Host-guest Assembly Research Articles

Host-Guest Assemblies of Polyoxovanadate Clusters as Supramolecular Catalysts.

Supramolecular functional materials can be used to overcome some of the most challenging tasks in materials science, where the dynamic nature of supramolecular interactions can be leveraged to fine-tune the properties of the material. The Lindqvist hexavanadate family of polyoxometalates are interesting candidates for supramolecular materials due to their redox and Lewis acid properties that enable their application inenergy conversion or catalysis. Despite their promising potential, hexavanadate clusters are underrepresented in supramolecular materials, mainly due to the synthetic challenges related to their inherent reactivity. In this work, pillar[5]arene was successfully grafted onto a Lindqvist hexavanadate and the resulting structure was confirmed by single crystal X-ray diffraction, presenting the first example of a crystal structure of a polyoxometalate covalently functionalized with a pillar[5]arene. By introducing a ditopic guest molecule that could interlink pillar[5]arene moieties, host-guest interactions were leveraged as the driving force for the formation of supramolecular assemblies incorporating hexavanadate clusters in a controlled manner. The enhanced catalytic performance of the resulting aggregates confirmed their potential application as functional catalytic materials. This novel approach for developing hexavanadate-based catalysts reported here showcases the potential of using host-guest interactions as a means to introduce catalytically active metal-oxo clusters into supramolecular frameworks.

Proximity Effects and Aggregation of Hamilton-Receptor Barbiturate Host-Guest Complexes Probed by Cross-Metathesis and ESI MS Analysis.

The molecular environment around supramolecular bonding systems significantly affects their stability and the assembly of host-guest complexes, most prominent for hydrogen bonds (H-bonds). Hamilton receptor-barbiturate host-guest complexes are well-known in solution, typically forming a 1:1 molar ratio complex. However, within a polymer matrix, these complexes can form higher-order assemblies, deviating from the standard 1:1 complex, which are challenging to characterize and often require lab-intensive methods. In this study, a novel Hamilton receptor (H) was equipped with cyclopentene moieties and used as a host to form host-guest complexes (H-B) with allobarbital (B), followed by covalent crosslinking. UV-Vis spectroscopy titration experiments in different solvents and at various temperatures revealed that polar solvents containing additional H-bonding sites significantly reduce the formation of the 1:1 H-B complex, as indicated by a reduced association constant. Higher-order aggregates (HH-dimer, HHH-trimer) were subsequently detected via an alkene cross-metathesis (CM) reaction to fix the assemblies covalently, followed by analysis via electrospray ionization mass spectrometry (ESI MS). This two-step method, firstly via CM fixation followed by ESI MS, was extended to study the H-B model complex within a polyisobutylene (PIB) matrix, presenting a direct method to analyze the complex host-guest assembly in solvent-free (polymer) environments.

Buckybowl-Based Fullerene Receptors.

Buckybowls, bowl-shaped polyaromatic hydrocarbons, have received intensive interest owing to their multifaceted potentials in supramolecular chemistry and materials science. Buckybowls possess unique chemical and physical properties associated with their concave and convex faces. In view of the shape complementarity, which is one of the key factors for host-guest assembly, buckybowls are ideal receptors for fullerenes. In fact, the host-guest assembly between buckybowls and fullerenes is one of the most active topics in buckybowls chemistry, and the resulting supramolecular materials show promising applications in optoelectronics, biomaterials, and so forth. In this tutorial review, we present an overview for the progress on fullerene receptors based on buckybowls over the last decade.

