Direct Laser Writing Photonic Crystal Hydrogels with a Supramolecular Sacrificial Scaffold.

Photonic crystal hydrogels (PCHs), with smart stimulus-responsive abilities, have been widely exploited as colorimetric sensors for years. However, the current fabrication technologies are mostly applicable to produce PCHs with simple geometries at the sub-millimeter scale, limiting the introduction of structural design into PCH sensors as well as the accompanied advanced applications. This paper reports the microfabrication of three-dimensional (3D) PCHs with the help of supramolecular agarose PCH as a sacrificial scaffold by two-photon lithography (TPL). The supramolecular PCHs, formulated with SiO2 colloidal nanoparticles and agarose aqueous solutions, show bright structural color and are degradable upon short-time dimethyl sulfoxide treatment. Leveraging the supramolecular PCH as a sacrificial scaffold, PCHs with precise 3D geometries can be fabricated in an economical and efficient way. This work demonstrates the application of such a strategy in the creation of structural-designed PCH mechanical microsensors that have not been explored before.

Organization of Carotenoid Aggregates in Membranes Studied Selectively using Resonance Raman Optical Activity.

In living organisms, carotenoids are incorporated in biomembranes, remarkably modulating their mechanical characteristics, fluidity, and permeability. Significant resonance enhancement of Raman optical activity (ROA) signals of carotenoid chiral aggregates makes resonance ROA (RROA), a highly selective tool to study exclusively carotenoid assemblies in model membranes. Hence, RROA is combined with electronic circular dichroism (ECD), dynamic light scattering (DLS), molecular dynamics, and quantum-chemical calculations to shed new light on the carotenoid aggregation in dipalmitoylphosphatidylcholine (DPPC) liposomes. Using representative members of the carotenoid family: apolar α-carotene and more polar fucoxanthin and zeaxanthin, the authors demonstrate that the stability of carotenoid aggregates is directly linked with their orientation in membranes and the monomer structures inside the assemblies. In particular, polyene chain distortion of α-carotene molecules is an important feature of J-aggregates that show increased orientational freedom and stability inside liposomes compared to H-assemblies of more polar xanthophylls. In light of these results, RROA emerges as a new tool to study active compounds and drugs embedded in membranes.

Self-Assembly of Uniaxial Fullerene Supramolecules Aligned within Carbon Nanotube Fibers.

The conductivity and strength of carbon nanotube (CNT) wires currently rival those of existing engineering materials; fullerene-based materials have not progressed similarly, despite their exciting transport properties such as superconductivity. This communication reveals a new mechanically robust wire of mutually aligned fullerene supramolecules self-assembled between CNT bundles, where the fullerene supramolecular internal crystal structure and outer surface are aligned and dispersed with the CNT bundles. The crystallinity, crystal dimensions, and other structural features of the fullerene supramolecular network are impacted by a number of important production processes such as fullerene concentration and postprocess annealing. The crystal spacing of the CNTs and fullerenes is not altered, suggesting that they are not exerting significant internal pressure on each other. In low concentrations, the addition of networked fullerenes makes the CNT wire mechanically stronger. More importantly, novel mutually aligned and networked fullerene supramolecules are now in a bulk self-supporting architecture.

Heterochiral π-stacking dimerization of helical secondary structures with emerging supramolecular chirality.

In this work, we report a new type of interface modes between helical secondary structures by noncovalent assembly along the helical axis. The dimerization of helical secondary structures mediated by aromatic π-stacking leads to discrete heterochiral dimeric helical rods consisting of left-handed helix and right-handed helix, which has been demonstrated by single-crystal X-ray diffraction. We conduct chiral induction studies on discrete heterochiral dimers to regulate the preference of the helical sense. Surprisingly, we found a novel supramolecular chirality potentially occurring inside the super-secondary structure of chirality-induced heterochiral helical dimers, rather than the racemization of helical chirality. Furthermore, chirality-induced heterochiral helical dimers can exhibit unique chiral switches when formed or not formed. In order to identify the emerging supramolecular chirality of discrete heterochiral dimeric helix, we covalently synthesized meso-helix structures with opposite helical handedness. The chirality of aromatic chromophore linker was confirmed by chiral induction despite competition from opposite handed helices, which strongly demonstrates the occurrence of emerging supramolecular chirality in heterochiral dimeric helix. This study not only reports the heterochiral π-stacking dimerization of helical secondary structures for the first time, but also discovers novel supramolecular chirality hidden in the structure of noncovalent and even covalent meso-helices.

