscale structure of the monolayer transforms from randomly oriented nanowires to tightly-packed nanowire domains, and finally to fragmented wire segments which diffuse locally above the film. These results provide a facile method for the preparation of compact, two-dimensional films of ambipolar DLC molecules with a tunable nanoarchitecture which will be crucial for their applications in nanoscale electronic devices.

Investigating the impact of inbuilt cold atmospheric pressure plasma on molecular assemblies of tryptophan enantiomers: in vitro fabrication of self-assembled supramolecular structures.

The advancements in understanding the phenomenon of plasma interactions with matter, coupled with the development of CAPP devices, have resulted in an interdisciplinary research topic of significant importance. This has led to the integration of various fields of science, including plasma physics, chemistry, biomedical sciences, and engineering. The reactive oxygen species and reactive nitrogen species generated from cold atmospheric plasma on interaction with biomolecules like proteins and peptides form various supramolecular structures. CAPP treatment of amino acids, which are the fundamental building blocks of proteins, holds potential in creating self-assembled supramolecular architectures. In this work, we demonstrate the process of self-assembly of aromatic amino acid tryptophan (Trp) enantiomers (l-tryptophan and d-tryptophan) into ordered supramolecular assemblies induced by the reactive species generated by a cold atmospheric pressure helium plasma jet. These enantiomers of tryptophan form organized structures as evidenced by FE-SEM. To assess the impact of CAPP treatment on the observed assemblies, we employed various analytical techniques such as zeta potential, dynamic light scattering and FTIR spectroscopy. Also, photoluminescence and time-resolved lifetime measurements revealed the transfiguration of individual Trp enantiomers. The LC-ESI-QTOF-MS analysis demonstrated that CAPP irradiation led to the incorporation of oxygenated ions into the pure Trp molecule. These studies of the self-assembly of Trp due to ROS and RNS interactions will help us to understand the assembly environment. This knowledge may be utilized to artificially design and synthesize highly ordered functional supramolecular structures using CAPP.

Surface Diffusion Aided by a Chirality Change of Self-Assembled Oligomers under 2D Confinement.

Chirality switching of self-assembled molecular structures is of potential interest for designing functional materials but is restricted by the strong interaction between the embedded molecules. Here, we report on an unusual approach based on reversible chirality changes of self-assembled oligomers using variable-temperature scanning tunneling microscopy supported by quantum mechanical calculations. Six functionalized diazomethanes each self-assemble into chiral wheel-shaped oligomers on Ag(111). At 130 K, a temperature far lower than expected, the oligomers change their chirality even though the molecules reside in an embedded self-assembled structure. Each chirality change is accompanied by a slight center-of-mass shift. We show how the identical activation energies of the two processes result from the interplay of the chirality change with surface diffusion, findings that open the possibility of implementing various functional materials from self-assembled supramolecular structures.

Controlling Trapping, Release, and Exchange Dynamics of Micellar Core Components.

Whereas the formation and overall stability of hierarchically organized self-assembled supramolecular structures have been extensively investigated, the mechanistic aspects of subcomponent dynamics are often poorly understood or controlled. Here we show that the dynamics of polyamidoamine (PAMAM) dendrimer based micelles can be manipulated by changes in dendrimer generation, pH, and stoichiometry, as proven by NMR and FRET. For this, dendrimers were functionalized with either fluorescein (donor) or rhodamine (acceptor) and encapsulated into separate micelles. Upon mixing, exchange of dendrimers is revealed by an increase in FRET. While dendrimicelles based on dendrimer generations 4 and 5 show a clear increase in FRET in time, revealing the dynamic exchange of dendrimers between micellar cores, generation 6 based micelles appear to be kinetically trapped systems. Interestingly, generation 6 based dendrimicelles prepared at a pH of 7.8 rather than 7.0 do show exchange dynamics, which can be attributed to about 25% less charge of the dendrimer, corresponding to the charge of a virtual generation 5.5 dendrimer at neutral pH. Changing the pH of dendrimicelle solutions prepared at a pH of 7.8 to 7.0 shows the activated release of dendrimers. High-resolution NMR spectra of the micellar core are obtained from a 1.2 GHz spectrometer with sub-micromolar sensitivity, with DOSY discriminating released dendrimers from dendrimers still present in the micellar core. This study shows that dendrimer generation, charge density, and stoichiometry are important mechanistic factors for controlling the dynamics of complex coacervate core micelles. This knowledge can be used to tune micelles between kinetically trapped and dynamic systems, with tuning of exchange and/or release speeds, to be tailored for applications in, e.g., material science, sensors, or drug delivery.