A combination of covalent and noncovalent restricted‐intramolecular‐rotation strategy for supramolecular AIE‐type photosensitizer toward photodynamic therapy

AbstractPhotodynamic therapy (PDT) is a promising noninvasive method for targeted cancer cell destruction. Still, its effectiveness is often hindered by the aggregation‐caused quenching effect of organic photosensitizer (PS) in aqueous environments. Here, we have employed a combination of covalent and noncovalent restricted‐intramolecular‐rotation strategies to develop supramolecular PSs with aggregation‐induced emission (AIE) characteristics. Firstly, a water‐soluble octacationic molecular cage (1) with a bilayer tetraphenylethene (TPE) structure has been designed and synthesized, which minimizes intramolecular rotation of TPE moieties and achieves the single‐molecule‐level aggregation by the covalent restriction of intramolecular rotation (RIR) via molecular engineering synthesis. Compared with its single‐layer TPE analog, 1 exhibits superior efficiency in generating reactive oxygen species (ROS) including superoxide radical (O2−•) and singlet oxygen (1O2) upon white‐light irradiation. Subsequently, by forming a 1:4 host–guest complex (1@CB[8]4) between 1 and cucurbit[8]uril (CB[8]), O2−• generation can be further enhanced by the noncovalent RIR via the host–guest assembly. Additionally, 1@CB[8]4 as a photocatalyst promotes rapid oxidation of nicotinamide adenine dinucleotide (NADH) in water. Given its Type‐I ROS generation and catalytic activity for NADH oxidation, 1@CB[8]4 acts as a supramolecular AIE‐type PS to exhibit strong photo‐induced cytotoxicity upon white‐light irradiation under hypoxic conditions, showcasing its potential for synergistic PDT.

Modular Customized Biomimetic Nanofluidic Diode for Tunable Asymmetric Ion Transport.

Artificial ion diodes, inspired by biological ion channels, have made significant contributions to the fields of physics, chemistry, and biology. However, constructing asymmetric sub-nanofluidic membranes that simultaneously meet the requirements of easy fabrication, high ion transport efficiency, and tunable ion transport remains a challenge. Here, a direct and flexible in situ staged host-guest self-assembly strategy is employed to fabricate ion diode membranes capable of achieving zonal regulation. Coupling the interfacial polymerization process with a host-guest assembly strategy, it is possible to easily manipulate the type, order, thickness, and charge density of each module by introducing two oppositely charged modules in stages. This method enables the tuning of ion transport behavior over a wide range salinity, as well as responsive to varying pH levels. To verify the potential of controllable diode membranes for application, two ion diode membranes with different ion selectivity and high charge density are coupled in a reverse electrodialysis device. This resulted in an output power density of 63.7W m-2 at 50-fold NaCl concentration gradient, which is 12 times higher than commercial standards. This approach shows potential for expanding the variety of materials that are appropriate for microelectronic power generation devices, desalination, and biosensing.

Facile preparation of self-healing, adhesive and patterned gels via frontal polymerization for wearable sensing and actuating applications

Flexible intelligent gel has garnered great research attention for its potential artificial intelligence applications. Herein, a facile method is provided for fabricating patterned gel materials with self-healing, adhesive, and responsive properties via frontal polymerization within 10 min. The resulting gels are able to self-repair spontaneously after damaged, and exhibit the highest self-healing efficiency (∼99 %) benefiting from the synergistic effect of hydrogen-bond and host–guest assemblies. Moreover, the adhesive gels display satisfactory mechanical properties with great stretchability (524 %), tensile strength (200 kPa) and flexibility. With these features, the gels are served as flexible wearable sensors which can detect a series of movements such as stretch, bend and touch. Furthermore, the dual-component gels are prepared by the metal–ligand interaction (Fe3+-carboxyl group) on the one side of the gel films. The gradient structure and swelling ability endow the gel with actuating behaviors. This research explores a convenient approach to construct functional patterned gels towards significant applications in the wearable sensor and actuator fields.

