Supramolecular Host-guest Chemistry Research Articles

Triplet Exciton Harvesting in Water by a Structurally Simple Organic Phosphor with Sustained Afterglow and Lifetime Tunability

AbstractUltra‐long room temperature phosphorescence (URTP) materials are extremely promising for applications in organic electronics. Creating materials with controlled photophysics to achieve this, however, is difficult due to the challenges in filling up and stabilizing the sensitive triplet excited states at ambient temperature. Herein, triplet excitons are harvested by an intuitively designed structurally simple organic phosphor in water under ambient conditions by using supramolecular host–guest chemistry with cucurbituril‐7 (CB7) and sodium dodecyl sulphate (SDS), a negatively charged surfactant, with high photoluminescence (PL) quantum yields (PLQYs) (69% and 73% for CB7 and SDS, respectively) and phosphorescence lifetimes (12.52 and 12.42 ms for CB7 and SDS, respectively). A protective polyvinyl alcohol (PVA) film successfully controls the afterglow emission, excited state lifetime as well as PLQY in a single organic phosphor (CzPy24+). While a 1% concentration of CzPy24+ in the PVA film shows blue phosphorescence with 78.82% PLQY having a lifetime of 1.9 s, a 5% of CzPy24+ addition shows a green afterglow with 67.52% PLQY and a lifetime of 1.3 s. Similarly, yellow afterglow is achieved on adding 20% CzPy24+ to the PVA film with a PLQY of 40.88%. The findings are promising and helpful in constructing tunable phosphors for suitable applications.

A novel approach to supramolecular Aggregation-Induced emission using tetracationic tetraphenylethylene and sulfated β-Cyclodextrin

The combination of aggregation-induced emission-based luminogens (AIEgens) with supramolecular chemistry has gained significant attention due to its ability to produce intense emission even at low concentrations. In this study, we report a supramolecular arrangement characterized by aggregation-induced emission through the integration of tetracationic tetraphenylethylene with a macrocyclic polyanionic derivative of β-cyclodextrin. Despite the exploration of ionic derivatives of cyclodextrins in pharmaceutical and host–guest supramolecular chemistry, the phenomenon of supramolecular aggregation-induced emission based on non-covalent interactions between the ionic derivative of β-cyclodextrin and derivatives of tetraphenylethyelene, a class of AIEgens, has received limited investigation. Our work explores AIE shown by the allylimidazolium derivative of tetracationic tetraphenylethyelene (ALITPE) induced by complexation with polyanionic sulfated β-cyclodextrin (SCD). The effectiveness of the emission intensity of this supramolecular assembly based on AIE is confirmed by steady-state and time-resolved fluorescence measurements, which are supported by ground-state absorption measurements. We also investigate the effect of changes in external environment, such as temperature, pH, and ionic strength, on the supramolecular assembly. Moreover, the aggregation behavior of ALITPE with SCD is comparatively studied with neutral native β-cyclodextrin, highlighting the contribution of high negative charge density on the surface of SCD for efficient aggregation with ALITPE molecules. Additionally, Molecular Docking calculations are employed to provide insights into the aggregation behavior of ALITPE molecules induced by SCD. Overall, our findings demonstrate the potential applicability of the ALITPE/SCD supramolecular assembly as a potential fluorescent sensing probe for various biological applications.

Light-adjusted supramolecular host–guest interfacial recognition for reconfiguring soft colloidal aggregates

The soft interfacial template-assisted confined self-assembly of block copolymers (BCPs) guiding colloidal aggregates has been extensively investigated by interfacial instability. Whether the macromolecular polymer architectonics possessed stimulus-responsive self-regulated structural controllability more readily implement the morphological diversity of colloidal aggregates. Herein, we in-situ constructed the alginate-modified β-cyclodextrin/azobenzene-functionalized alkyl chains (Alg-β-CD/AzoC12) system by supramolecular host–guest interfacial recognition-engineered strategy, in which possessed photo-stimulated responsive structural reconfigurability by modulating assembly/disassembly behaviors between CD and Azo at oil/water interface. The host–guest droplet interfaces acted as soft templates managing interfacial instability by synergistically integrating supra-amphiphilic host–guest polymers with cosurfactants, further constructing various soft supracolloidal aggregates, including soft nanoaggregates, microspheres with tunable degrees of surface roughness. Additionally, the stimuli-altering structural reconfigurability of supramolecular host–guest polymers was regulated by ultraviolet/visible irradiation, endowing soft aggregates with structural diversity. It’s highly anticipated that the supramolecular host–guest interfacial recognition self-assembly establishes great bridge between supramolecular host–guest chemistry and colloid interface science.

