Host-guest Recognition Research Articles

A bipolar Electrode-Electrochemiluminescence sensor for Salmonella typhimurium detection based on β-cyclodextrin Host-Guest recognition

A bipolar electrode electrochemiluminescence (BPE-ECL) with β-cyclodextrin (β-CD) host–guest recognition was constructed for the rapid detection of Salmonella typhimurium (S. typhimurium). Firstly, the sulfhydryl β-CD (SH-β-CD, with inner diameter size: 6.0–6.5 Å) was assembled on the gold-plated cathode of BPE. Ferrocene (Fc, length: 3.5 Å; width: 4.4 Å) labelled signal probe and parts Fc-aptamer complement each other to form a double-stranded DNA (dsDNA). Due to its large size, the dsDNA with a double Fc (width > 8.8 Å) could not be embedded into the cavities of β-CD. In the presence of S. typhimurium, Fc-aptamer bond specifically to S. typhimurium, and the signal probe was shed from the dsDNA. Then, the signal probe (guest) was captured by the SH-β-CD (host) on the surface of the BPE. Due to the principle of spatial matching between Fc and SH-β-CD, a stable inclusion complex could be formed, which made Fc close to the cathode surface of the BPE. When a certain driving voltage was applied, Fc was oxidized to Fc+. The cathode surface of Fc+ would promote electron transfer, causing the [Ru(bpy)3]2+ at the anode emit light, and effectively convert the electrochemical signal into an ECL signal. 101-105 CFU mL−1S. typhimurium was positively correlated with Fc+ and ECL intensity, with a detection limit of 101 CFU mL−1. Therefore, S. typhimurium can be quantitatively detected by the electron transfer rate of the BPE.

Design and Synthesis of New Type of Macrocyclic Architectures Used for Optoelectronic Materials and Supramolecular Chemistry.

Supramolecular chemistry has received much attention for decades. Macrocyclic architectures as representative receptors play a vital role in supramolecular chemistry and are applied in many fields such as supramolecular assembly and host-guest recognition. However, the classical macrocycles generally lack functional groups in the scaffolds, which limit their further applications, especially in optoelectronic materials. Therefore, developing a new design principle is not only essential to better understand macrocyclic chemistry and the supramolecular behaviors, but also further expand their applications in many research fields. In recent years, the doping compounds with main-group heteroatoms (B, N, S, O, P) into the carbon-based π-conjugated macrocycles offered a new strategy to build macrocyclic architectures with unique optoelectronic properties. In particular, the energy gaps and redox behavior can be effectively tuned by incorporating heteroatoms into the macrocyclic scaffolds. In this Minireview, we briefly summarize the design and synthesis of new macrocycles, and further discuss the related applications in optoelectronic materials and supramolecular chemistry.

Interfacial Rheological and Emulsion Properties of Self-Assembled Cyclodextrin-Oil Inclusion Complexes.

To investigate the effect of the molecular size of alkanes and the cavity size of cyclodextrins (CDs) on the formation of interfacial host-guest inclusion complexes, the interfacial tension (IFT) of CD (α-CD, β-CD, γ-CD) solutions against oils (hexadecane, dodecylbenzene) was determined by interfacial dilational rheology measurements. The results show that the "space compatibility" between CDs and oil molecules is crucial for the formation of interface host-guest inclusion complexes. Hexadecane with a smaller molecular size can form host-guest inclusion complexes with small cavities of α-CD and β-CD, dodecylbenzene with a larger molecular size can form interfacial aggregates with the medium-sized cavity of β-CD easily, and the polycyclic aromatic hydrocarbon molecules in kerosene can form inclusion complexes with the large cavity of γ-CD. The formation of interfacial inclusion complexes leads to lower IFT values, higher interfacial dilational modulus, nonlinear IFT responses to the interface area oscillating, and skin-like films at the oil-water interface. What's more, the phase behavior of Pickering emulsions formed by CDs with different oils is explored, and the phenomena in alkane-CD emulsions are in line with the results in dilatation rheology. The interfacial active host-guest structure in the kerosene-γ-CD system improves the stability of the Pickering emulsion, which results in smaller emulsion droplets. This unique space compatibility characteristic is of great significance for the application of CDs in selective host-guest recognition, sensors, enhanced oil recovery, food industries, and local drug delivery.