Salt Weakens Intermicellar Interactions and Structuring in Bulk Solutions and Foam Films.

Drainage via stratification in micellar foam films formulated with ionic surfactants shows dramatic changes on salt addition: both the step size and the number of steps in their stepwise thinning diminish. As the stratification process is governed by supramolecular oscillatory structural forces that arise due to confinement-induced structuring of micelles, it is apparent that salt addition reduces the magnitude, periodicity, and decay length of the oscillatory forces. In this contribution, we characterize the changes in micellar size, shape, and interactions on salt addition in bulk solutions using small-angle X-ray scattering (SAXS) to understand and elucidate the influence of salt on stratification in micellar foam films and, more broadly, on the oscillatory structural forces. Adding salt leads to a significant reduction in long-range correlations between micelles and smaller intermicellar distances. These effects manifest as a weakening of the primary peak of the structure factor, ascertained from SAXS spectra, accompanied by its shift to higher wave vectors. Weakened long-range correlations diminish the magnitude and periodicity of the oscillatory disjoining pressure leading to smaller step sizes, fewer steps, and a rich nanoscopic topography, due to the influence of disjoining pressure on the deformable interfaces. The step sizes in stratifying thin films and intermicellar distances in bulk solutions present incongruous values, implying an imperfect analogy with studies on charged nanoparticles with matched and salt concentration-independent values of measured interparticle distances that equal the periodicity of force-distance curves. We anticipate that our findings are significant for multicomponent soft and biological matter containing self-assembled supramolecular structures wherein screened Coulomb interactions govern the self-assembly, interfacial adsorption, interactions, dynamics, and stability.

Mono- and binuclear copper(II) complexes with different structural motifs and geometries: Synthesis, spectral characterization, DFT calculations and superoxide dismutase enzymatic activity

Several new copper(II) mono- and binuclear complexes, [Cu(HL)(ClO4)(H2O)]CH3OH (1), [Cu(HL)(DMF)](ClO4)CH3OH (2), [Cu2(HL)2(pyrazine)](ClO4)2(3) and [Cu2(HL)2(4,4-bipy)(ClO4)2]2H2O (4) (HL = 4-bromo-2-(pyridine-2-ylhydrazonomethyl)-phenol, 4,4-bipy = 4,4-bipyridyl) have been synthesized and characterized by elemental analysis, FTIR, UV–vis and electron paramagnetic resonance (Epr) spectroscopy. Molecular structures of all complexes have been obtained using single crystal X-ray analysis. The geometry of copper(II) in 1 is distorted square pyramidal and distorted square planar in 2. In binuclear complexes each copper(II) centre has distorted square planar and distorted square pyramidal geometry in 3 and 4, respectively. The complexes 1–4 possess the self-assembled supramolecular structures via different molecular interactions (hydrogen bondings, CH ⋯π and π⋯π stacking interactions). The possible intermolecular interactions were explored using 3D Hirshfeld surface and related 2D fingerprint plots, spectroscopic properties were studied using UV–visible and electron paramagnetic resonance techniques. Optimized geometry, frontier molecular orbital (FMO) and natural bond order (NBO) analysis were performed using density functional theory (DFT) calculations. To predict the chemical reactivity of complexes some global reactivity descriptors (chemical potential μ, electronegativity χ, hardness η and electrophilicity index ω) have been evaluated using DFT. The low temperature magnetic susceptibility measurements of binuclear complexes have been obtained predicts the magnetic exchange coupling value (J) by variable temperature measurements. The magnetic exchange coupling value (J) obtained are −8.1 and −2.4 cm−1 for 3 and 4, respectively. The superoxide dismutases (SOD) of all complexes were measured using NBT assay method. The complexes show moderate superoxide dismutase (SOD) mimetic activity.