A comparative study on stabilizing and releasing thymol by pre-formed V-type starch and β-cyclodextrin

Cyclodextrins (CD) are well known to form host-guest assemblies with hydrophobic compounds. As a structural homologue, starch-guest inclusion complexes (ICs) have become promising in the food, agriculture, and pharmaceutical industries due to their low cost and versatility. This study compared the stabilizing and releasing abilities for thymol of three kinds of pre-formed V-type starch (Water-V, Salt-V, and Alkali-V) and β-CD. The loading efficiency for thymol decreased in the order of Water-V > Alkali-V > CD > Salt-V when removing the free thymol. Water-V, β-CD, and their ICs had better thermal stability with maximum thermal decomposition temperatures over 320 °C. Under non-cold chain daily storage conditions for 4 d, the percentage of thymol released from starch/CD-thymol ICs was 14% (Water-V), 35% (Salt-V), 34% (Alkali-V), and 43% (CD). The Water-V made ICs had good sustained release properties and long-term antibacterial activity, which kept strawberries fresh for 6 d without decay.

Double-crosslinked self-healing hydrogel alleviates osteoarthritis by protecting from wearing and targeting NF-kB signaling

Osteoarthritis (OA) is a chronic disease that causes pain, morbidity, and disability. The main strategy for OA treatment focuses on inflammation suppression, inhibition of osteoclastogenesis, and protection of articular cartilage. These functions cannot be performed effectively by monotherapy. Therefore, an effective drug delivery system is required, capable of containing and controlling the efflux of various drugs to alleviate osteoclastogenesis, protect cartilage and subchondral bone, and suppress inflammation. In this work, an encapsulation system is constructed using a self-healing chitosan hydrogel and allocated compound drugs. The self-healing gel is composed of branched-functionalized chitosan, created by simultaneously using polycaprolactone polyethylene glycol azide as a block polymer and the host-guest assembly of β-cyclodextrin and adamantane. Inhibitors of the NFkB pathway are loaded into the cavities of β-cyclodextrin and the spring-like structure of the block polymer, which can be rapidly released upon joint friction (due to the reassembly of β-cyclodextrin and adamantane by shear stress and the stretch of the block polymer). In vitro experiments using BMMs and the ATDC5 cell line confirm that the developed hydrogel can simultaneously suppress osteoclastogenesis and induce chondrogenesis. Additionally, a model of knee arthritis in C57 mice was used to confirm that this double-crosslinked encapsulation system can lubricate the knee joint surface and provide adequate protection on demand through shear-responsive drug release.

Multidimension‐Regulated Dynamic Timing Control Over Multicolor Emission of Host–Guest Assemblies for Information Encryption and Advanced Anti‐Counterfeiting

AbstractDynamical control over molecular luminescence, especially in a time‐dependent manner, holds great promise for the development of smart luminescent materials for anti‐counterfeiting and preventing information leakage. Herein, a series of self‐assembled systems are reported using pillar[5]arene (DMP[5]) and spiropyran derivatives (SP‐C4‐Py). The assemblies rely on the time‐encoded locking and unlocking ring‐switching and fluorescence resonance energy transfer (FRET) units for information camouflage and multilevel encryption. DMP[5] with cyan solid fluorescence color acts as the host and energy transfer (EnT) donor, while photochromic SP‐C4‐Py with the ring‐opened and closed isomers acts as guest and EnT acceptor. When irradiated, the assemblies undergo a time‐dependent luminescence color change ranging from cyan to yellow to red through a FRET process. The molar ratio of host and guest in the assembly systems affects the FRET efficiency, and the power of the irradiation source influences the isomerization degree and rate of SP‐C4‐Py, allowing for precise control over the fluorescent color transition time. The combination of molecular composition and external stimuli governs the kinetics of color change, resulting in a difference in the appearance time of a specific fluorescent color pre‐designed as correct authorized information. By combining these diverse assembles in one label, information encryption and dynamic information identification are achieved in the dimensions of time, ratio, and light power. This time‐dependent feature offers the assembly materials with a multilevel security and provides new possibilities for anti‐counterfeiting and blocking information leakage.