Recent advances in the modulation of amyloid protein aggregation using the supramolecular host-guest approaches

Misfolding of proteins is associated with many incurable diseases in human beings. Understanding the process of aggregation from monomers to fibrils, the characterization of all intermediate species, and the origin of toxicity is very challenging. Extensive research including computational and experimental shed some light on these tricky phenomena. Non-covalent interactions between amyloidogenic domains of proteins play a major role in their self-assembly which can be disrupted by designed chemical tools. This will lead to the development of inhibitors of detrimental amyloid formations. In supramolecular host-guest chemistry approaches, different macrocycles function as hosts for encapsulating hydrophobic guests, i.e. phenylalanine residues of proteins, in their hydrophobic cavities via non-covalent interactions. In this way, they can disrupt the interactions between adjacent amyloidogenic proteins and prevent their self-aggregation. This supramolecular approach has also emerged as a prospective tool to modify the aggregation of several amyloidogenic proteins. In this review, we discussed recent supramolecular host-guest chemistry-based strategies for the inhibition of amyloid protein aggregation.

Chemically Enhanced Immunogenicity of Bacteria by Supramolecular Functionalization with an Adjuvant.

Many pathogens blunt immune responses because they lack immunogenic structural features, which typically results in disease. Here, we show evidence suggesting that pathogen immunogenicity can be chemically enhanced. Using supramolecular host-guest chemistry, we complexed onto the surface of a poorly immunogenic bacterium (Staphylococcus aureus) a TLR7 agonist-based adjuvant. "Adjuvanted" bacteria were readily recognized by macrophages and induced a more pro-inflammatory immunophenotype. Future applications of this concept could yield treatment modalities that bolster the immune system's response to pathogenic microbes.

Circular Dichroism Based Chirality Sensing with Supramolecular Host-Guest Chemistry.

Optical methods are promising to address the ever-increasing demands for chirality analysis in drug discovery and related fields because they are amenable to high-throughput screening. Circular dichroism-based chiroptical sensing using host-guest chemistry is especially appealing due to the fast equilibrium kinetics, wide substrate scope, and potential for sustainable development. In this Minireview, we give an overview on this emerging field. General aspects of molecular recognition and chirality transfer are analyzed. Chirality sensors are discussed by dividing them into three classes according to their structural features. Applications of these chirality sensors for chirality analysis of the products of asymmetric reactions and for the real-time monitoring of reaction kinetics are demonstrated with selected examples. Moreover, challenges and research directions in this field are also highlighted.

Circular Dichroism Based Chirality Sensing with Supramolecular Host–Guest Chemistry

AbstractOptical methods are promising to address the ever‐increasing demands for chirality analysis in drug discovery and related fields because they are amenable to high‐throughput screening. Circular dichroism‐based chiroptical sensing using host‐guest chemistry is especially appealing due to the fast equilibrium kinetics, wide substrate scope, and potential for sustainable development. In this Minireview, we give an overview on this emerging field. General aspects of molecular recognition and chirality transfer are analyzed. Chirality sensors are discussed by dividing them into three classes according to their structural features. Applications of these chirality sensors for chirality analysis of the products of asymmetric reactions and for the real‐time monitoring of reaction kinetics are demonstrated with selected examples. Moreover, challenges and research directions in this field are also highlighted.

Oligopyrrolic Cages: From Classic Molecular Constructs to Chemically Responsive Polytopic Receptors.

