Many conductive hydrogels have been developed for wearable electronics; however, it remains a challenge to achieve simultaneous mechanical robustness, stable electrical properties, and tissue-compliant interfaces. Herein, we report a mechanically interlocked polyrotaxane hydrogel prepared via one-pot photopolymerization. The designed network integrates the energy-dissipative "pulley effect" of sliding macrocycles with a stable covalent network. The resulting hydrogel exhibits skin-like softness (modulus ∼8.5 kPa), ultrahigh stretchability (2450%), strong adhesion, and high ionic conductivity (7.46 mS/cm). It functions as a durable strain sensor with a broad sensing range and stable cyclic performance over 10 000 cycles. As an epidermal electrode, it acquires high‑fidelity electrocardiogram (ECG) and electromyogram (EMG) signals with a superior signal‑to‑noise ratio (>42 dB), even during motion, and maintains high signal quality over 24 h. Furthermore, a wearable five‑sensor array demonstrates its capability for real‑time gesture recognition and wireless robotic control. This work provides a robust and multifunctional material platform for advanced wearable bioelectronics.

Given the rapid increase in breast cancer incidence, the Automated Breast Volume Scanner (ABVS) is developed to screen breast tumours efficiently and accurately. However, reviewing ABVS images is a challenging task owing to the significant variations in sizes and shapes of breast tumours. We propose a novel 3D segmentation network (i.e., DST-C) that combines a convolutional neural network (CNN) with a dilated sampling self-attention Transformer (DST). In our network, the global features extracted from the DST branch are guided by the detailed local information provided by the CNN branch, which adapts to the diversity of tumour size and morphology. For medical images, especially ABVS images, the scarcity of annotation leads to difficulty in model training. Therefore, a self-supervised learning method based on a dual-path approach for mask image modelling is introduced to generate valuable representations of images. In addition, a unique postprocessing method is proposed to reduce the false-positive rate and improve the sensitivity simultaneously. The experimental results demonstrate that our model has achieved promising 3D segmentation and detection performance using our in-house dataset. Our code is available at: https://github.com/magnetliu/dstc-net.

The skeleton editing strategy has emerged as a transformative approach in drug discovery and agrochemical innovation, enabling precise modifications through the insertion, elimination, or substitution of specific atoms within the core carbon‐ or heterocyclic frameworks of molecules. Recent advancements in carbene chemistry have led to significant breakthroughs in single‐carbon‐atom insertion reactions, particularly in the context of five‐membered carbon‐ and heterocyclic systems. However, the application of this strategy to six‐membered arenes and heteroarenes has faced considerable challenges, largely due to the thermodynamic and kinetic barriers associated with disrupting the inherent aromaticity of these systems and driving their conversion to seven‐membered rings. In recent years, the development of novel catalytic paradigms, including photo‐ and electro‐catalytic methods, has catalyzed groundbreaking progress in this area. Notably, the design and implementation of asymmetric skeletal editing systems for arenes have significantly expanded the scope and versatility of this methodology, offering new avenues for the rational manipulation of molecular architectures. This review aims to offer a detailed summary and analysis of recent progress in skeletal editing reactions associated with single‐carbon‐atom insertion and outlining the future potential applications of this technology.

Self-assembly of nanomaterials into hierarchical structure is of great interest to fabricate functional materials. However, programmable design of the assembled structures remains a great challenge. Herein, we reported a programmable self-assembly strategy to customize the assembled structure. The self-assembly strategy is designed to orderly transform the two-dimensional (2D) Ca ions assembled F127 nanosheets (Ca-F127 NSs) into spiral nanosheet structures (S-Ca-F127 NSs), branched nanosheet structures (B-Ca-F127 NSs), branched-spiral nanosheet structures (B-S-Ca-F127 NSs), and twisted-branched structures (T-Ca-F127 NBs). Wide-angle X-ray scattering (WAXS) and X-ray absorption spectroscopy (XAS) indicate that these different structures maintain the same orthorhombic phase and Ca-O octahedral coordination structure. Selected area electron diffraction (SAED) in the double-tilt liquid nitrogen cooling holder identifies the Eshelby twist in the twisted structures, demonstrating the spiral structure are formed by screw dislocation growth. Cryo-electron microscopy (cryo-EM) proves the oriented epitaxial growth in the B-Ca-F127 NSs. Furthermore, the formation mechanisms of spiral structure and branched structure can be recombined to form complex hierarchical structures. The epitaxial growth along screw dislocation can lead to the formation of B-S-Ca-F127 NSs, while the twisted epitaxial growth in the screw dislocation can lead to the formation of T-Ca F127 NBs.