Supramolecular Modulation of Tumor Microenvironment through Pillar[5]arene-Based Host-Guest Recognition to Synergize Cancer Immunotherapy.

Despite the tremendous breakthrough of immunotherapy, the low response rate and resistance of immune checkpoint inhibitors (ICIs) toward solid tumors occur frequently. A highly hypoxic tumor microenvironment (TME) provides tumor cells with high concentrations of HIF-1α and polyamines to evade immune cell destruction. Reprogramming of an immunogenic TME has exhibited a brilliant future to boost immunotherapeutic performances. Herein, a supramolecular nanomedicine (TAPP) is developed on the basis of host-guest molecular recognition and metal coordination, showing the capability to remodel the immunosuppressive TME. Tamoxifen (Tmx) and Fe3+ are encapsulated into TAPP to achieve the combination of chemotherapy and chemodynamic therapy (CDT). Tmx directly downregulates HIF-1α, and a pillar[5]arene-based macrocyclic host successfully eliminates polyamines in tumors. Enhanced immunogenic cell death is achieved by Tmx and Fe3+, and the therapeutic efficacy is further synergized by immune checkpoint blockade (ICB) therapy. This supramolecular reprogramming modality encourages cytotoxic T lymphocyte infiltration, achieving pre-eminent immune response and long-term tumor suppression.

Calix[4]arene-based covalent organic frameworks with host-guest recognition for selective adsorption of six per- and polyfluoroalkyl substances in food followed by UHPLC-MS/MS detection

Long-term ingestion or exposure to food contaminated with per- and polyfluoroalkyl substances (PFASs) may cause potential harm to human health. Due to the low contents of PFASs in complex food matrices, it is of great significance to develop adsorbents with excellent properties to enrich PFASs before analysis. Herein, calix[4]arene (CX4) was used as building block to prepare ordered crystalline covalent organic frameworks (COFs). The perfect combination of the host-guest recognition ability of CX4 and the porosity of COFs makes the CX4-COFs selective and high adsorption capacity for linear molecular PFASs (261–1055 mg/g). The adsorption behavior and mechanism were verified by isotherm adsorption experiments and simulation calculations. The CX4-COFs were then used as adsorbents for membrane solid-phase extraction (M-SPE), combined with ultra-high performance liquid chromatography tandem mass spectrometry (UHPLC-MS/MS) to determine PFASs in food. The method has low detection limits (0.11–0.28 ng/kg) and good precision (1.3%−9.8%), and has been successfully applied to the simultaneous enrichment and determination of six PFASs in fish, shrimp and shellfish. Satisfactory recoveries (79.9%−118%) were obtained. This study provides a new strategy for preparing CX4-COFs containing macrocyclic molecules with different morphologies and expands the application of COFs as attractive enrichment media for sample pretreatment.

A novel host–guest recognition electrochemiluminescence system for phenylalanine detection based on Ir@ZnO nanocomposites and cucurbit[8]uril

Iridium complexes have been considered as potential promising electrochemiluminescent (ECL) reagents in recent years. However, the instability of ECL signal and easy leaching from the electrode severely limit their applications. In this work, iridium complex doped zinc oxide (ZnO) nanocomposites (Ir@ZnO) were synthesized, which could not only increase the loading amount of iridium complex, but also improve the stability of ECL signal. A sensitive ECL sensor for the detection of phenylalanie (Phe) was proposed via the host–guest recognition of cucurbit[8]uril (Q[8]) and Phe with Ir@ZnO nanocomposites as a signal probe. Q[8] was combined with Ir@ZnO nanocomposites via coordinate bond between carbonyl group of Q[8] and Ir and Zn atoms, which could quench the ECL intensity due to the accommodating ability of Q[8] for dissolved oxygen. In the presence of Phe, Q[8] could be released from the electrode surface through the strong host–guest interaction, and the ECL intensity was restored. The ECL system performed high sensitivity and low detection limit, indicating that the proposed ECL strategy was suitable for the detection of amino acids. Moreover, this work provided a new avenue for the application of water insoluble Ir complexes in ECL sensing field.