"Functional molecular systems", discrete and self-assembled constructs where control over molecular recognition, structure, bonding, transport, release, catalytic activity, etc., is readily achieved, are a topic of current interest. Within this broad paradigm, oligopyrrolic cages have garnered attention due to their responsive recognition features. Due to the presence of slightly polar pyrrole subunits which can also behave as hydrogen-bonding donors, these oligopyrrolic cages are potential receptors for various polarized species. In this Account, we summarize recent advances involving the syntheses and study of (1) covalent oligopyrrolic macrobicyclic cages, (2) oligopyrrolic metallacages, and (3) oligopyrrolic noncovalently linked cages. Considered in concert, these molecular constructs have allowed advances in applied supramolecular chemistry; to date, they have been exploited for selective guest encapsulation studies, anion binding and ion-channel formation, and gas absorption, among other applications. While key findings from others will be noted, in this Account will focus on our own contributions to the chemistry of discrete oligopyrrolic macrocycles and their use in supramolecular host-guest chemistry and sensing applications. In terms of specifics, we will detail how oligopyrrole cages with well-defined molecular geometries permit reversible guest binding under ambient conditions and how the incorporation of pyrrole subunits within larger superstructures allows effective control over anion/conjugate acid binding activity under ambient conditions. We will also provide examples that show how derivatization of these rudimentary macrocyclic cores with various sterically congested β-substituted oligopyrroles can provide entry into more complex supramolecular architectures. In addition, we will detail how hybrid systems that include heterocycles other than pyrrole, such as pyridine and naphthyridine, can be used to create self-assembled materials that show promise as gas-absorbing materials and colorimetric reversible sensors. Studies involving oligopyrrolic polymetallic cages and oligopyrrolic supramolecular cages will also be reviewed. First, we will discuss all-carbon-linked oligopyrrolic bicycles and continue on to present systems linked via amines and imines linkages. Finally, we will summarize recent work on pyrrolic cages created through the use of metal centers or various noncovalent interactions. We hope that this Account will provide researchers with an initial foundation for understanding oligopyrrolic cage chemistry, thereby allowing for further advances in the area. It is expected that the fundamental design and recognition principles made in the area of oligopyrrole cages, as exemplified by our contributions, will be of general use to researchers targeting the design of functional molecular systems. As such, we have structured this Account so as to summarize the past while setting the stage for the future.

Polyanionic Cyclodextrin-Induced Supramolecular Assembly of a Cationic Tetraphenylethylene Derivative with Aggregation-Induced Emission.

The combination of supramolecular chemistry and aggregation-induced emission-based luminogens (AIEgens) has recently attracted tremendous attention because of its ability to offer large emission enhancement even in substantially dilute solutions. In this work, a new aggregation-induced emission (AIE)-based supramolecular assembly has been reported, which consists of a polyanionic cyclodextrin derivative and a tetracationic tetraphenylethylene (TPE) derivative. Ionic cyclodextrins have attracted significant attention in host-guest supramolecular chemistry and pharmaceutical industry. However, ionic derivatives of β-cyclodextrins have not been explored to establish noncovalent interactions-based aggregation assembly of the most popular class of AIEgens, i.e., tetraphenylethylene derivatives. The current report demonstrates AIE of a tetracationic methyl pyridinium derivative of tetraphenylethylene (TPy-TPE) induced by a polyanionic sulfated β-cyclodextrin (S-βCD). The AIE-based supramolecular assembly has been thoroughly investigated using steady-state fluorescence, ground-state absorbance, and time-resolved fluorescence measurements. Further, the response of the supramolecular assembly towards external stimuli, such as, ionic strength, pH, and temperature, has been investigated. In addition, the complexation behavior of the TPE derivative has also been compared with the native neutral β-cyclodextrin derivative, which delineates the important role of the negatively charged portal of S-βCD in inducing aggregation of the TPy-TPE. The stoichiometry of the complex has been found to be 3:1 for TPy-TPE:S-βCD, using Job's plot analysis. Finally, to get insights into the underlying interactions between the supramolecular assembly components, molecular docking calculations have been performed.

Calixarene-mediated host-guest interactions leading to supramolecular assemblies: visualization by microscopy.