The dynamic control of chiral (enantiomeric) responses in chiral host-guest complexes through external stimuli is a significant challenge in modern chemistry for developing smart stimuli-responsive materials. Herein, we report the (chir)optical properties and chiral recognition behavior of water-soluble chiral naphthotubes (1) under the influence of hydrostatic pressure as an external stimulus. The hydrostatic pressure spectral profiles compared to those obtained at normal pressure revealed the dynamic behavior of 1 under hydrostatic pressure, owing to the flexible linker. In chiral recognition experiments, hydrophilic amino acids such as phenylalanine (Phe) and tryptophan (Trp) exhibited reaction volume changes (Delta V degrees) of -0.9 cm(3) mol(-1) for d-Phe, -1.2 cm(3) mol(-1) for l-Phe, -5.6 cm(3) mol(-1) for d-Trp, and -7.0 cm(3) mol(-1) for l-Trp, with enantioselectivity ranging from 1.2 to 1.6. In contrast, hydrophobic chiral styrene oxide (2) showed Delta V degrees values of 1.5 cm(3) mol(-1) for R-2 and 3.5 cm(3) mol(-1) for S-2, with a relatively higher enantioselectivity of up to 7.6. These contrasting effects of hydrostatic pressure primarily originate from the dynamics of chiral naphthotubes.

Studying molecular recognition in aqueous environments is crucial for understanding biological processes. Herein, we present a series of N-doped endo-functionalized anthracene-based cavities by introducing inward-directed pyridine units. The subtle modifications can significantly affect the binding properties of these receptors, which is similar to the mutations in biological systems. Combining theoretical calculations and molecular recognition experiments demonstrated that these “mutations” have an impact on the hydrophobicity and charge distribution of the hosts, consequently significantly influencing molecular recognition. This is crucial for understanding the intricate mechanisms of molecular-level interactions in biological receptors.

The separation of BTEX [benzene, toluene, ethylbenzene (EB), and xylene isomers] poses a huge challenge in the industry, attributed to their similar structures and physical properties. Supramolecular compounds show great promise for hydrocarbon separation. Herein, we designed two pairs of endo-functionalized amide naphthotubes with methyl and benzyl side chains, which were first employed as chromatographic separation materials and exhibited high shape-selectivity for BTEX. In particular, the amide naphthotubes with methyl side chains provided complete separation toward BTEX and anti-3a showed high selectivity for the p-xylene over other isomers with alpha(PX/OX) = 9.34, alpha(PX/MX) = 5.50, and alpha(PX/EB) = 4.30. The mechanism of BTEX separation originates from the synergistic effect of specially confined tandem N-Hpi and C-Hpi interactions toward aromatic compounds. The findings of this research show promise for practical applications in efficiently separating crucial aromatic isomers.

Active compound protection can allow inherently unstable molecules to be stabilized and latent reactivity to be masked. Synthetic receptors are attractive in terms of providing such protection. Nevertheless, preserving the activity and functionality of organic molecules in water poses a challenge. Here, we show that biomimetic receptors, specifically amide naphthotubes and an amide anthryltube, allow the efficient preservation of functional organic molecules in water. In particular, the amide naphthotubes were found to extend the half-lives of acetal-containing substrates ("acetals") against acid-catalyzed hydrolysis by up to 3000 times. This kinetic protection effect was ascribed to hydrogen bond-based recognition of the organic guests. A substrate dependence was seen that was further exploited to achieve the kinetic resolution of acetal isomers. To the best of our knowledge, the present study constitutes one of the most effective acetal protection strategies reported to date. The recognition-based protection approach reported here appears generalizable as evidenced by the protection of eight different substrates against six distinct chemical reactions. Based on the present findings, we propose that it is possible to design receptors that provide for the protection of specific substrates under a variety of reaction conditions including those carried out in water.