Non-Equilibrium Dissipative Assembly with Switchable Biological Functions.

Natural dissipative assembly (DSA) often exhibit energy-driven shifts in natural functions. However, creating man-made DSA that can mimic such biological activities transformation remains relatively rare. Herein, we introduce a cytomembrane-like dissipative assembly system based on chiral supramolecules. This system employs benzoyl cysteine in an out of equilibrium manner, enabling the shifts in biofunctions while minimizing material use. Specifically, aroyl-cystine derivatives primarily assemble into stable M-helix nanofibers under equilibrium conditions. These nanofibers enhance fibroblast adhesion and proliferation through stereospecific interactions with chiral cellular membranes. Upon the addition of chemical fuels, these functional nanofibers temporarily transform into non-equilibrium nanospheres, facilitating efficient drug delivery. Subsequently, these nanospheres revert to their original nanofiber state, effectively recycling the drug. The programmable function-shifting ability of this DSA establishes it as a novel, fuel-driven drug delivery vehicle. And the bioactive DSA not only addresses a gap in synthetic DSAs within biological applications but also sets the stage for innovative designs of 'living' materials.

Hourglass-Shaped Nanocages with Concaved Structures Based on Selective Self-Complementary Coordination Ligands and Tunable Hierarchical Self-Assembly.

Three-dimensional (3D) structures constructed via coordination-driven self-assemblies have recently garnered increasing attention due to the challenges in structural design and potential applications. In particular, developing new strategy for the convenient and precise self-assemblies of 3D supramolecular structures is of utmost interest. Introducing the concept of self-coordination ligands, herein the design and synthesis of two meta-modified terpyridyl ligands with selective self-complementary coordination moiety are reported and their capability to assemble into two hourglass-shaped nanocages SA and SB is demonstrated. Within these 3D structures, the meta-modified terpyridyl unit preferably coordinates with itself to serve as concave part. By changing the arm length of the ligands, hexamer (SA) and tetramer (SB) are obtained respectively. In-depth studies on the assembly mechanism of SA and SB indicate that the dimers could be formed first via self-complementary coordination and play crucial roles in controlling the final structures. Moreover, both SA and SB can go through hierarchical self-assemblies in solution as well as on solid-liquid interface, which are characterized by transmission electron microscope (TEM) and scanning tunneling microscopy (STM). It is further demonstrated that various higher-order assembly structures can be achieved by tuning the environmental conditions.

Photoswitchable Chiral Organocatalysts: Photocontrol of Enantioselective Reactions.

This study presents recent advances in photoswitchable chiral organocatalysts and their applications in the photomodulation of enantioselective reactions. Under irradiation with an appropriate wavelength of light, the E/Z-photoisomerization of the photoresponsive units on the catalysts leads to the control of the catalytic activity and/or selectivity of the enantioselective reactions. Additionally, this study elucidates the design, synthesis, and catalytic application of the fabricated azobenzene BINOL-based photoswitchable chiral phase-transfer catalysts. This account will provide insights into the appropriate design of a photoswitchable chiral organocatalyst that can achieve both good enantioselectivity and photocontrol.

Eco-Friendly One-Pot Supramolecular-Assembly of P-N Flame Retardant for Fire-Safe Epoxy Resin.