Host-guest chemistry, particularly of supramolecules, has been an intriguing topic for researchers for a long time due to its multiplicative applications ranging from chemical to biological to materials science. Supramolecules, such as calixarenes, are excellent host molecular systems due to their controllable cavity along with the ease of functionalization both at the lower and upper rims. The host-guest interactions involving calixarenes have been primarily studied using physical methods, such as absorption, fluorescence and nuclear magnetic resonance spectroscopy, isothermal titration calorimetry and mass spectrometry. The corresponding literature as disseminated through review articles triggered broadening of the spectrum of research. Depending upon the nature of the derivatization, the supramolecular conjugates of calixarenes have been shown to form different morphologies of micro and nanometric size as reported in the literature. Pertinent research performed in our own group was based on atomic force microscopy, transmission electron microscopy and scanning electron microscopy studies. The literature reveals that such morphologies are modified in the presence of guest species. Thus, the supramolecular host-guest complexation of calixarenes leading to the formation of various architectures has been studied using both spectroscopy and microscopy techniques to obtain complimentary data. However, there are no review articles that provide discussions on this exciting area of supramolecular science involving microscopy. Therefore, in the present article, for the first time, we have brought together the research reported in the literature during the past decade, including ours, in demonstrating the supramolecular architectures formed from the host-guest interactions extended by the conjugates of calixarenes, and their applications using microscopy. The scope of this article spans across various features of interaction in these systems: (i) in solution, (ii) at the air-water interface and (iii) on solid surfaces. The application domain includes sensing of organic explosives and drugs, exhibiting antibacterial activity, supramolecular self-assembly or co-assembly resulting in gels, micelles and vesicles, and the consequent aggregation-induced emission and a few others.

Higher-order assembly of BSA gold nanoclusters using supramolecular host-guest chemistry: a 40% absolute fluorescence quantum yield.

Herein, we report for the first time a highly emissive higher-order assembled structure of BSA-Au NCs in the presence of cucurbit[7]uril, which enhances the absolute fluorescence quantum yield of BSA-Au NCs up to 40%. Cucurbit[7]uril neutralizes the surface charge of BSA-Au NCs, and hence aggregation happens. This aggregation shows reversible disaggregation in the presence of adamantylamine.

Tuning Supramolecular Polymers' Amphiphilicity via Host-Guest Interfacial Recognition for Stabilizing Multiple Pickering Emulsions.

Supramolecular host-guest chemistry bridging the adjustable amphiphilicity and macromolecular self-assembly is well advanced in aqueous media. However, the interfacial self-assembled behaviors have not been further exploited. Herein, we designed a β-cyclodextrin-grafted alginate/azobenzene-functionalized dodecyl (Alg-β-CD/AzoC12) supra-amphiphilic system that possessed tunable amphiphilicity by host-guest interfacial self-assembly. Especially, supra-amphiphilic aggregates could be utilized as highly efficient soft colloidal emulsifiers for stabilizing water-in-oil-water (W/O/W) Pickering emulsions due to the excellent interfacial activity. Meanwhile, the assembled particle structures could be modulated by adjusting the oil-water ratio, resulting from the tunable aggregation behavior of supra-amphiphilic macromolecules. Additionally, the interfacial adsorption films could be partially destroyed/reconstructed upon ultraviolet/visible irradiation due to the stimuli-altering balance of amphiphilicity of Alg-β-CD/AzoC12 polymers, further constructing the stimulus-responsive Pickering emulsions. Therefore, the supramolecular interfacial self-assembly-mediated approach not only technologically advances the continued development of creative templates to construct multifunctional soft materials with anisotropic structures but also serves as a creative bridge between supramolecular host-guest chemistry, colloidal interface science, and soft material technology.

A Review on Nanopesticides for Plant Protection Synthesized Using the Supramolecular Chemistry of Layered Hydroxide Hosts.