Conformational changes in non-covalent complexes are of fundamental importance to many chemical and biological processes. Yet, these low-energy structural changes are usually fast and difficult to monitor, which poses challenges in their detailed kinetic understanding. The correlation between kinetics and thermodynamics of the conformational change of a model supramolecular system featuring a flexible naphthocage and quaternary ammonium guests is described in this work. Guest binding initially locks the host in two major conformations, which then equilibrates over time to the more stable conformer. The overall rate of the system to attain conformational equilibrium is found to inversely correlate with the thermodynamic stability of the host-guest complexes, and hence not only can the kinetic parameters of the conformational exchange be predicted from the easily obtainable thermodynamic data, but the kinetic profile can also be rationalized by using the structural properties of the different guests.

An endo -functionalized molecular cage for selective recognition of creatinine was developed and employed as an ionophore, which enables the accurate potentiometric determination of creatinine levels in biological samples.

New stimulus-responsive scaffolds are of interest as constituents of hierarchical supramolecular ensembles. 1,3,5–2,4,6-Functionalized, facially segregated benzene moieties have a time-honored role as building blocks for host molecules. However, their user as switchable motifs in the construction of multi-component supramolecular structures remains poorly explored. Here, we report a molecular cage  1 , which consists of a bent anthracene dimer 3 paired with 1,3,5-tris(aminomethyl)-2,4,6-triethylbenzene 2 . As the result of the pH-induced ababab ↔ bababa isomerization of the constituent-functionalized benzene units derived from 2 , this cage can reversibly convert between an open state and a closed form, both in solution and in the solid state. Cage  1 was used to create stimuli-responsive hierarchical superstructures, namely Russian doll-like complexes with [K⊂18-crown-6⊂ 1 ] + and [K⊂cryptand-222⊂ 1 ] + . The reversible assembly and disassembly of these superstructures could be induced by switching cage  1 from its open to closed form. The present study thus provides an unusual example where pH-triggered conformation motion within a cage-like scaffold is used to control the formation and disassociation of hierarchical ensembles.

Naphthotubes are a class of macrocycles with welldefined cavities and are appealing for molecular recognition and smart materials. In this research, we report two types of hybridized naphthotubes (HNT) which were synthesized through the condensation of a phenyl-bis-naphthalene (PN) tweezer and a bisnaphthalene cleft. The naphthyls attached to the PN tweezer can rotate around the single bonds to form conformational mixtures. When substituents are present at the ortho positions of the naphthyls, four atropisomers are formed. The water-soluble HNT could recognize phenylpyrimidine, phenyltetrazine, and drug intermediates effectively by adopting a syn conformation in aqueous environments (up to 10 5 M -1 ). Moreover, a series of shear-induced hydrogels have been prepared with the newly developed hybridized naphthotube, PEGs, and different transition-metal ions, which showed much stronger gelation properties compared to the previously reported amide naphthotubes.

A novel cooperative pseudo[3]rotaxane system was successfully constructed by the inclusion complexation of two identical amine naphthotubes with a bis-pyridinium/isoquinolinium guest. Single crystal structure analysis revealed that weak Csp3-H & ctdot;O hydrogen bonds between the two hosts are responsible for the positive cooperativity during the formation of pseudo[3]rotaxanes. Moreover, intermolecular charge-transfer interactions between the electron-rich host and the electron-poor guests were observed. The pseudo[3]rotaxanes showed pH-controllable association/dissociation processes with naked-eye color changes in solution. A pH-controllable pseudo[3]rotaxane system with naked-eye color changes in solution from electron-rich amine naphthotubes and bis-pyridinium/isoquinolinium salts was achieved with positive cooperativity.

