Aggregation-induced emission in synthetic macrocycle-based supramolecular systems.

Aggregation-induced emission (AIE) has emerged as an effective strategy to overcome the traditional aggregation-caused quenching (ACQ) effect, offering great promise for developing advanced luminescent materials. Synthetic macrocycles, owing to their preorganized cavities and well-defined geometries, provide unique platforms for constructing supramolecular assemblies with tunable photophysical properties. This review summarises recent advances in the construction of AIE-active supramolecular architectures through macrocycle-directed assembly, with a particular focus on systems based on tetraphenylethylene (TPE) and triphenylamine (TPA).

Design and Synthesis of Box[6]arenes for 3D Charge-Transfer Co-Crystal Engineering via Macrocyclic Self-Complementary and Exo-Wall Interactions.

The construction of well-defined 3D charge-transfer (CT) co-crystals using new macrocyclic hosts to enable programmable functionality remains challenging due to the dimensional constraints imposed by conventional assembly strategies. Herein, we address this limitation using a new synthetic macrocycle named box[6]arene (B[6]A) with a flexible skeleton, which adopts two distinct conformations (B[6]Aα and B[6]Aβ). Crucially, the self-complementary and exo-wall CT co-assembly of B[6]A facilitates the construction of 3D macrocycle-based co-crystals (MCCs) with planar electron-deficient guests, including 1,2,4,5-tetracyanobenzene (TCNB), tetrafluoroterephthalonitrile (TFTN), and tetrachloroterephthalonitrile (TClTN).

Bacteria-Targeted Single-Atom Nanozyme With Photothermal-Augmented Multi-Enzymatic Cascade and NO Delivery for Enhanced Infected Wound Healing.

Infected diabetic wound management confronts significant challenges, including bacterial resistance, oxidative stress, and impaired vascular repair, resulting in substantial unmet clinical needs. To address these issues, a multifunctional therapeutic nanoplatform, mCu-SAE@BNN6@PEG-Van (CBPV), is developed by sequentially functionalizing mesoporous copper single-atom nanozymes (mCu-SAE) loaded with the nitric oxide (NO) donor BNN6 and vancomycin-conjugated polyethylene glycol (PEG-Van). CBPV integrates three synergistic therapeutic modalities: 1) pathogen-specific targeting via Van-mediated bacterial recognition; 2) NIR-II photothermally enhanced catalytic therapy via Cu-N centers in mCu-SAE, generating reactive oxygen species; 3) photoactivated NO release from BNN6, enabling peroxynitrite (ONOO) formation through radical coupling.

From Consultation to Collaboration: A Patient-Centered Approach to Shingles Pain and Postherpetic Neuralgia Management.

: Herpes zoster (shingles), caused by reactivation of the varicella zoster virus, often leads to acute pain that may progress to postherpetic neuralgia (PHN). Current evidence is insufficient to determine the optimal interventional treatment for these conditions. This study aimed to evaluate the effectiveness of shared decision-making (SDM) forms developed by MacKay Memorial Hospital (MMH) in reducing patient anxiety and improving personalized care.

Proton-Mediated ROS Amplification in Hydrazone-Linked Pillararene Microspheres for Photocatalysis.

Smart materials that adapt to environmental stimuli have massive technological potential. Translating well-established molecular-level responsiveness to macroscopic systems, particularly complex systems for photocatalysis, remains a significant hurdle. Herein, we introduce a new approach using a hydrazone-linked pillararene microsphere (NP5-TF-HPM) as a smart stimuli-responsive photocatalyst.

Regulating Enol-to-Keto Tautomerization of Pillararene-Based Conjugated Macrocycle Polymers for HO Photosynthesis.

Porous organic polymers have emerged as promising materials for energy conversion, pollutant adsorption, and heterogeneous catalysis because of their tunable pore structures and high surface areas. However, most porous organic polymers are still limited by insufficient conjugation and inefficient electron-hole separation, hindering the tunability of their photoelectric properties and overall functionality. By integrating macrocyclic compounds as a new building block, which feature electron-rich cavities and rigid ring structures, into the polymer network, the resulting conjugated macrocycle polymers are expected to provide an innovative approach to enrich the photoelectric functionalities of porous organic polymers.

A Dual-Pipeline Lactate Removal Strategy to Reverse Vascular Hyperpermeability for the Management of Lipopolysaccharide-Induced Sepsis.

Sepsis is an underappreciated yet severe threat to human life, marked by organ dysfunction and high mortality resulting from disordered inflammatory responses to blood infection. Unfortunately, no specific drugs are available for effective sepsis treatment. As a pivotal biomarker for sepsis, lactate levels are closely related to vascular permeability and sepsis-associated mortality.