Self-assembly pathways in a triphenylalanine peptide capped with aromatic groups

Peptide derivatives and, most specifically, their self-assembled supramolecular structures are being considered in the design of novel biofunctional materials. Although the self-assembly of triphenylalanine homopeptides has been found to be more versatile than that of homopeptides containing an even number of residues (i.e. diphenylalanine and tetraphenylalanine), only uncapped triphenylalanine (FFF) and a highly aromatic analog blocked at both the N- and C-termini with fluorenyl-containing groups (Fmoc-FFF-OFm), have been deeply studied before. In this work, we have examined the self-assembly of a triphenylalanine derivative bearing 9-fluorenylmethyloxycarbonyl and benzyl ester end-capping groups at the N- and C-termini, respectively (Fmoc-FFF-OBzl). The antiparallel arrangement clearly dominates in β-sheets formed by Fmoc-FFF-OBzl, whereas the parallel and antiparallel dispositions are almost isoenergetic in Fmoc-FFF-OFm β-sheets and the parallel one is slightly favored for FFF. The effects of both the peptide concentration and the medium on the self-assembly process have been examined considering Fmoc-FFF-OBzl solutions in a wide variety of solvent:co-solvent mixtures. In addition, Fmoc-FFF-OBzl supramolecular structures have been compared to those obtained for FFF and Fmoc-FFF-OFm under identical experimental conditions. The strength of π-π stacking interactions involving the end-capping groups plays a crucial role in the nucleation and growth of supramolecular structures, which determines the resulting morphology. Finally, the influence of a non-invasive external stimulus, ultrasounds, on the nucleation and growth of supramolecular structures has been examined. Overall, FFF-based peptides provide a wide range of supramolecular structures that can be of interest in the biotechnological field.

Cryogenic TEM imaging of artificial light harvesting complexes outside equilibrium

The energy transport in natural light-harvesting complexes can be explored in laboratory conditions via self-assembled supramolecular structures. One such structure arises from the amphiphilic dye C8S3 molecules, which self-assemble in an aqueous medium to a double-wall cylindrical nanotube reminiscent of natural light-harvesting complexes found in green sulphur bacteria. In this paper, we report a way to investigate the structure of inner nanotubes (NTs) alone by dissolving the outer NTs in a microfluidic setting. The resulting thermodynamically unstable system was rapidly frozen, preventing the reassembly of the outer NT from the dissolved molecules, and imaged using cryogenic transmission electron microscopy (cryo-TEM). The experimental cryo-TEM images and the molecular structure were compared by simulating high-resolution TEM images, which were based on the molecular modelling of C8S3 NTs. We found that the inner NT with outer walls removed during the flash-dilution process had a similar size to the parent double-walled NTs. Moreover, no structural inhomogeneity was observed in the inner NT after flash-dilution. This opens up exciting possibilities for functionalisation of inner NTs before the reassembly of the outer NT occurs, which can be broadly extended to modify the intra-architecture of other self-assembled nanostructures.

Rapid Production of Multifunctional Self-Assembling Peptides for Incorporation and Visualization within Hydrogel Biomaterials.

