Host-guest Interactions Research Articles

A novel electrochemical sensor based on ꞵ-cyclodextrin/bismuth oxybromide/multi-walled carbon nanotubes modified electrode with in situ addition of tetrabutylammonium bromide for the simultaneous detection and degradation of tebuconazole.

A novel electrochemical sensor-based glassy carbon electrode (GCE) was fabricated and appliedtosimultaneous detection and degradation of tebuconazole (TBZ) for the first time.TheGCE was consecutively modified by multi-walled carbon nanotubes (MWCNTs), bismuth oxybromide (BiOBr), ꞵ-cyclodextrin (ꞵ-CD), and in situ addition of tetrabutylammonium bromide (TBABr). The detection was based on the decreasing of Bi signal at its anodic potential (Epa) of 0.05V. Under the optimum conditions, the modified electrode exhibited a linear response to TBZ in the concentration range 1-100μg L-1 with a detection limit of 0.9μg L-1. TBZ was firstly adsorbed on the surface of the modified electrode through host-guest molecule interactions of the ꞵ-CD. The adsorption was further enhanced by the large surface area of BiOBr and MWCNTs. The adsorbed TBZ on the electrode surface hindered the electron transfer of Bi, thus decreasing the oxidation of Bi. In addition, the in situ addition of tetrabutylammonium bromide (TBABr) enriched TBZ via electrostatic interactions, increasing its detection sensitivity. The fabricated electrochemical sensor was applied to determine TBZ in water and soil samples from rice fields with recoveries of 80.5-100.5% and 87.6-112%, respectively. Furthermore, the degradation of TBZ on the modified electrode was studied under a solar light simulator. The degradation percentage (100%) of TBZ (50µg L-1) was achieved in5min owing to the excellent photocatalytic properties of BiOBr.

The Swiss Army Knife of Electrodes: Pillar[6]arene‐Modified Electrodes for Molecular Electrocatalysis Over a Wide pH Range

AbstractMolecularly‐modified electrode materials that maintain stability over a broad pH range are rare. Typically, each electrochemical transformation necessitates a specifically tuned system to achieve strong binding and high activity of the catalyst. Here, we report the functionalisation of mesoporous indium tin oxide (mITO) electrodes with the macrocyclic host molecule pillar[6]arene (PA[6]). These electrodes are stable within the pH range of 2.4–10.8 and can be equipped with electrochemically active ruthenium complexes through host–guest interactions to perform various oxidation reactions. Benzyl alcohol oxidation serves as a model reaction in acidic media, while ammonia oxidation is conducted to assess the systems performance under basic conditions. PA[6]‐modified electrodes demonstrate catalytic activity for both reactions when complexed to different guest molecules and can be reused by reabsorption of the catalyst after its degradation. Furthermore, the system can be employed to perform subsequent reactions in electrolyte with varying pH, enabling the same electrode to be utilised in multiple different electrocatalytic reactions.

Hydrogen‐Bonded Organic Frameworks as a Carrier for Nanodrugs with Host–Guest Interaction for Smart Wound Dressing Applications

AbstractThis study introduces surface modification to conventional dressings utilizing adducts of a hydrogen‐bonded organic framework (HOF) with curcumin, curcumin–silver, curcumin‐zinc oxide nanoparticles, and citric acid drugs. Accordingly, eight HOF‐AMs and dressings modified with them were studied. The synthesized structures underwent characterization using various methods, including IR, 1H NMR, XRD, FE‐SEM, and EDX. FE‐SEM results show that the hexagonal morphology is maintained along with the crystal growth in the form of hexagonal tubes. In order to confirm the nanoscale nature of the structures, TEM analysis was conducted specifically for curcumin‐Ag nanoparticles and curcumin–ZnO nanoparticles which confirms the particle size smaller than 50 nm. Knowing the sensitivity of the release of the incorporated substances to temperature and pH, the controlled release of the drugs at two different temperatures (37 °C and 40 °C) and pH levels of 5.5, 7.4, and 9 at the modified dressings was investigated. Investigating the release of HOF‐AMs particles and modified dressings indicates that these products in both cases provide the possibility of drug release in alkaline and acidic pHs. Also, the results showed that increasing the temperature increases the release of curcumin particles in all its types. The modified dressings showed a loading capacity of more than 50 mg g−1.