An electrochemical biosensor for detection of T4 polynucleotide kinase activity based on host-guest recognition between phosphate pillar[5]arene and methylene blue

T4 polynucleotide kinase (T4 PNK) is an important DNA repair-related enzyme that plays a crucial role in DNA recombination, replication and damage repair. Herein, an electrochemical biosensor was developed for detection of T4 PNK activity and inhibitor screening based on supramolecular host–guest recognition between phosphate pillar (Dumitrache and McKinnon, 2017) [5] arene (PP5) and methylene blue (MB). The water-soluble PP5 employed as the host for complexation of MB guest molecules. The substrate DNA with 5′-hydroxyl group was first self-assembled on the gold electrode surface through the chemical adsorption of the thiol group, which was phosphorylated in the presence of T4 PNK and adenosine triphosphate (ATP). TiO2 served as a bridge to link phosphorylated DNA and PP5 via the robust phosphate-Ti4+-phosphate chemistry. The immobilized PP5 captured the MB on electrode surface via the supramolecular host–guest recognition interaction, resulting in an enhanced electrochemical response signal. The electrochemical signal is proportional to the T4 PNK concentration in the range of 2 × 10−4 to 5 U mL−1 with a detection limit of 1 × 10−4 U mL−1. It was also successfully used for PNK inhibitor screening and PNK activity assay in HeLa cell lysates sample. The proposed strategy provides a novel sensing platform for kinase activity assay and inhibitor screening, holding a great potential in clinical diagnostics, inhibitor screening, and nucleotide kinase-target drug discovery.

Pillar[5]arene-Based AIE Supramolecular Polymer Networks Exhibiting Various Fluorescence to Achieve Visible Surveillance.

Supramolecular polymer networks (SPNs) based on pillar[n]arene are widely studied and it is known that evolution from linear polymers to SPNs occurs as a progressive process, which is of importance to monitor the detailed morphology throughout the process. Yet, the current reports related to that distinction by employing fluorescence approach have realized confined success, it still remains a challenge to distinguish the various states visually. Herein, a fluorescent group of the pyrene benzohydrazonate-based (PBHZ-based) derivative is introduced into the pillar[5]arene based SPNs gained from host-guest recognition, enabling the visual monitoring during the formation of SPNs. The whole visual detection was based on the fluorescence color transition ranging from blue to green relying on the gradual aggregated PBHZ molecules upon the increasing cross-linking degree. Besides, the stimuli-responsiveness of this SPNs was confirmed that increasing the temperature or adding a reducing agent would reduce the cross-linking degree.

Reversible control of tetrazine bioorthogonal reactivity by naphthotube-mediated host-guest recognition