Peptides are of continued interest for therapeutic applications, from soluble and immobilized ligands that promote desired binding or uptake to self-assembled supramolecular structures that serve as scaffolds in vitro and in vivo. These applications require efficient and scalable synthetic approaches because of the large amounts of material that often are needed for studies of bulk material properties and their translation. In this work, we establish new methods for the synthesis, purification, and visualization of assembling peptides, with a focus on multifunctional collagen mimetic peptides (mfCMPs) relevant for formation and integration within hydrogel-based biomaterials. First, a methodical approach useful for the microwave-assisted synthesis of assembling peptide sequences prone to deletions was established, beginning with the identification of the deleted residues and their locations and followed by targeted use of dual chemistry couplings for those specific residues. Second, purification techniques that integrate the principles of heating and ion displacement with traditional chromatography and dialysis were implemented to improve separation and isolation of the desired multifunctional peptide product, which contained blocks for thermoresponsiveness and ionic interactions. Third, an approach for fluorescent labeling of these mfCMPs, which is orthogonal to their assembly and their covalent incorporation into a bulk hydrogel material, was established, allowing visualization of the resulting hierarchical fibrillar structures in three dimensions within hydrogels using confocal microscopy. The methods presented in this work allow the production of multifunctional peptides in scalable quantities and with minimal deletions, enabling future studies for better understanding of composition-structure-property relationships and for translating these biomaterials into a range of applications. Although mfCMPs are the focus of this work, the methods demonstrated could prove useful for other assembling peptide systems and for the production of peptides more broadly for therapeutic applications.

Macrochirality of Self-Assembled and Co-assembled Supramolecular Structures of a Pair of Enantiomeric Peptides.

Although macrochirality of peptides’ supramolecular structures has been found to play important roles in biological activities, how macrochirality is determined by the molecular chirality of the constituted amino acids is still unclear. Here, two chiral peptides, Ac-LKLHLHLQLKLLLVLFLFLALK-NH2 (KK-11) and Ac-DKDHDHDQDKDL DVDFDFDADK-NH2 (KKd-11), which were composed entirely of either L- or D-amino acids, were designed for studying the chiral characteristics of the supramolecular microstructures. It was found that monocomponent KK-11 or KKd-11 self-assembled into right- or left-handed helical nanofibrils, respectively. However, when they co-assembled with concentration ratios varied from 1:9 to 9:1, achiral nanowire-like structures were formed. Both circular dichroism and Fourier transform infrared spectra indicated that the secondary structures changed when the peptides co-assembled. MD simulations indicated that KK-11 or KKd-11 exhibited a strong propensity to self-assemble into right-handed or left-handed nanofibrils, respectively. However, when KK-11 and KKd-11 were both presented in a solution, they had a higher probability to co-assemble instead of self-sort. MD simulations indicated that, in their mixtures, they formed nanowires without handedness feature, a good agreement with experimental observation. Our results shed light on the molecular mechanisms of the macrochirality of peptide supramolecular microstructures.

Polymerization of Self-Assembled Tetraazaporphyrins

Polymerization of self-assembled supramolecular structures considerably increases their often limiting thermal and chemical stability, which widens their potential application in commercial products. Particularly interesting for self-assembled materials is the topochemical polymerization of diacetylenes to polydiacetylenes because it can be initiated photochemically and thermally without the need for additives, it proceeds with minimal structural changes, and it generates new functionality since polydiacetylene is a 1-dimensional organic semiconductor and absorbs visible light. Polydiacetylenes have been generated in single crystals, gel phases, thin films, and membranes but their formation in mesophases, such as liquid crystals, has been surprisingly little studied although higher ordered mesophases should support the topochemical polymerization of diacetylenes (1,3-butadiyne groups) and may give access to large domains of uniformly aligned materials.Presented here are tetraazaporphyrins that contain eight alkyl chains with diacetylene groups to probe their mesomorphism and conversion into multifunctional polydiacetylene materials. While incorporation of diacetylene groups supports columnar mesomorphism, successful photopolymerization required the presence of directing amide groups that suppressed columnar in favour of nematic mesomorphism. Still, polymerization of the nematic mesophase generated a soluble nematic polydiacetylene of significantly higher molecular weight (Mn = 77 kDa or 25 monomer units by GPC) than what has been obtained in gel phases of related compounds. Formation of polydiacetylene was confirmed by Raman spectroscopy and its nematic structure was verified by UV-vis spectroscopy, polarized optical microscopy, and X-ray diffraction. Both, its nematic structure and the incorporation of eight side-chains per discotic unit provide the polydiacetylene with sufficient solubility for casting thin films on substrates. AFM studies of films casted onto silicon wafers revealed a grid-like structure of connected nanofibers.Tahir et al. Langmuir 2019, 35, 15158