Color-Tunable Thermally Activated Delayed Fluorescence Polymeric Materials Constructed by Host–Guest Complexation Revealing Rewritable Advanced Information Encryption

Color-Tunable Thermally Activated Delayed Fluorescence Polymeric Materials Constructed by Host–Guest Complexation Revealing Rewritable Advanced Information Encryption

Assembling a new generation of radiopharmaceuticals with supramolecular theranostics.

Supramolecular chemistry has been used to tackle some of the major challenges in modern science, including cancer therapy and diagnosis. Supramolecular platforms provide synthetic flexibility, rapid generation through self-assembly, facile labelling, unique topologies, tunable reversibility of the enabling noncovalent interactions, and opportunities for host-guest chemistry and mechanical bonding. In this Review, we summarize recent advances in the design and radiopharmaceutical application of discrete self-assembled coordination complexes and mechanically interlocked molecules - namely, metallacages and rotaxanes, respectively - as well as in situ-forming supramolecular aggregates, specifically pinpointing their potential as next-generation radiotheranostic agents. The outlook of suchsupramolecular constructs for potential applications in the clinic is discussed.

The Swiss Army Knife of Electrodes: Pillar[6]arene-Modified Electrodes for Molecular Electrocatalysis Over a Wide pH Range.

Molecularly-modified electrode materials that maintain stability over a broad pH range are rare. Typically, each electrochemical transformation necessitates a specifically tuned system to achieve strong binding and high activity of the catalyst. Here, we report the functionalisation of mesoporous indium tin oxide (mITO) electrodes with the macrocyclic host molecule pillar[6]arene (PA[6]). These electrodes are stable within the pH range of 2.4-10.8 and can be equipped with electrochemically active ruthenium complexes through host-guest interactions to perform various oxidation reactions. Benzyl alcohol oxidation serves as a model reaction in acidic media, while ammonia oxidation is conducted to assess the systems performance under basic conditions. PA[6]-modified electrodes demonstrate catalytic activity for both reactions when complexed to different guest molecules and can be reused by reabsorption of the catalyst after its degradation. Furthermore, the system can be employed to perform subsequent reactions in electrolyte with varying pH, enabling the same electrode to be utilised in multiple different electrocatalytic reactions.

Solvent- and Concentration-Induced Topological Transformation of a Ruthenium(II)-Based Trigonal Prism to a Triply Interlocked [2] Catenane.

Synthesis of interlocked supramolecular cages has been a growing field of interest due to their structural diversity. Herein, we report the template-free synthesis of a Ru(II) triply interlocked [2] catenane using coordination-driven self-assembly. The self-assembly of a triazine-based tripyridyl donor L (2,4,6-tris(5-(pyridin-4-yl)thiophen-3-yl)-1,3,5-triazine) with a dinuclear Ru(II) acceptor M (Ru2(dhnq)(η6-p-cymene)2)(CF3SO3)2) yielded two distinct structures depending on the solvent and concentration. In methanol, a triply interlocked metalla [2] catenane (MC2) was formed, whereas in nitromethane, a non-interlocked cage (MC1) was obtained. The non-interlocked cage MC1 was gradually converted to MC2 in nitromethane by the increase in the concentration of cage MC1 from 0.5 to 9 mM. The interlocked cage (MC2) was stable after formation and was unaffected by the change in concentration. Notably, the free cage (MC1) exhibited host-guest interactions with polycyclic aromatic aldehydes, stabilizing the non-interlocked structure even at higher concentrations. In contrast, the triply interlocked [2] catenane (MC2) remains stable due to self-penetration and does not encapsulate guest molecules. This work showcases the stimuli-induced irreversible structural transformation of a triangular prismatic cage to its triply interlocked [2] catenane by employing metal-ligand coordination chemistry.

In Situ Self-Assembly of Antibody-Rhamnose Complex as a Pre-Targeting Strategy for Enhanced Cancer Immunotherapy.