Flame retardant treatment of epoxy resins (EP) to reduce their flammability for extending their range of applications attracts considerable attention. However, the synthesis process of conventional flame retardants is complicated and involves organic hazardous solvents. Meanwhile, how to ensure both the flame-retardant and mechanical properties is a long-standing and actual difficult problem. In this work, a supramolecular flame retardant (named ATPFR) is facilely created by one-pot reaction, using cheap and accessible raw materials in an ecologically benign aqueous solvent. ATPFR is applied to improve the fire safety of EP. With only 5 wt% ATPFR addition, EP can reach the limiting oxygen index of 28.5% and the UL-94 V-0 rating with a significant "blow-out effect." The cone calorimetry test reveals that the EP thermoset with 5 wt% ATPFR has a 75.8% reduction in the peak heat release rate (p-HRR) and a 67.3% reduction in the peak smoke production rate (p-SPR), respectively, compared with the pure EP. Additionally, EP composites with the small amount of ATPFR exhibit a slight decrease and maintain good mechanical properties. Therefore, the facile synthesis and application of this supramolecular flame retardant provide a reliable way for the construction of polymer materials with environment-friendly and effective flame-retardant system.

Characterization and Application of Supramolecular Junctions.

The convergence of supramolecular chemistry and single-molecule electronics offers a new perspective on supramolecular electronics, and provides a new avenue toward understanding and application of intermolecular charge transport at the molecular level. In this review, we will provide an overview of the advances in the characterization technique for the investigation of intermolecular charge transport, and summarize the experimental investigation of several non-covalent interactions, including π-π stacking interactions, hydrogen bonding, host-guest interactions and σ-σ interactions at the single-molecule level. We will also provide a perspective on supramolecular electronics and discuss the potential applications and future challenges.

Multi-Decker Emissive Supramolecular Architectures Based on Shape-Complementary Ligands Pair.

Dye aggregates have attracted a great deal of attention due to their widespread applications in organic light-emitting devices, light-harvesting systems, etc. However, the strategies to precisely control chromophores with specific spatial arrangements still remain a great challenge. In this work, a series of double- and triple-decker supramolecular complexes are successfully constructed by coordination-driven self-assembly of carefully designed shape-complementary ligands, one claw-like tetraphenylethylene (TPE)-based host ligand and three tetratopic or ditopic guest ligands. The spatial configurations of these assemblies (one double-decker and three "S-shaped" or "X-shaped" triple-decker structures) depend on the angles of these TPE-derived ligands. Notably, the three triple-decker structures are geometric isomers. Furthermore, photophysical studies show that these complexes exhibit different ratios of radiative (kr ) and non-radiative (knr ) rate constant due to the different spatial arrangements of TPE moieties. This study provides not only a unique strategy for the construction of multi-stacks with specific spatial arrangement, but also a promising platform for investigating the aggregation behavior of fluorescent chromophores.

Recent Updates on Supramolecular-Based Drug Delivery - Macrocycles and Supramolecular Gels.

Supramolecules-based drug delivery has attracted significant recent research attention as it could enhance drug solubility, retention time, targeting, and stimuli responsiveness. Among the different supramolecules and assemblies, the macrocycles and the supramolecular hydrogels are the two important categories investigated to a greater extent. Here, we provide the most recent advancements in these categories. Under macrocycles, reports on drug delivery by cyclodextrins, cucurbiturils, calixarenes/pillararenes, crown ethers and porphyrins are detailed. The second category discusses the supramolecular hydrogels of macrocycles/polymers and low molecular weight gelators. The updated information provided could be helpful to advance R & D in this vital area.

Optical Chemical Sensing of Iodide Ions: A Comprehensive Review for the Synthetic Strategies of Iodide Sensing Probes, Challenges, and Future Aspects.