The interactions between ether naphthotube and a series of dication guests in organic solution were investigated. It was found that ether naphthotube formed stable host-guest complexes selectively with these guests in a 1 : 1 stoichiometric ratio with association constants ranging from 102 to 106 M-1, which were confirmed by 1H-NMR spectra and ITC experiments. The host-guest interactions are driven by enthalpy change as the entropic factors are unfavorable. Positive correlations between Delta H and Delta S have been observed in the host-guest complexes. Furthermore, the para-substitution of the guests can significantly affect the binding affinities through a combination of field/inductive and resonance effects by following a linear free energy relationship. Based on the host-guest complexes composed of ether naphthotube and organic cations, two interlocked [2]rotaxanes were prepared by cationization reaction and Huisgen cycloaddition between the cations and the stopper components. The ether naphthotube-based host-guest complexes are useful for creating sophisticated interlocked molecules. Ether naphthotube was able to complex strongly with organic dications in organic solution to give an association constant up to 106 M-1. Thermodynamically, the host-guest interactions are exclusively enthalpically driven and enthalpy-entropy compensation phenomena have been observed. Besides, a linear free energy correlation was observed between binding strengths and the Hammett substituent constants. The host-guest system can be directly applied for the preparation of more complex interlocked molecules by simple stoppering. image

A hexagonal anthracene-based nanotube (1) was synthesized through a one-pot Suzuki–Miyaura cross-coupling reaction. 1 shows high binding affinity and selectivity to C 70 over C 60 in toluene, resulting in enrichment of C 70 .

Enantioselective recognition of functional organic molecules in water is routine in nature but remains a formidable challenge for synthetic hosts. Here, we reported two pairs of chiral naphthotubes with chiral centers located in the neighborhood of the inward-directing amide groups. These naphthotubes, with a chiral twisted cavity, show highly enantioselective recognition in water to a wide scope of organic molecules (90 chiral guests). The highest enantioselectivity of 34 was achieved with neotame. Small differences between all of the noncovalent interactions shielded in the hydrophobic cavity were revealed to be responsible for the enantioselective recognition in water, which is different from the traditional views. Moreover, these hosts can differentiate the analogues of aspartame using fluorescence spectroscopy. These chiral naphthotubes have made unprecedented achievements in enantioselective recognition, providing the basis for their applications in chiral analysis and separations.

Aqueous soluble and stable Cu(I) molecular catalysts featuring a catenane ligand composed of two mechanically interlocked, cationic macrocycles are reported. The mechanical bond in the catenane ligand not only fine-tunes the coordination sphere and kinetically stabilizes the Cu(I) against air oxidation and disproportionation, but also prevents the dissociation of the otherwise electrostatically repulsive cationic macrocycles which are essential for the good water solubility and sustained reactivity of the catalyst. These catenane Cu(I) complexes are active catalysts for the oxidative C–C coupling of indoles and tetrahydroisoquinolines in water with a good substrate scope. The successful use of the catenane ligands in exploiting Cu(I) for oxidative catalysis under aqueous conditions using H2O2 as a green oxidant thus highlights the many unexplored potential of mechanical bonding as a molecular design element in developing new transition metal catalysts.

Precise binding towards structurally similar substrates is a common feature of biomolecular recognition. However, achieving such selectivity-especially in distinguishing subtle differences in substrates-with synthetic hosts can be quite challenging. Herein, we report a novel design strategy involving the combination of different rigid skeletons to adjust the distance between recognition sites within the cavity, which allows for the highly selective recognition of hydrogen-bonding complementary substrates, such as 4-chromanone. X-ray single-crystal structures and density functional theory calculations confirmed that the distance of endo-functionalized groups within the rigid cavity is crucial for achieving high binding selectivity through hydrogen bonding. The thermodynamic data and molecular dynamics simulations revealed a significant influence of the hydrophobic cavity on the binding affinity. The new receptor possesses both high selectivity and high affinity, which provide valuable insights for the design of customized receptors.

An indicator displacement assay for colorimetric and fluorometric dual-mode detection of urinary uric acid (UA) was constructed using a water-soluble naphthalene-based tetralactam macrocycle and the phenoxazine dye, resorufin (RF). The visual detection of UA levels of volunteers was successfully realized using modified paper assays, which could be used for the home monitoring of urinary UA.

The expression level of GSK3β/β-catenin in SiHa and MS751 cells with PIK3CA-WT and E545K after 4Gy of IR exposure pretreated with AKT inhibitor for 24h.