Enhancing the Fc effector functions of monoclonal antibodies (mAbs) is a proven strategy for improving cancer immunotherapy. In this study, we present a novel pre-targeting approach that integrates host-guest chemistry with an antibody-recruiting concept to create mAbs with superior effector functions. Using rituximab (RTX), a clinically approved anti-CD20 mAb, as our model, we modified RTX by conjugating it with adamantane (Ada) derivatives and various polyethylene glycol (PEG) linkers to produce RTX-Ada conjugates. These conjugates effectively formed RTX-rhamnose (Rha) complexes in situ through self-assembly, driven by host-guest interactions with Rha-modified β-cyclodextrin. This mechanism successfully redirected endogenous anti-Rha antibodies to target cells, enhancing the availability of Fc domains for improved effector functions, including complement-dependent cytotoxicity (CDC). A structure-activity relationship study indicated that the potency of these in situ complexes was significantly influenced by the length of the PEG linker used; shorter PEG linkers correlated with higher CDC activity. Given the variability in endogenous antibody levels among individuals, this strategy presents a flexible and promising platform for enhancing the efficacy of mAb-based cancer immunotherapy.

Supramolecular assembly of antibody-rhamnose complex to enhance the complement-dependent cytotoxicity for cancer immunotherapy

Enhancing the complement-dependent cytotoxicity (CDC) of monoclonal antibodies (mAbs) has the potential to improve their clinical performance. In this study, we describe an innovative antibody-hapten supramolecular complex strategy to amplify CDC activity. We selected Rituximab (RTX), an approved anti-CD20 mAb, and conjugated it with adamantane (Ada) to generate RTX-Ada. After targeting CD20-positive cells, this conjugate can interact with rhamnose (Rha)-modified β-cyclodextrin via host-guest interaction, in situ forming a supramolecular complex that can recruit anti-Rha antibodies onto CD20-positive cancer cells. This complex provides a larger number of Fc domains for complement system activation, leading to enhanced CDC. Our study demonstrates the potential of antibody-based supramolecular complexes for cancer immunotherapy, offering a promising approach to improve the efficacy of mAb-based cancer treatments.

Separation performances of extended pillar[6]arenes, a new stationary phase for gas chromatography

Pillar[n]arenes (P[n]As, n = 5–10), a new generation of macrocyclic hosts, display interesting properties such as 3D π-electron cavity, host-guest interactions, good stability, and easy functionalization, which make these polymers very promising for separation applications. In particular, extended P[n]As (EP[n]As) show large-sized cavities, structural flexibility, cavity adaptability, and synthetic accessibility. These characteristics have been exploited in this work, which reports for the first time the investigation of two EP[n]As (LP6A-C10 and BpP6A-C10) as stationary phases for gas chromatography (GC). LP6A-C10 and BpP6A-C10 columns exhibited moderate polarity (average polarity 117 and 118) and high column efficiencies (3000 plates/m and 3235 plates/m). These columns achieved complete challenging separation of halogenated benzene, benzaldehyde, phenol, and aniline isomers, which are difficult to resolve due to their high resemblance in structures and properties. Experimental results demonstrate the high selectivity and inertness of the prepared columns and their distinct advantages if compared with commercial HP-5 and HP-35 columns. EP[n]As columns displayed good separation repeatability with RSD values of 0.01%–0.02 % for run-to-run, 0.01%–0.22 % for day-to-day, and 1.36–3.56 % for column-to-column. This work demonstrates the promising future of EP[n]A stationary phases for chromatographic separations.

Constructing Quasi‐Single Ion Conductors by a β‐Cyclodextrin Polymer to Stabilize Zn Anode