Among several anions, iodide (I- ) ions play a crucial role in human biological activities. In it's molecular form (I2 ), iodine is utilized for several industrial applications such as syntheses of medicines, fabric dyes, food additives, solar cell electrolytes, catalysts, and agrochemicals. The excess or deficiency of I- ions in the human body and environmental samples have certain consequences. Therefore, the selective and sensitive detection of I- ions in the human body and environment is vital for monitoring their overall profile. Amongst various analytical techniques for the estimation of I- ions, optical-chemical sensing possesses the merits of high sensitivity, selectivity, and utilizing the least amount of sensing materials. The distinctive aims of this manuscript are (i) To comprehensively review the development of optical chemical sensors (fluorescent & colorimetric) reported between 2001-2021 using organic fluorescent molecules, supramolecular materials, conjugated polymers, and metal-organic frameworks (MOFs). (ii) To illustrate the design and synthetic strategies to create specific binding and high affinity of I- ions which could help minimize negative consequences associated with its large size and high polarizability. (iii) The challenges associated with sensitivity and selectivity of I- ions in aqueous and real samples. The probable future aspects concerning the optical chemical detection of I- ions have also been discussed in detail.

Supramolecular Engineering of Alkylated, Fluorinated, and Mixed Amphiphiles.

The rational design of perfluorinated amphiphiles to control the supramolecular aggregation in an aqueous medium is still a key challenge for the engineering of supramolecular architectures. Here, the synthesis and physical properties of six novel non-ionic amphiphiles are presented. The effect of mixed alkylated and perfluorinated segments in a single amphiphile is also studied and compared with only alkylated and perfluorinated units. To explore their morphological behavior in an aqueous medium, dynamic light scattering (DLS) and cryogenic transmission electron microscopy/electron microscopy (cryo-TEM/EM) measurements are used. The assembly mechanisms with theoretical investigations are further confirmed, using the Martini model to perform large-scale coarse-grained molecular dynamics simulations. These novel synthesized amphiphiles offer a greater and more systematic understanding of how perfluorinated systems assemble in an aqueous medium and suggest new directions for rational designing of new amphiphilic systems and interpreting their assembly process.

Hierarchical Chiral Supramolecular Nanoarchitectonics with Molecular Detection: Helical Structure Controls upon Self-Assembly and Coassembly.

The morphological transformation from microspheres to helical supramolecular nanofibers with controllable handedness is achieved by the introduction of molecular chirality based on amino acid derivatives (TDAP), and the chirality of the supramolecular architectures that are achieved is nullified through the coassembly of the equivalent TDAP enantiomers. The molecular detection of achiral melamine based on the R-TDAP-COOH supramolecular system is achieved by the appearance of helicity and inversion.

Terpyridine-Based 3D Discrete Metallosupramolecular Architectures.

Terpyridine (tpy)-based 3D discrete metallosupramolecular architectures, which are often inspired by polyhedral geometry and the biological structures found in nature, have drawn significant attention from the community of metallosupramolecular chemistry. Because of the linear tpy-M(II)-tpy connectivity, the creation of sophisticated 3D metallosupramolecules based on tpy remains a formidable synthetic challenge. Nevertheless, with recent advancement in ligand design and self-assembly, diverse 3D metallosupramolecular polyhedrons, such as Platonic solids, Archimedean solids, prims as well as Johnson solids, have been constructed and their potential applications have been explored. This review summarizes the progress on tpy-based discrete 3D metallosupramolecules, aiming to shed more light on the design and construction of novel discrete architectures with molecular-level precision through coordination-driven self-assembly.

Study on Supramolecules in Traditional Chinese Medicine Decoction.

With the application of the concept of supramolecular chemistry to various fields, a large number of supramolecules have been discovered. The chemical components of traditional Chinese medicine have various sources and unique structures. During the high-temperature boiling process, various active components form supramolecules due to complex interactions. The supramolecular structure in a traditional Chinese medicine decoction can not only be used as a drug carrier to promote the absorption and distribution of medicinal components but may also have biological activities superior to those of single active ingredients or their physical mixtures. By summarizing the relevant research results over recent years, this paper introduces the research progress regarding supramolecules in various decoctions, laying a foundation for further research into supramolecules in traditional Chinese medicine decoctions, and provides a new perspective for revealing the compatibility mechanisms of traditional Chinese medicine, guiding clinical medications, and developing new nanometers materials.