•Naphthotubes can recognize phenyltetrazine-modified biomolecules with high affinity •Reversible control of phenyltetrazine reactivity through molecular recognition •Selective tetrazine residue caging enables sequential IEDDA reactions on proteins •Reversible caging of phenyltetrazine activity in living cells and animals Tetrazine-mediated inverse electron demand Diels-Alder (IEDDA) reactions are widely used ultrafast bioorthogonal reactions, and methods to control such reactions would be extremely useful. Here, we identified a high-affinity host-guest pair between synthetic macrocyclic naphthotubes and phenyltetrazine and developed a molecular-recognition strategy for controlling tetrazine reactions by host caging. Naphthotubes can recognize phenyltetrazine on various biomolecules with low-micromolar and sub-micromolar binding affinities and thus cage their IEDDA reactivity efficiently in a reversible manner. For tetrazine residues on proteins encoded by non-canonical amino acid mutagenesis, their positions could be computationally designed such that exposed residues could be reversibly caged, whereas semiburied residues that were resistant to caging retained their reactivity, thus allowing preparation of site-specific protein dual conjugates and dual protein labeling on living cells with IEDDA reactions. The reactivity of tetrazine can be further regulated in living animals. Our strategy is thus expected to expand the applications of tetrazine chemistry. Tetrazine-mediated inverse electron demand Diels-Alder (IEDDA) reactions are widely used ultrafast bioorthogonal reactions, and methods to control such reactions would be extremely useful. Here, we identified a high-affinity host-guest pair between synthetic macrocyclic naphthotubes and phenyltetrazine and developed a molecular-recognition strategy for controlling tetrazine reactions by host caging. Naphthotubes can recognize phenyltetrazine on various biomolecules with low-micromolar and sub-micromolar binding affinities and thus cage their IEDDA reactivity efficiently in a reversible manner. For tetrazine residues on proteins encoded by non-canonical amino acid mutagenesis, their positions could be computationally designed such that exposed residues could be reversibly caged, whereas semiburied residues that were resistant to caging retained their reactivity, thus allowing preparation of site-specific protein dual conjugates and dual protein labeling on living cells with IEDDA reactions. The reactivity of tetrazine can be further regulated in living animals. Our strategy is thus expected to expand the applications of tetrazine chemistry. Bioorthogonal chemistry: Bridging chemistry, biology, and medicineHartung et al.ChemJune 5, 2023In BriefBioorthogonal chemistry has become a flourishing toolbox of approaches for performing selective reactions in complex biological systems without perturbing natural processes. Through the implementation of this chemistry, chemical biologists have answered previously unanswerable questions, made new and exciting discoveries, and even begun to have an impact on important therapies, including implementing a bioorthogonal reaction at the center of a new cancer-treatment clinical trial. We highlight some key advances and anticipate next steps within this latest Nobel Prize-winning field. Full-Text PDF

Phototriggered Formation of a Supramolecular Polymer Network Based on Orthogonal H-Bonding and Host-Guest Recognition

Phototriggered Formation of a Supramolecular Polymer Network Based on Orthogonal H-Bonding and Host-Guest Recognition

Alkali Metal Ion Recognition by 18-Crown-6 in Aqueous Solutions: Evidence from Local Structures

The underlying recognition mechanisms of alkali metal ions by crown ethers in aqueous solutions are yet to be fully understood at the molecular level. We report direct experimental and theoretical evidence for the structure and recognition sequence of alkali metal ions (Li+, Na+, K+, Rb+, and Cs+) by 18-crown-6 in aqueous solutions by wide-angle X-ray scattering combined with an empirical potential structure refinement modeling and ab initio molecular dynamics simulation. Li+, Na+, and K+ are located in the negative potential cavity of 18-crown-6, with Li+ and Na+ deviating from the centroid of 18-crown-6 by 0.95 and 0.35 Å, respectively. Rb+ and Cs+ lie outside the 18-crown-6 ring and deviate from the centroid of 18-crown-6 by 0.05 and 1.35 Å, respectively. The formation of the 18-crown-6/alkali metal ion complexes is dominated by electrostatic attraction between the cations and the oxygen atoms (Oc) of 18-crown-6. Li+, Na+, K+, and Rb+ form the H2O···18-crown-6/cation···H2O "sandwich" hydrates, while water molecules only hydrate with Cs+ of the 18-crown-6/Cs+ complex on the same side of Cs+. Based on the local structure, the recognition sequence of 18-crown-6 for alkali metal ions in an aqueous solution follows K+ > Rb+ >Na+ >Li+, which is completely different from that (Li+ > Na+ > K+ > Rb+ > Cs+) in the gas phase, confirming that the solvation medium seriously affects the cation recognition of crown ethers. This work provides atomic insights into understanding the host-guest recognition and solvation behavior of crown ether/cation complexes.