AbstractAqueous Zn‐ion batteries (AZIBs) are promising for the next‐generation large‐scale energy storage. However, the Zn anode remains facing challenges. Here, we report a cyclodextrin polymer (P‐CD) to construct quasi‐single ion conductor for coating and protecting Zn anodes. The P‐CD coating layer inhibited the corrosion of Zn anode and prevented the side reaction of metal anodes. More important is that the cyclodextrin units enabled the trapping of anions through host–guest interactions and hydrogen bonds, forming a quasi‐single ion conductor that elevated the Zn ion transference number (from 0.31 to 0.68), suppressed the formation of space charge regions and hence stabilized the plating/striping of Zn ions. As a result, the Zn//Zn symmetric cells coated with P‐CD achieved a 70.6 times improvement in cycle life at high current densities of 10 mA cm−2 with 10 mAh cm−2. Importantly, the Zn//K1.1V3O8 (KVO) full‐cells with high mass loading of cathode materials and low N/P ratio of 1.46 reached the capacity retention of 94.5 % after 1000 cycles at 10 A g−1; while the cell without coating failed only after 230 cycles. These results provide novel perspective into the control of solid‐electrolyte interfaces for stabilizing Zn anode and offer a practical strategy to improve AZIBs.

Rational screening of metal single-atom-doped ZSM-5 to promote ring-opening cracking of cycloalkanes to light olefins

The ring-opening cracking of cycloalkanes to light olefins poses a formidable challenge due to the sluggish activation of the C–C bond. In this study, we realize the rational screening of various single metal doped M−ZSM−5 catalysts (M = Mn, Co, Ni, Cu, Zn, Zr, Ru, Rh, Pd, Ag, Pt) to promote the ring-opening cracking of cycloalkanes to light olefins. Our calculation results show that methyl cyclopentane, a model compound of cycloalkanes, tends to adsorb in the form of a “half-chair” configuration in the intersecting channels of the M−ZSM−5, which is caused by the drastic distortion of the five-membered ring, accompanied by large changes in the bond angles. Based on the host–guest interaction between the active site and hydrocarbon in ring-opening cleavage, we reveal that the binding energies of metals to H and C can respectively quantify the metal’s ability to activate C–H and C–C bonds in cycloalkanes. By solving the microkinetic model, we plot activity-selectivity TOF volcano diagrams, where Mn, Ru, Rh-ZSM-5 within the EH range of −2.5 to −3.5 eV and the EC range of −6 to −8 eV can efficiently induce the ring-opening reaction of cycloalkanes without excessive dehydrogenation leading to aromatic hydrocarbon formation. The calculation shows good agreement with catalytic experimental tests and in situ DRIFT spectra results, providing a series of potential candidate catalysts for the ring-opening cracking of cycloalkane-rich diesel fuel.

Constructing Quasi-Single Ion Conductors by a β-Cyclodextrin Polymer to Stabilize Zn Anode.

Aqueous Zn-ion batteries (AZIBs) are promising for the next-generation large-scale energy storage. However, the Zn anode remains facing challenges. Here, we report a cyclodextrin polymer (P-CD) to construct quasi-single ion conductor for coating and protecting Zn anodes. The P-CD coating layer inhibited the corrosion of Zn anode and prevented the side reaction of metal anodes. More important is that the cyclodextrin units enabled the trapping of anions through host-guest interactions and hydrogen bonds, forming a quasi-single ion conductor that elevated the Zn ion transference number (from 0.31 to 0.68), suppressed the formation of space charge regions and hence stabilized the plating/striping of Zn ions. As a result, the Zn//Zn symmetric cells coated with P-CD achieved a 70.6 times improvement in cycle life at high current densities of 10 mA cm-2 with 10 mAh cm-2. Importantly, the Zn//K1.1V3O8 (KVO) full-cells with high mass loading of cathode materials and low N/P ratio of 1.46 reached the capacity retention of 94.5 % after 1000 cycles at 10 A g-1; while the cell without coating failed only after 230 cycles. These results provide novel perspective into the control of solid-electrolyte interfaces for stabilizing Zn anode and offer a practical strategy to improve AZIBs.

Supramolecular Assemblies via Host-Guest Interactions for Tumor Immunotherapy.

Cancer immunotherapy has emerged as one of the most promising modalities for cancer treatment providing hopes of cancer patients with the significant advantages over traditional antitumor therapy methods. Supramolecular assemblies based on host-guest interactions have been widely explored in the field of cancer immunotherapy as the delivery systems. A variety of supramolecular materials show unique features for efficient drug encapsulation, targeting delivery and release, which are favorable to activate antitumor immune responses especially through combination of different treatment strategies. In this review article, we summarize the research progresses of supramolecular assemblies via host-guest interactions for tumor immunotherapy. The construction of various drug delivery systems including hydrogels, liposomes, and polymeric nanoparticles, the drug encapsulation and delivery, as well as advantages and disadvantages are discussed. The perspectives related to future developments in this field are also described.