Supramolecular Switching-Enabled Quorum Sensing Trap for Pathogen-Specific Recognition and Eradication to Treat Enteritis.

Intestinal bacterial infections have become a significant threat to human health. However, the current typical antibiotic-based therapies not only contribute to drug resistance but also disrupt gut microbiota balance, resulting in additional adverse effects on life activities. There is an urgent need to develop new antibacterial materials that selectively eliminate pathogenic bacteria without disrupting beneficial bacterial communities or promoting drug resistance.

Covalent Organic Frameworks for Membrane Separation.

Membranes with switchable wettability, solvent resistance, and toughness have emerged as promising materials for separation applications. However, challenges like limited mechanical strength, poor chemical stability, and structural defects during membrane fabrication hinder their widespread adoption. Covalent organic frameworks (COFs), crystalline materials constructed from organic molecules connected by covalent bonds, offer a promising solution due to their high porosity, stability, and customizable properties.

Metal-organic framework-based dual function nanosystems for aluminum detoxification and plant growth in acidic soil.

Plants encounter various abiotic stresses throughout growth and development, with aluminum stress emerging as a major global agricultural challenge that hinders plant growth and limits crop yields in acidic soils. In this study, nanomaterials with dual functions, controlled release and adsorption, were constructed to alleviate aluminum toxicity. Specifically, two metal-organic frameworks, UiO-66 and ZIF-8, were used to load naphthylacetic acid and tryptophan, respectively.

Reactive Oxygen Species-Responsive Pillararene-Embedded Covalent Organic Frameworks with Amplified Antimicrobial Photodynamic Therapy for the Targeted Elimination of Periodontitis Pathogens.

Reactive oxygen species (ROS)-responsive drug delivery systems possess immense potential for targeted delivery and controlled release of therapeutics. However, the rapid responsiveness to ROS and sustained release of antibacterial drugs are often limited by the challenging microenvironment of periodontitis. Integrating ROS-responsive drug delivery systems with photocatalytic technologies presents a strategic approach to overcome these limitations.

Self-Assembled Nanohelixes Driven by Host-Guest Interactions and Metal Coordination.

Helical nanostructures fabricated via the self-assembly of artificial motifs have been a captivating subject because of their structural aesthetics and multiple functionalities. Herein, we report the facile construction of a self-assembled nanohelix (NH) by leveraging an achiral aggregation-induced emission (AIE) luminogen (G) and pillar[5]arene (H), driven by host-guest interactions and metal coordination. Inspired by the "sergeants and soldiers" effect and "majority rule" principle, the host-guest complexation between G and H is employed to fixate the twisted conformation of G for the generation of "contortion sites", which further induced the emergence of helicity as the 1D assemblies are formed via Ag(I) coordination and hexagonally packed into nano-sized fibers.

Guest-Induced Helical Superstructure from a Gold Nanocluster-Based Supramolecular Organic Framework Enables Efficient Catalysis.

Mimicking hierarchical assembly in nature to exploit atomically precise artificial systems with complex structures and versatile functions remains a long-standing challenge. Herein, we report two single-crystal supramolecular organic frameworks (MSOF-4 and MSOF-5) based on custom-designed atomically precise gold nanoclusters Au(4-Mpy)(PPh), showing distinct and intriguing host-guest adaptation behaviors toward 1-/2-bromopropane (BPR) isomers. MSOF-4 exhibits topology and cylindrical channels with 4-mercaptopyridine (4-Mpy) ligands matching well with guest 1-BPR.

Enhancing contrast distribution with the far lateral approach in lumbar transforaminal epidural steroid injections: A retrospective analysis.

Background: Herniated intervertebral disc (HIVD) with radiculopathy is a common degenerative spine disorder. Transforaminal epidural steroid injection (TFESI) is one of the pain relief treatments for lumbar radiculopathy recommended by evidence-based guidelines. Adequate contrast distribution is correlated with better pain control, but the best approach has not been confirmed yet.

Phenyl-Extended Resorcin[4]arenes: Synthesis and Highly Efficient Iodine Adsorption.

The continuous exploration of new analogs of calixarenes and pillararenes unlocks infinite opportunities in supramolecular chemistry and materials. In this work, we introduce a new class of macrocycle, phenyl-extended resorcin[4]arenes (ExR4), a unique and innovative design that incorporates unsubstituted phenylene moieties into the resorcin[4]arene scaffold. Single-crystal analysis reveals a chair-like conformation for per-methylated ExR4 (Me-ExR4) and a twisted "Figure-of-eight" shaped conformation for per-hydroxylated ExR4 (OH-ExR4).