Simple SummaryNanoscience and nanotechnology offer a new life for conventional pesticides with superior qualities by virtue of the physicochemical properties of the nanosized materials. These properties will improve bioavailability through different kinetics, mechanisms and pathways on their target organisms; enabling them to properly bypass biological and other unwanted resistances and therefore increase plant disease control efficacy. Inorganic two-dimensional (2D) layered hydroxides and layered double hydroxides were used as hosts, to act as functional nanocarriers for the delivery of various pesticides in combating various pests and diseases, in order to aid plant protection. This leads toward a new generation of more effective agrochemicals which are safe to life, humans and the environment.The rapid growth in the human population has triggered increased demand for food supply, and in turn has prompted a higher amount of agrochemical usage to meet the gaps between food production and consumption. The problem with conventional agro-nanochemicals is the reduced effectiveness of the active ingredient in reaching the target, along with leaching, evaporation, etc., which ultimately affect the environment and life, including humans. Fortunately, nanotechnology platforms offer a new life for conventional pesticides, which improves bioavailability through different kinetics, mechanisms and pathways on their target organisms, thus enabling them to suitably bypass biological and other unwanted resistances and therefore increase their efficacy. This review is intended to serve the scientific community for research, development and innovation (RDI) purposes, by providing an overview on the current status of the host–guest supramolecular chemistry of nanopesticides, focusing on only the two-dimensional (2D), brucite-like inorganic layered hydroxides, layered hydroxide salts and layered double hydroxides as the functional nanocarriers or as the hosts in smart nanodelivery systems of pesticides for plant protection. Zinc layered hydroxides and zinc/aluminum-layered double hydroxides were found to be the most popular choices of hosts, presumably due to their relative ease to prepare and cheap cost. Other hosts including Mg/Al-, Co/Cr-, Mg/Fe-, Mg/Al/Fe-, Zn/Cr- and Zn/Cu-LDHs were also used. This review also covers various pesticides which were used as the guest active agents using supramolecular host–guest chemistry to combat various pests for plant protection. This looks towards a new generation of agrochemicals, “agro-nanochemicals”, which are more effective, and friendly to life, humans and the environment.

Carbo-mer of Barrelene: A Rigid 3D-Carbon-Expanded Molecular Barrel.

After extensive studies of 1D and 2D skeletal carbo-mers based on C8 π-conjugating dialkynylbutatriene units (DABs: ∼C≡C-(R)C=C=C=C(R)-C≡C∼) bridging sp or sp2 centers in carbo-butene, carbo-xylylene or carbo-benzene derivatives, 3D versions are envisaged through carbo-barrelenes and partially reduced derivatives thereof where two or three DAB blades span a bridge between sp3 carbinol vertices or ether thereof. For R=Ph, stable representatives were synthesized through a pivotal [6]pericyclynedione, and extensively characterized by spectroscopic, electrochemical and crystallographic methods. Density functional theory calculations allow detailed analysis of structural and electronic features of the 7 Å high C26 barrel-shaped molecules, and show that they can behave as cages for ionic species. Beyond aesthetical concerns, the results could open prospects of applications in host-guest supramolecular chemistry and single molecule charge transport.

A reference scale of cucurbit[7]uril binding affinities.

The accurate determination of ultra-high binding affinities in supramolecular host-guest chemistry is a challenging endeavour because direct binding titrations are generally limited to affinities <106 M-1 due to sensitivity constraints of common titration methods. To determine higher affinities, competitive titrations are usually performed, in which one compound with a well established binding affinity serves as a reference. Herein, we propose a reference scale for such competitive titrations with the host cucurbit[7]uril (CB7) comprising binding affinities in the range from 103 to 1015 M-1. The suggested reference compounds are commercially available and will aid in the future determination of CB7 binding affinities for stimuli-responsive host-guest systems.

Biomimetic nanochannels platform for detecting N-acetylglucosamine analogues

N-acetylglucosamine analogues exist in nature as an important saccharide in human body and can regulate a variety of life activities captured through biological nanochannels. Herein we describe a biomimetic strategy via supramolecular host-guest chemistry for constructing artificial nanochannels to detect N-acetylglucosamine analogues. The functional nanochannels exhibited a high selectivity and good reversibility towards N-acetylglucosamine. Further studies indicate that the detecting behaviors was probably due to the multiple hydrogen bonding interactions and an appropriately fitting the functional and geometric requirements between the tryptophan-decorated pillararenes and N-acetylglucosamine, leading to the change of the surface charge and wettability within the nanochannels. These studies can give interesting insight for the research of biological processes caused by N-acetylglucosamine-sensitive ion channels, and also help to develop the platform for detecting N-acetylglucosamine in vitro.