Synthesis and applications of conjugated pillar[5]arenes

Pillar[n]arenes, as a new class of macrocyclic hosts, show bright prospect due to their rigid cavity structures, rich host-guest interactions, and easy functionalization. How to improve the host-guest recognition selectivity, signal report sensitivity and host-guest assembly properties of the pillar[n]arene-based hosts by rational functionalization is an attractive issue. Among various of functionalization approaches for pillar[5]arenes, constructing conjugated systems through the A, A′-sites of pillar[5]arenes is a very crucial method. In contrast to conventional alkoxy chain-functionalized pillar[5]arenes, conjugated pillar[5]arenes exhibit superior charge transfer and signal response capabilities, as well as a rigid structure that facilitates the construction of framework materials. Furthermore, they readily facilitate collaborative effects through functionalized groups within the cavity of the pillar[5]arenes. There are many nice works on design synthesis and applications of conjugated pillar[5]arenes in various fields. This minireview presents a systematic introduction on the synthesis of conjugated pillar[5]arenes and their applications in different fields.

Multi-step FRET systems based on discrete supramolecular assemblies.

Fluorescence resonance energy transfer (FRET) from the excited state of the donor to the ground state of the acceptor is one of the most important fluorescence mechanisms and has wide applications in light-harvesting systems, light-mediated therapy, bioimaging, optoelectronic devices, and information security fields. The phenomenon of sequential energy transfer in natural photosynthetic systems provides great inspiration for scientists to make full use of light energy. In recent years, discrete supramolecular assemblies (DSAs) have been successively constructed to incorporate donor and multiple acceptors, and to achieve multi-step FRET between them. This perspective describes recent advances in the fabrication and application of DSAs with multi-step FRET. These DSAs are categorized based on the non-covalent scaffolds, such as amphiphilic nanoparticles, host-guest assemblies, metal-coordination scaffolds, and biomolecular scaffolds. This perspective will also outline opportunities and future challenges in this research area.

Thermodynamic regulation of electrolyte to achieve air-tolerant viologen-based flow battery

Aqueous organic redox flow battery (AORFB) is one promising grid-scale energy storage technology. However, the application is seriously hindered as AORFB cannot be stably operated in air, and the reason lies in the poor air tolerance of electroactive organics. Herein, we develop a thermodynamic regulation strategy through host-guest assembly to improve the air tolerance of the viologen-based anolyte. It is found that the reduced state of viologen forms a host-guest complex with the hydroxyethyl-β-cyclodextrin (HE-β-CD) molecule via hydrophobic effect, and the host HE-β-CD serves as a steric hindrance to kinetically shield the reduced viologen against oxygen attack. As demonstration, a flow battery fed with the viologen/HE-β-CD anolyte achieves a high Coulombic efficiency (∼99.9 %) and superior cyclability (∼97.73 % capacity retention rate over 300 cycles) when operated in air. This work provides a facile supramolecular method to tackle the most urgent issue of AORFB, which paves the way for its practical application.

Surficial Host-Guest Responsive CsPbBr3 Perovskite Nanocrystals for Programmable Multi-Level Information Encryption.

The design of smart stimuli-responsive photoluminescent materials capable of multi-level encryption and complex information storage is highly sought after in the current information era. Here, a novel adamantyl-capped CsPbBr3 (AD-CsPbBr3) perovskite NCs, along with its supramolecular host-guest assembly partner a modified β-CD (mCD), mCD@AD-CsPbBr3, are designed and prepared. By dispersing these two materials in different solvents, namely, AD-CsPbBr3 in toluene, mCD@AD-CsPbBr3 in toluene, and mCD@AD-CsPbBr3 in methanol, the three solutions exhibit diverse photoluminescence (PL) turn-on/off or PL discoloration response upon supramolecular stimulus. Based on these responses, a proof-of-principle programmable Multi-Level Photoluminescence Encoding System (MPLES) is established. Three types of four-level and three types of three-level information encoding are achieved by the system. A layer-by-layer four-level information encryption and decryption as well as a two-level encrypted 3D code are successfully achieved.

Branched-Chain-Induced Host-Guest Assembly in Covalent-Organic Frameworks for Efficient Separation of No-Carrier-Added 177Lu.