Supramolecular nanoparticles constructed by orthogonal assembly of pillar[5]arene-cyclodextrin dimacrocycle for chemo-photodynamic combination therapy

Chemotherapy combined with photodynamic therapy has emerged as a promising strategy for cancer treatment. However, simultaneously delivering chemotherapeutic drugs and photosensitizers and precisely adjusting the ratio of the two components as needed remains a challengeable task. Herein, novel supramolecular nanoparticles (donated as BODIPY-CPT-NPs) for chemo-photodynamic combination cancer therapy are constructed from a glutathione-responsive camptothecin-based prodrug, BODIPY photosensitizer, and dimacrocyclic host molecule through orthogonal host-guest recognitions and co-assembly. With this strategy, the ratio of prodrugs and photosensitizers in nanoparticles can be easily and precisely controlled as needed. Benefiting from the strong host-guest interactions and stable self-assembly, the nanoparticles exhibit excellent stability and photobleaching resistance. Furthermore, camptothecin can be released from nanoparticles for chemotherapy in the presence of reduction agent and single oxygen can be efficiently generated for PDT with light irradiation. The combined effects of the BODIPY-CPT-NPs have been verified in CT26 and HeLa cancer cells.

2D MOF-enhanced SPR sensing platform: Facile and ultrasensitive detection of Sulfamethazine via supramolecular probe

Sulfamethazine (SMZ) is widely present in the environment and can cause severe allergic reactions and cancer in humans. Accurate and facile monitoring of SMZ is crucial for maintaining environmental safety, ecological balance, and human health. In this work, a real-time and label-free surface plasmon resonance (SPR) sensor was devised using a two-dimensional metal-organic framework with superior photoelectric performance as an SPR sensitizer. The supramolecular probe was incorporated at the sensing interface, allowing for the specific capture of SMZ from other analogous antibiotics through host-guest recognition. The intrinsic mechanism of the specific interaction of the supramolecular probe-SMZ was elucidated through the SPR selectivity test in combination with analysis by density functional theory, including p-π conjugation, size effect, electrostatic interaction, π-π stacking, and hydrophobic interaction. This method facilitates a facile and ultrasensitive detection of SMZ with a limit of detection of 75.54 pM. The accurate detection of SMZ in six environmental samples demonstrates the potential practical application of the sensor. Leveraging the specific recognition of supramolecular probes, this direct and simple approach offers a novel pathway for the development of novel SPR biosensors with outstanding sensitivity.

A general supramolecular adjuvant for pesticides based on host-guest recognition.

Pesticides are indispensable in agriculture and can effectively improve the yields and quality of crops. Due to their weak water solubility, most pesticides need to be dissolved by adding solubilizing adjuvants. In this work, based on molecular recognition of the macrocyclic host, we developed a novel supramolecular adjuvant, called sulfonated azocalix[4]arene (SAC4A), which significantly improves the water solubility of pesticides. SAC4A presents multiple advantages, including high water solubility, strong binding affinity, universality, and simple preparation. SAC4A showed an average binding constant value of 1.66 × 105 M-1 for 25 pesticides. Phase solubility results indicated that SAC4A increased the water solubility of pesticides by 80-1310 times. The herbicidal, fungicidal, and insecticidal activities of supramolecular formulations were found to be superior to those of technical pesticides, and the herbicidal effects were even better than those of commercial formulations. Overall results revealed the potential of SAC4A to improve the solubility and effectiveness of pesticides, providing a new development idea for the application of adjuvants in agriculture. © 2023 Society of Chemical Industry.

Highly Strong and Tough Supramolecular Polymer Networks Enabled by Cryptand-Based Host-Guest Recognition.

Supramolecular polymer networks (SPNs) demonstrate great potential in the development of smart materials owing to their attractive dynamic properties. However, as they suffer from the inherent weak bonding of most noncovalent cross-links, it remains a significant challenge to construct SPNs with outstanding mechanical performance. Herein, we exploit the cryptand/paraquat host-guest recognition motifs as cross-links to prepare a class of highly strong and tough SPNs. Unlike those supramolecular cross-links with relatively weak binding abilities, the cryptand-based host-guest interactions have a high association constant and steady complexing structure, which effectively stabilizes the network and resists mechanical deformation under external force. Such favorable structural stability endows our SPNs with greatly enhanced mechanical performance, compared with the control-1 cross-linked by the weakly complexed crown ether/secondary ammonium salt motif (tensile strength: 21.1±0.5 vs 2.8±0.1 MPa; Young's modulus: 102.6±4.8 vs 2.1±0.3 MPa; toughness: 90.4±2.0 vs 10.8±0.6 MJ m-3 ). Moreover, our SPNs also retain abundant dynamic properties including good abilities in energy dissipation, reprocessability, and stimuli-responsiveness. These findings provide novel insights into the preparation of SPNs with enhanced mechanical properties, and promote the development of high-performance intelligent supramolecular materials.