Effect of Cu2+ on the Laccase-Inducted Formation of Non-Extractable Residues of Tetrabromobisphenol A in Humic Acids.

We used 14 C-radiolabelling to study the non-extractable residues (NERs) formation of tetrabromobisphenol A (TBBPA) in a humic acid (HA) suspension under catalysis of laccase in the presence of copper. When entering the suspension after TBBPA adsorbing to HA supramolecular associates, Cu2+ at low concentrations (even without toxicity to laccase) significantly reduced the amount and first-order kinetic constant of the NER formation, while Cu2+ had no significant effect on the formation after it was complexed with HA. The inhibition effect of Cu2+ on the NER formation is explained to be attributed to the prevention of laccase-induced oxidation of TBBPA in the voids of HA associates by complexation of Cu2+ with periphery molecules of the associates. The results provide insights into varying effects of heavy metals on the environmental fate of organic contaminants and suggest that co-existing heavy metals could increase their environmental risk by reducing their NER formation.

Chirality of Perylene Diimides: Design Strategies and Applications.

Chirality is a particularly important concept in nature and exists at all length scales, ranging from the molecular level to the supramolecular level. Over the last two decades, various design strategies have been developed to construct chiral materials based on perylene diimides (PDIs) and to mimic the chiral assembly process in biological systems, but applications of these chiral aggregates are still at an early stage. This Minireview summarizes recent progress in the synthesis and properties of chiral PDIs. The chirality in PDI-based materials can be generated by three different approaches: from the twisted planes of PDIs, the chiral substituents of PDIs, and the co-assembly of achiral PDIs and chiral guests. A comprehensive understanding of the applications of chiral PDIs as well as potential future developments is also provided.

Highly Accurate Synthesis of Quasi-sub-nanoparticles by Dendron-assembled Supramolecular Templates.

Quasi-sub-nanomaterials (1-3 nm) have been predicted to exhibit unique properties originating from the gray structures considered both bulk solids and molecules, while their synthesis is extremely difficult. The present study describes a new template synthesis method for quasi-sub-nanosized materials using a combination of coordination chemistry and polymer chemistry. Utilizing self-assembly of guest basic phenylazomethine dendron units onto host acidic core units with six tritylium cations, the dendron-assembled supramolecules were constructed easily and quantitatively without costly techniques. This huge supramolecular capsule accumulating multiple acidic rhodium salts in its basic ligands enabled a precise synthesis of rhodium particles via formation of multinuclear complexes. The obtained particles (Rh84 , ≈1.5 nm) have particle sizes within 1-3 nm range and were larger than conventional sub-nanoparticles (Rh14 , ≈0.85 nm), therefore the precise template synthesis of quasi-sub-nanoparticles was successfully demonstrated.

Tunable Second-Level Room-Temperature Phosphorescence of Solid Supramolecules between Acrylamide-Phenylpyridium Copolymers and Cucurbit[7]uril.

A series of solid supramolecules based on acrylamide-phenylpyridium copolymers with various substituent groups (P-R: R=-CN, -CO2 Et, -Me, -CF3 ) and cucurbit[7]uril (CB[7]) are constructed to exhibit tunable second-level (from 0.9 s to 2.2 s) room-temperature phosphorescence (RTP) in the amorphous state. Compared with other solid supramolecules P-R/CB[7] (R=-CN, -CO2 Et, -Me), P-CF3 /CB[7] displays the longest lifetime (2.2 s), which is probably attributed to the fluorophilic interaction of cucurbiturils leading to a uncommon host-guest interaction between 4-phenylpyridium with -CF3 and CB[7]. Furthermore, the RTP solid supramolecular assembly (donors) can further react with organic dyes Eosin Y or SR101 (acceptors) to form ternary supramolecular systems featuring ultralong phosphorescence energy transfer (PpET) and visible delayed fluorescence (yellow for EY at 568 nm and red for SR101 at 620 nm). Significantly, the ultralong multicolor PpET supramolecular assembly can be further applied in fields of anti-counterfeiting and information encryption and painting.