Self-assembled peptide-conjugated rosemary extract derivatives as drug delivery vehicles for targeting tumor cells

ABSTRACT Self-assembled supramolecular structures have gained attention due to their wide range of applications. In this work, we have created two novel drug delivery systems for targeting MCF-7 breast cancer cells using polyphenols derived from rosemary extract. The assemblies were synthesized by conjugating rosmarinic acid (RMA) and carnosic acid (CSA) with the peptide sequence H-A-I-L-L-I-T-K-G-I-F-K known for its ability to target MCF-7 breast cancer cells. The products were self-assembled into nanofibers or oblong shaped nanoassemblies. The mechanism of self-assembly was probed by COSMOS-RS computational studies. The assemblies were utilized to entrap the drug topotecan. Entrapment efficiency varied based on the morphology of the assemblies and concentration (42.3% for carnosic acid-peptide assemblies and 59.11% for rosmarinic acid-peptide assemblies). Furthermore, the RMA-peptide and CSA-peptide assemblies were found to be cytotoxic toward MCF-7 breast cancer cells, with relatively higher cytotoxicity observed for the topotecan entrapped CSA-peptide assemblies compared to topotecan entrapped RMA-peptide assemblies. Docking studies were conducted to examine binding interactions of the RMA-peptide and CSA-peptide conjugates with Src kinase receptor and estrogen receptor. Furthermore, CSA-peptide assemblies induced apoptosis while RMA-peptide assemblies induced necrosis. Our results indicate that such new biomimetic materials derived from naturally occurring polyphenols may be developed for dual targeting tumor cells.

DNA nanotechnology provides an avenue for the construction of programmable dynamic molecular systems.

Self-assembled supramolecular structures in living cells and their dynamics underlie various cellular events, such as endocytosis, cell migration, intracellular transport, cell metabolism, and gene expression. Spatiotemporally regulated association/dissociation and generation/degradation of assembly components is one of the remarkable features of biological systems. The significant advancement in DNA nanotechnology over the last few decades has enabled the construction of various-shaped nanostructures via programmed self-assembly of sequence-designed oligonucleotides. These nanostructures can further be assembled into micrometer-sized structures, including ordered lattices, tubular structures, macromolecular droplets, and hydrogels. In addition to being a structural material, DNA is adopted to construct artificial molecular circuits capable of activating/inactivating or producing/decomposing target DNA molecules based on strand displacement or enzymatic reactions. In this review, we provide an overview of recent studies on artificially designed DNA-based self-assembled systems that exhibit dynamic features, such as association/dis­sociation of components, phase separation, stimulus responsivity, and DNA circuit-regulated structural formation. These biomacromolecule-based, bottom-up approaches for the construction of artificial molecular systems will not only throw light on bio-inspired nano/micro engineering, but also enable us to gain insights into how autonomy and adaptability of living systems can be realized.

Flexible Alkyl Tails Help Shape Matching and Close Packing in Self-Assembly of Supramolecular Structure

Due to the flexibility and bowl-shaped cavity, C-alkylpyrogallol[4]arenes (PgCx, where x represents the length of alkyl chains) have garnered much attention over the past decade in supramolecular chemistry. Such cyclic polyphenolic compounds have been shown to be an excellent molecular building block for self-assembly of a variety of crystalline materials and have been applied in many frontier research areas ranging from ion transport to gas absorption/separation and biomedicine. In this work, we demonstrate that the long flexible alkyl tails play a critical role in the self-assembly of PgCx. It is found that they help the shape matching between the self-assembled building blocks and improve the packing density, thus promoting formation of an unprecedented “tails-driven” supramolecular structure. The successful demonstration of this work paves a new route to self-assembly materials by tuning the functional alkyl tails of the building blocks.