Intracellular Delivery of Adamantane-Tagged Small Molecule, Proteins, and Liposomes Using an Octaarginine-Conjugated β-Cyclodextrin.

Herein, we demonstrate a convenient technique for the intracellular delivery of proteins and liposomes based on supramolecular host-guest chemistry. First, we prepared the R8-CDOH carrier molecule, which is a β-cyclodextrin derivative bearing an octaarginine (R8) chain, as a cell-penetrating peptide, at the primary hydroxyl group. The surface amino groups of proteins (GFP, β-gal, and IgG) were then partly modified with adamantane (Ad) tags using 1-Ad-carboxylic acid N-hydroxysuccinimide ester (Ad-NHS). These Ad-tagged proteins were effectively delivered into HeLa cells though supramolecular host-guest interactions with R8-CDOH. A 100 nm sized liposome bearing Ad-tags on its surface was also delivered into these cells by the action of R8-CDOH. The present method does not require any genetic manipulation, and only easy chemical modification processes are used to facilitate intracellular delivery; therefore, we believe that the present method is applicable to a variety of bioengineering processes, such as protein-based therapeutics, cellular reprogramming, and genome-editing, among others.

2D host–guest supramolecular chemistry for an on-monolayer graphene emitting platform

Electronic decoupling of molecular emitters from monolayer graphene allows luminescence of the hybrid platform, opening new perspectives for 2D materials-based nanophotonics.

Orthogonal Supramolecular Assembly Triggered by Inclusion and Exclusion Interactions with Cucurbit[7]uril for Photocatalytic H2 Evolution.

The fabrication of efficient and convenient photocatalytic H2 evolution systems is a fascinating research topic in the field of solar energy conversion. A ternary self-assembled photocatalytic H2 evolution system was fabricated through supramolecular host-guest chemistry. The system consisted of the H2 evolution catalyst [Co(dmgH)2 (4-ppy)2 ]NO3 (1; dmgH2 =dimethylglyoxime, 4-ppy=4-phenylpyridine) and the photosensitizer Eosin Y (EY) assembled with the macrocyclic compound cucurbit[7]uril (CB[7]) to form the 1@CB[7]/EY complex through inclusion and exclusion interactions, respectively. The synchronous self-assembly drives an orthogonal arrangement of the 1@CB[7]/EY system. The inclusion complex 1@CB[7] was successfully characterized by 1 H NMR spectroscopy and single-crystal XRD. The exclusion process of CB[7] with EY was identified by NMR titration and the optimized geometry of the exclusion structure was determined by DFT calculations. The use of CB[7] resulted in a 6-fold increase in turnover number, a 3-fold increase in turnover frequency, and a 3-fold extension of lifetime for photocatalytic H2 evolution as compared with the system in the absence of CB[7]. The improvement of the light-driven H2 evolution activity was ascribed to the ability of CB[7] to link the photosensitizer and catalyst.

On-Flow Immobilization of Polystyrene Microspheres on β-Cyclodextrin-Patterned Silica Surfaces through Supramolecular Host-Guest Interactions.

Species-specific isolation of microsized entities such as microplastics and resistant bacteria from waste streams is becoming a growing environmental challenge. By studying the on-flow immobilization of micron-sized polystyrene particles onto functionalized silica surfaces, we ascertain if supramolecular host–guest chemistry in aqueous solutions can provide an alternative technology for water purification. Polystyrene particles were modified with different degrees of adamantane (guest) molecules, and silica surfaces were patterned with β-cyclodextrin (β-CD, host) through microcontact printing (μCP). The latter was exposed to solutions of these particles flowing at different speeds, allowing us to study the effect of flow rate and multivalency on particle binding to the surface. The obtained binding profile was correlated with Comsol simulations. We also observed that particle binding is directly aligned with particle’s ability to form host–guest interactions with the β-CD-patterned surface, as particle binding to the functionalized glass surface increased with higher adamantane load on the polystyrene particle surface. Because of the noncovalent character of these interactions, immobilization is reversible and modified β-CD surfaces can be recycled, which provides a positive outlook for their incorporation in water purification systems.