Robust antifogging coatings with ultra-fast self-healing performances through host-guest strategy

Given the vulnerability of conventional antifogging coatings to mechanical damage, self-healing capability can significantly restore their functionality, but are difficult to materialize quickly and effectively. Herein, we report a facile UV-curable antifogging coating, based on host–guest interaction to obtain both ultra-fast self-healing performance and robust mechanical properties. Initially, a pair of host–guest supermolecules (HGSM) consisting of acrylic β-cyclodextrin (Aβ-CD) and acrylic adamantane (AAM) are synthesized and utilized as cross-linkers. Together with hydrophilic and hydrophobic moieties, 2-acrylamide-2-methylpropane sulfonic acid (AMPS) and methyl methacrylate (MMA), a robust antifogging coating with ultra-fast self-healing ability is developed via a facile UV curing process. Benefitting from the delicate balance of both hydrophilic and hydrophobic constituents, the resultant coatings display excellent antifogging performance with ∼90 % of light transmission, ranging from −20 °C to 85 °C. The unique non-covalent host–guest structure was covalently integrated into a cross-linked network, as-prepared coating and bulk gel exhibited ultra-fast self-healing capability, needing only ∼15 s to completely heal the cracks under the hot-steam environment (85 °C). And the bulk gels with host–guest recognition can significantly improve its self-healing efficiency to ∼88.3 %, significantly greater than its H-bonding counterpart (43.5 %). Notably, the prepared coating with strong adhesion properties (∼431 KPa) is robust enough to withstand 1,000 cycles of abrasion and 2 h of water immersion to maintain excellent antifogging performance. This strategy might open new avenues for accelerating the use of host–guest assembly to rapidly build effective antifogging/self-healing coatings and promote their applications in more harsh fogging conditions.

The Green Box: Selenoviologen-Based Tetracationic Cyclophane for Electrochromism, Host–Guest Interactions, and Visible-Light Photocatalysis

The novel selenoviologen-based tetracationic cyclophanes (green boxes 3 and 5) with rigid electron-deficient cavities are synthesized via SN2 reactions in two steps. The green boxes exhibit good redox properties, narrow energy gaps, and strong absorption in the visible range (370-470 nm), especially for the green box 5 containing two selenoviologen (SeV2+) units. Meanwhile, the femtosecond transient absorption (fs-TA) reveals that the green boxes have a stabilized dicationic biradical, high efficiency of intramolecular charge transfer (ICT), and long-lived charge separation state due to the formation of cyclophane structure. Based on the excellent photophysical and redox properties, the green boxes are applied to electrochromic devices (ECDs) and visible-light-driven hydrogen production with a high H2 generation rate (34 μmol/h), turnover number (203), and apparent quantum yield (5.33 × 10-2). In addition, the host-guest recognitions are demonstrated between the green boxes and electron-rich guests (e.g., G1:1-naphthol and G2:platinum(II)-tethered naphthalene) in MeCN through C-H···π and π···π interactions. As a one-component system, the host-guest complexes of green box⊃G2 are successfully applied to visible-light photocatalytic hydrogen production due to the intramolecular electron transfer (IET) between platinum(II) of G2 and SeV2+ of the green box, which provides a simplified system for solar energy conversion.