Emerging strategies for combating in colorectal cancer treatment: Systematic review, improvements and future challenges.

Colorectal cancer (CRC) is generally characterized by a high prevalence of (), a spindle-shaped, Gram-negative anaerobe pathogen derived from the oral cavity. This tumor-resident microorganism has been closely correlated with the occurrence, progression, chemoresistance and immunosuppressive microenvironment of CRC. Furthermore, can specifically colonize CRC tissues through adhesion on its surface, forming biofilms that are highly resistant to commonly used antibiotics.

An Antibiotic Nanobomb Constructed from pH-Responsive Chemical Bonds in Metal-Phenolic Network Nanoparticles for Biofilm Eradication and Corneal Ulcer Healing.

In the treatment of refractory corneal ulcers caused by Pseudomonas aeruginosa, antibacterial drugs delivery faces the drawbacks of low permeability and short ocular surface retention time. Hence, novel positively-charged modular nanoparticles (NPs) are developed to load tobramycin (TOB) through a one-step self-assembly method based on metal-phenolic network and Schiff base reaction using 3,4,5-trihydroxybenzaldehyde (THBA), ε-poly-ʟ-lysine (EPL), and Cu as matrix components. In vitro antibacterial test demonstrates that THBA-Cu-TOB NPs exhibit efficient instantaneous sterilization owing to the rapid pH responsiveness to bacterial infections.

Pillararene-Based Stimuli-Responsive Supramolecular Delivery Systems for Cancer Therapy.

Cancer poses a significant challenge to global public health, seriously threatening human health and life. Although various therapeutic strategies, such as chemotherapy (CT), radiotherapy, phototherapy, and starvation therapy, are applied to cancer treatment, their limited therapeutic effect, severe side effects, and unsatisfactory drug release behavior need to be carefully considered. Thus, there is an urgent need to develop efficient drug delivery strategies for improving cancer treatment efficacy and realizing on-demand drug delivery.

Metal-Phenolic Nanocapsules with Photothermal Antibacterial and Ros Scavenging Ability for Diabetic Wound Healing.

The presence of bacteria in diabetic wounds not only leads to the formation of biofilms but also triggers oxidative stress and inflammatory responses, which hinder the wound-healing process. Therefore, it is imperative to formulate a comprehensive strategy that can proficiently eliminate bacteria and enhance the wound microenvironment. Herein, this work develops multifunctional metal-phenolic nanozymes (TA-Fe/Cu nanocapsules), wherein the one-pot coordination of tannic acid (TA)and Fe/Cu using a self-sacrificial template afforded hollow nanoparticles (NPs) with exceptional photothermal and reactive oxygen species scavenging capabilities.

[2]Biphenyl-extended pillar[6]arene functionalized silver nanoparticles for catalysis and label-free detection.

Synthetic macrocycles have served as principal tools for supramolecular chemistry since their establishment, and the investigation of macrocycles-aided organic-inorganic hybrid nanomaterials has also attracted broad interest in chemistry and material communities during the past decade owing to their widespread applications in optical sensing, catalytic degradation, biomedicine, and other related fields. Herein, a new class of silver nanoparticles (AgNPs) modified by anionic water-soluble [2]biphenyl-extended pillar[6]arene (WBpP6), namely WBpP6-AgNPs, is designed and synthesized through a facile one-pot method. WBpP6-AgNPs with good dispersion and stability exhibit efficient catalytic properties toward the hydrogenation of a series of aromatic nitro compounds and also show good performance in label-free detection toward diquat.

Superstructure-Induced Hierarchical Assemblies for Nanoconfined Photocatalysis.

Most attempts to synthesize supramolecular nanosystems are limited to a single mechanism, often resulting in the formation of nanomaterials that lack diversity in properties. Herein, hierarchical assemblies with appropriate variety are fabricated in bulk via a superstructure-induced organic-inorganic hybrid strategy. The dynamic balance between substructures and superstructures is managed using covalent organic frameworks (COFs) and metal-organic frameworks (MOFs) as dual building blocks to regulate the performances of hierarchical assemblies.

Grinding-induced supramolecular charge-transfer assemblies with switchable vapochromism toward haloalkane isomers.

Synthetic macrocycles have proved to be of great application value in functional charge-transfer systems in the solid state in recent years. Here we show a switchable on-off type vapochromic system toward 1-/2-bromoalkane isomers by constructing solid-state charge-transfer complexes between electron-rich perethylated pillar[5]arene and electron-deficient aromatic acceptors including 4-nitrobenzonitrile and 1,4-dinitrobenzene. These charge-transfer complexes with different colors show opposite color changes upon exposure to the vapors of 1-bromoalkanes (fading) and 2-bromoalkanes (deepening).