No-carrier-added (NCA) 177Lu is one of the most interesting nuclides for endoradiotherapy. With the dramatically rapid development of radiopharmaceutical and nuclear medicine, there is a sharp increase in the radionuclide supply of NCA 177Lu, which has formed a great challenge to current radiochemical separation constituted on classical materials. Hence, it is of vital importance to design and prepare new functional materials able of recovering 177Lu from an irradiated target with excellent efficacy. In this work, we proposed to apply noncovalent interactions to regulate the porous properties of covalent organic frameworks (COFs) by tuning the branched chain, rendering related covalent hosts different encapsulation abilities toward a flexible guest, 2-ethylhexylphosphonic acid mono-2-ethylhexyl ester (P507). More interestingly, we found that the noncovalent interaction has a great effect on the host-guest complexes, which can achieve efficient NCA 177Lu separation with high recovery (95.97%). A systematic mechanism combined with experimental and theoretical investigations has confirmed that the noncovalent interactions between COFs and P507 play a preeminent role in adjusting the macroscopic properties of the host-guest complexes. This work not only uncovers that noncovalent interactions can affect the basic properties of covalent organic bonded materials but also provides a strategy for the design and preparation of other new moieties with specific functionalities.

Supramolecular Assembly Based on Calix(4)arene and Aggregation-Induced Emission Photosensitizer for Phototherapy of Drug-Resistant Bacteria and Skin Flap Transplantation.

Photodynamic therapy as a burgeoning and non-invasive theranostic technique has drawn great attention in the field of antibacterial treatment but often encounters undesired phototoxicity of photosensitizers during systemic circulation. Herein, a supramolecular substitution strategy is proposed for phototherapy of drug-resistant bacteria and skin flap repair by using macrocyclic p-sulfonatocalix(4)arene (SC4A) as a host, and two cationic aggregation-induced emission luminogens (AIEgens), namely TPE-QAS and TPE-2QAS, bearing quaternary ammonium group(s) as guests. Through host-guest assembly, the obtained complex exhibits obvious blue fluorescence in the solution due to the restriction of free motion of AIEgens and drastically inhibits efficient type I ROS generation. Then, upon the addition of another guest 4,4'-benzidine dihydrochloride, TPE-QAS can be competitively replaced from the cavity of SC4A to restore its pristine ROS efficiency and photoactivity in aqueous solution. The dissociative TPE-QAS shows a high bacterial binding ability with an efficient treatment for methicillin-resistant Staphylococcus aureus (MRSA) in dark and light irradiation. Meanwhile, it also exhibits an improved survival rate for MRSA-infected skin flap transplantation and largely accelerates the healing process. Thus, such cascaded host-guest assembly is an ideal platform for phototheranostics research.

Assembly and Utility of a Drawstring‐Mimetic Supramolecular Complex

AbstractInspired by the drawstring structure in daily life, here we report the development of a drawstring‐mimetic supramolecular complex at the molecular scale. This complex consists of a rigid figure‐of‐eight macrocyclic host molecule and a flexible linear guest molecule which could interact through three‐point non‐covalent binding to form a highly selective and efficient host‐guest assembly. The complex not only resembles the drawstring structure, but also mimics the properties of a drawstring with regard to deformations under external forces. The supramolecular drawstring can be utilized as an interlocked crosslinker for poly(methyl acrylate), and the corresponding polymer samples exhibit comprehensive enhancement of macroscopic mechanical performance including stiffness, strength, and toughness.

Assembly and Utility of a Drawstring-Mimetic Supramolecular Complex.

Inspired by the drawstring structure in daily life, here we report the development of a drawstring-mimetic supramolecular complex at the molecular scale. This complex consists of a rigid figure-of-eight macrocyclic host molecule and a flexible linear guest molecule which could interact through three-point non-covalent binding to form a highly selective and efficient host-guest assembly. The complex not only resembles the drawstring structure, but also mimics the properties of a drawstring with regard to deformations under external forces. The supramolecular drawstring can be utilized as an interlocked crosslinker for poly(methyl acrylate), and the corresponding polymer samples exhibit comprehensive enhancement of macroscopic mechanical performance including stiffness, strength, and toughness.