A Double‐walled Noncovalent Carbon Nanotube by Columnar Packing of Nanotube Fragments

Herein, we report the synthesis of double‐walled noncovalent carbon nanotubes (CNTs) through host–guest complexation of nanotube fragments and tube‐forming crystal engineering. As the smallest fragment of double‐walled CNTs, a host–guest complex of perfluorocycloparaphenylene (PFCPP) and carbon nanobelt (CNB) was synthesized by mixing them in solvents. The immediate complexation of the PF[12]CPP⊃(6,6)CNB complex with a remarkably high association constant (Ka) of 2×105 L/mol was observed. Time‐dependent 1H NMR and thermogravimetry measurements revealed that the stability of (6,6)CNB was significantly improved by encapsulation. X‐ray crystallography confirmed the robust belt‐in‐ring structure of this complex. As indicated by the short distance between PF[12]CPP and (6,6)CNB (2.8 Å), intermolecular orbital interactions exist between the belt and the ring, which were further supported by theoretical calculation and phosphorescence quenching experiments. While the PF[12]CPP⊃(6,6)CNB complex adopts various crystal packing structures, chloroform was discovered to be a magic “glue” solvent inducing one‐dimensional alignment of the PF[12]CPP⊃(6,6)CNB complex to build an unprecedented double‐walled noncovalent CNT structure.

Hierarchical assembly of Ag40 nanowheel ranging from building blocks to diverse superstructure regulation

Achieving precise and controllable hierarchical self-assembly of functional nanoclusters within crystal lattices to create distinct architectures is of immense significance, yet it creates considerable challenges. Here we successfully synthesized a silver nanowheel Ag40, along with its optically pure enantiomers S-/R-Ag40. Each species possesses an internal nanospace and exhibits host-guest interactions. These structures are constructed from primary building blocks (Ag9). By manipulating the surface anions and guest molecules, the nanowheels function as secondary building blocks, spontaneously organizing into complex double- and triple-helical crystalline superstructures or one-dimensional chains {Ag41}n through conformational matching and diverse noncovalent interactions. Moreover, we demonstrate that the water-mediated complex specifically assembled with uridine monophosphate nucleotides, resulting in chiral assemblies of Ag40 that exhibit chiroptical activity for specific recognition. Our findings provide insights into the efficient construction of assemblies with hollow frameworks and propose strategies for superstructure engineering by manipulating surface motifs.

A Double-walled Noncovalent Carbon Nanotube by Columnar Packing of Nanotube Fragments.

Herein, we report the synthesis of double-walled noncovalent carbon nanotubes (CNTs) through host-guest complexation of nanotube fragments and tube-forming crystal engineering. As the smallest fragment of double-walled CNTs, a host-guest complex of perfluorocycloparaphenylene (PFCPP) and carbon nanobelt (CNB) was synthesized by mixing them in solvents. The immediate complexation of the PF[12]CPP⊃(6,6)CNB complex with a remarkably high association constant (Ka) of 2×105 L/mol was observed. Time-dependent 1H NMR and thermogravimetry measurements revealed that the stability of (6,6)CNB was significantly improved by encapsulation. X-ray crystallography confirmed the robust belt-in-ring structure of this complex. As indicated by the short distance between PF[12]CPP and (6,6)CNB (2.8 Å), intermolecular orbital interactions exist between the belt and the ring, which were further supported by theoretical calculation and phosphorescence quenching experiments. While the PF[12]CPP⊃(6,6)CNB complex adopts various crystal packing structures, chloroform was discovered to be a magic "glue" solvent inducing one-dimensional alignment of the PF[12]CPP⊃(6,6)CNB complex to build an unprecedented double-walled noncovalent CNT structure.

Local Regulation of Mitochondrial Respiratory for Enhancing Photodynamic Therapy and Breaking Chemoresistance in Hypoxia.