A General Picture of Cucurbit[8]uril Host–Guest Binding: Recalibrating Bonded Interactions

Atomic-level understanding of the dynamic feature of host-guest interactions remains a central challenge in supramolecular chemistry. The remarkable guest binding behavior of the Cucurbiturils family of supramolecular containers makes them promising drug carriers. Among Cucurbit[n]urils, Cucurbit[8]uril (CB8) has an intermediate portal size and cavity volume. It can exploit almost all host-guest recognition motifs formed by this host family. In our previous work, an extensive computational investigation of the binding of seven commonly abused and structurally diverse drugs to the CB8 host was performed, and a general dynamic binding picture of CB8-guest interactions was obtained. Further, two widely used fixed-charge models for drug-like molecules were investigated and compared in great detail, aiming at providing guidelines in choosing an appropriate charge scheme in host-guest modelling. Iterative refitting of atomic charges leads to improved binding thermodynamics and the best root-mean-squared deviation from the experimental reference is 2.6 kcal/mol. In this work, we focus on a thorough evaluation of the remaining parts of classical force fields, i.e., the bonded interactions. The widely used general Amber force fields are assessed and refitted with generalized force-matching to improve the intra-molecular conformational preference, and thus the description of inter-molecular host-guest interactions. The interaction pattern and binding thermodynamics show a significant dependence on the modelling parameters. The refitted system-specific parameter set improves the consistency of the modelling results and the experimental reference significantly. Finally, combining the previous charge-scheme comparison and the current force-field refitting, we provide general guidelines for the theoretical modelling of host-guest binding.

Polymerizable rotaxane hydrogels for three-dimensional printing fabrication of wearable sensors

While hydrogels enable a variety of applications in wearable sensors and electronic skins, they are susceptible to fatigue fracture during cyclic deformations owing to their inefficient fatigue resistance. Herein, acrylated β-cyclodextrin with bile acid is self-assembled into a polymerizable pseudorotaxane via precise host-guest recognition, which is photopolymerized with acrylamide to obtain conductive polymerizable rotaxane hydrogels (PR-Gel). The topological networks of PR-Gel enable all desirable properties in this system due to the large conformational freedom of the mobile junctions, including the excellent stretchability along with superior fatigue resistance. PR-Gel based strain sensor can sensitively detect and distinguish large body motions and subtle muscle movements. The three-dimensional printing fabricated sensors of PR-Gel exhibit high resolution and altitude complexity, and real-time human electrocardiogram signals are detected with high repeating stability. PR-Gel can self-heal in air, and has highly repeatable adhesion to human skin, demonstrating its great potential in wearable sensors.

Nitrogen Doped Porous Biochar/β-CD-MOFs Heterostructures: Bi-Functional Material for Highly Sensitive Electrochemical Detection and Removal of Acetaminophen.

Acetaminophen (AC) is one of the most common over-the-counter drugs, and its pollutant in groundwater has attracted more attention due to its serious risk to human health. Currently, the research on AC is mainly focused on its detection, but few are concerned about its removal. In this work, for the first time, nitrogen-doped Soulangeana sepals derived biochar/β-cyclodextrin-Metal-organic frameworks (N-SC/β-CD-MOFs) composite was proposed for the simultaneous efficient removal and detection of AC. N-SC/β-CD-MOFs combined the properties of host-guest recognition of β-CD-MOFs and porous structure, high porosity, and large surface area of N-SC. Their synergies endowed N-SC/β-CD-MOFs with a high adsorption capacity toward AC, which was up to 66.43 mg/g. The adsorption type of AC on the surface of N-SC/β-CD-MOFs conformed to the Langmuir adsorption model, and the study of the adsorption mechanism showed that AC adsorption on N-SC was mainly achieved through hydrogen bonding. In addition, the high conductivity, large specific surface area and abundant active sites of N-SC/β-CD-MOFs were of great significance to the high-performance detection of AC. Accordingly, the sensor prepared with N-SC/β-CD-MOFs presented a wide linear range (1.0-30.0 μM) and a low limit of detection of 0.3 nM (S/N = 3). These excellent performances demonstrate that N-SC/β-CD-MOFs could act as an efficient dual-functional material for the detection and removal of AC.