Host-guest assembly triggered lower critical solution temperature behavior with reversible photo-regulation

The less frequent lower critical solution temperature (LCST) phenomenon has attracted extensive attention due to the foresighted application in smart materials. Nevertheless, the existing LCST-type materials are mainly dominated by a few polymers with specific moieties due to the damped hydration at a higher temperature and the lack of reversible regulations of the corresponding temperature sensitivity. Herein, an unanticipated and reversibly photo-responsive LCST behavior was uncovered in the BSC4/Azo-4 assembly solution. Such behavior arose from the host-guest binding between BSC4 and Azo-4 in an aqueous solution since neither the guest nor host alone exhibited an LCST property. Ascribing to the distinct π-π stacking between the trans- and cis-isomers of Azo-4, a reversible regulation of LCST behavior was achieved by irradiating UV and blue light alternately. Our study demonstrated the complexity and possibility of supramolecular self-assembly, opening a new avenue in the fabrication and adjustment of LCST-type materials in the future.

Regulation of microtubule dynamics and function in living cells via cucurbit[7]uril host-guest assembly.

Living systems utilize sophisticated biochemical regulators and various signal transduction mechanisms to program bio-molecular assemblies and their associated functions. Creating synthetic assemblies that can replicate the functional and signal-responsive properties of these regulators, while also interfacing with biomolecules, holds significant interest within the realms of supramolecular chemistry and chemical biology. This pursuit not only aids in understanding the fundamental design principles of life but also introduces novel capabilities that contribute to the advancements in medical and therapeutic research. In this study, we present a cucurbit[7]uril (CB[7]) host-guest system designed to regulate the dynamics and functions of microtubules (MTs) in living cells. To establish communication between MTs and CB[7] and to reversibly control MT function through host-guest recognition, we synthesized a two-faced docetaxel-p-xylenediamine (Xyl-DTX) derivative. While Xyl-DTX effectively stabilized polymerized MTs, inducing MT bundling and reducing dynamics in GFP-α-tubulin expressing cells, we observed a significant reduction in its MT-targeted activity upon threading with CB[7]. Leveraging the reversible nature of the host-guest complexation, we strategically reactivated the MT stabilizing effect by programming the guest displacement reaction from the CB[7]·Xyl-DTX complex using a suitable chemical signal, namely a high-affinity guest. This host-guest switch was further integrated into various guest activation networks, enabling 'user-defined' regulatory control over MT function. For instance, we demonstrated programmable control over MT function through an optical signal by interfacing it with a photochemical guest activation network. Finally, we showcased the versatility of this supramolecular system in nanotechnology-based therapeutic approaches, where a self-assembled nanoparticle system was employed to trigger the MT-targeted therapeutic effect from the CB[7]·Xyl-DTX complex.

Red Room-Temperature Phosphorescence Supramolecular Assemblies Based on Cucurbit[7]uril: Reversible Temperature Stimulation Response and Cell-Specific Silver Ion Imaging.

Solid-state materials with efficient room-temperature phosphorescence (RTP) emission have been widely used in materials science, and organic RTP-emitting systems with heavy-metal doping in aqueous solutions have attracted much attention in recent years. A novel supramolecular interaction was induced by host-guest assembly using cucurbit[7]uril (Q[7]) as the host and brominated naphthalimide phosphor as the guest. This interaction was further enhanced through synergistic chelation stimulated by analytical silver ion complexation. This approach facilitated the system's structural rigidity, intersystem crossing, and oxygen shielding. We achieved deep red phosphorescence emission in aqueous solution and ambient conditions along with quantitative determination of silver ions. The new complex exhibited good reversible thermoresponsive behavior and was successfully applied for the first time to target phosphorescence imaging of silver ions in the mitochondria of A549 cancer cells. These results are beneficial for constructing novel RTP systems with stimulus-responsive luminescence in aqueous solution, contributing to future research in bioimaging, detection, optical sensors, and thermometry materials.