The hypoxic condition in solid tumors induces therapy resistance, limited therapeutic efficacy, and tumor recurrence, especially for chemotherapy and aerobic photodynamic therapy (PDT). To address this matter, an O2 regulator (SNP@Ato) is designed for breaking chemoresistance and enhancing PDT, which is constructed by loading Atovaquone (Ato) through self-assembly and host-guest interaction between β-cyclodextrin functionalized tetraphenylporphyrin (TPP-CD4) and thioketal-linked camptothecin/azobenzene (Azo-TK-CPT). Specifically, the porphyrin units in SNP@Ato are in "Off state" due to the photoinduced electron transfer (PET) effect between the porphyrin units and azobenzene. After encountering the hypoxic condition in solid tumors, SNP@Ato is dissociated by the cleaved azobenzene on account of over-expressed azo-reductase. Then the mitochondrial respiratory of cancer cells would be suppressed with the participation of Ato, generating a local hypoxia relief for sensitized chemotherapy and enhanced PDT. Accompanied by efficient PDT, the TK linker is broken by ROS, and the CPT is released from the prodrugs. Compared with the SNP group without oxygen-regulator, SNP@Ato exhibits a remarkable improvement of the therapeutic effect against hypoxic tumors in vitro and in vivo. This work proposes a novel paradigm for overcoming hypoxia-induced therapeutic resistance.

Ultrasensitive detection of hazardous gas at room temperature enabled by MOF@MXene 0D-2D heterostructure

Achieving high sensitivity in detecting trace concentrations of toxic gases, particularly under room temperature (RT) conditions, remains a significant challenge. Herein, a 0D-2D heterostructure that can detect ppb-level H2S at RT is proposed by self-assembling cobalt-based metal–organic framework (Co-MOF) on Ti3C2Tx MXene. Co-MOFs with high specific surface areas can capture and concentrate target gas molecules, enhancing host-guest interactions and thereby boosting the selectivity and sensitivity. MXene nanosheets with high conductivity enable rapid electron transport at heterointerface, hence efficiently accelerating the reaction kinetics. Thereby, the as-prepared chemiresistive gas sensor based on Co-MOF@MXene 0D–2D heterostructure possessed excellent sensitivity against interfering gases and delivered an excellent response value of 11.1 to 400 ppb H2S at RT. The judicious design of MOF@MXene heterostructure may spur advanced hybrid material systems for superior sensing applications.

Tetraphenylethene-Based Molecular Cage with Coenzyme FAD: Conformationally Isomeric Complexation toward Photocatalysis-Assisted Photodynamic Therapy.

Flavin adenine dinucleotide (FAD), serving as a light-absorbing coenzyme factor, can undergo conformationally isomeric complexation within different enzymes to form various enzyme-coenzyme complexes, which exhibit photocatalytic functions that play a crucial role in physiological processes. Constructing an artificial photofunctional system using FAD or its derivatives can not only develop biocompatible photocatalytic systems with excellent activities but also further enhance our understanding of the role of FAD in biological systems. Here, we demonstrate a supramolecular approach for constructing an artificial enzyme-coenzyme-type host-guest complex with photoinduced catalytic function in water. First, we have designed and synthesized a water-soluble tetraphenylethene (TPE)-based octacationic molecular cage (1) with a large and flexible cavity, which can adaptively encapsulate with two FAD molecules with "U-shaped" conformation (uFAD) to form a 1:2 host-guest complex (1⊃uFAD2) in water. Second, based on the conformationally isomeric complexation of FAD within 1, the 1⊃uFAD2 complex facilitates electron and energy transfers to molecular oxygen upon the white-light illumination, efficiently producing reactive oxygen species (ROS) such as superoxide radical (O2•-) and singlet oxygen (1O2). To our knowledge, the 1⊃uFAD2 complex acts as a photocatalyst to achieve the highest turnover frequency (TOF) of 35.6 min-1 for the photocatalytic oxidation reaction of NADH via a photoinduced superoxide radical catalysis mechanism in an aqueous medium. At last, combining the cytotoxic effects of ROS and the disruption of the intracellular redox balance involving NADH, 1⊃uFAD2 as a supramolecular photosensitizer displays an excellent oxygen-independent photocatalysis-assisted photodynamic therapy in hypoxic tumors.