Hydrogen-Bonded Bottlebrush Copolymers Carrying "Two-in-One" Prodrug for Boosting Synergistic Chemo/Photothermal Antitumor Therapy.

Employing hydrogen-bonded (H-bonded) bottlebrush architecture to realize intelligent therapeutics is particularly advantageous but rare. Herein, we target the construction of H-bond-mediated supramolecular bottlebrush copolymer micelles, FU-IR780@P1, for synergistic cancer chemo/photothermal therapies (CT/PTT). To do so, we first design an H-bonding amphiphilic bottlebrush random copolymer carrier, P(NBDAP--NBPEO) (i.

"Mix-and-Match": Self-Sorting Assembly Governed Supramolecular Polymeric Nanomedicine for Boosting Combined Chemo/Phototherapy.

Precise cancer nanomedicine requires rational molecular instructions of therapeutic agents. Harnessing the structure-property-function relationships represents a practical strategy toward smart and effective nanomedicine. A structurally novel hydrogen-bonded (H-bonded) supramolecular nanoformulation generated by orthogonal self-sorting assembly of chemo-prodrug (FPtF) and phototherapeutics (BPeB) is here reported, to reach an autonomous nanomedicine with improved anti-tumor efficacy by combining chemo/phototherapy (CT/PT).

Adhesives That Contains Ionic Liquids Segment: From Synthesis to Applications.

As technology has developed by leaps and bounds over decades, the development of high-performance supramolecular adhesives has become crucial in both scientific and industrial fields. Ionic liquids (ILs)-based adhesives, containing ILs segment, utilizing ILs chemical structure as either the primary adhesive component or key functional group, have materialized as a highly transformative subject matter for cutting-edge and emerging applications. Rational adhesive design strategies, carefully balancing adhesion and cohesion behavior, are also required when constructing ILs-based adhesives.

Robust and Reversible Thermal/Electro-Responsive Supramolecular Polymeric Adhesives via Synergistic Hydrogen-Bonds and Ionic Junctions.

Adhesive conducting elastomers are rising materials towards cutting-edge applications in wearable and implantable soft electronics. Yet, engineering the conductive adhesives with robust and tunable interfacial bonding strength is still in its infancy stage. We herein identify a structurally novel supramolecular polymer scaffold, characterized by synergistic coexistence of hydrogen-bonding (H-bonding) interactions and electrostatic ionic junctions, endowing the robust and tunable elastic conducting adhesives with remarkable thermal/electro-responsive performance.

Multilevel Hollow-Structured Particles through Halogen-Bond Regulated Polymer Assembly under 3D Confinement.

Engineering of hollow particles with tunable internal structures often requires complicated processes and/or invasive cleavage. Halogen-bond driven 3D confined-assembly of block copolymers has shed light on the engineering of polymer organization along with the fabricating of unique nanostructures. Herein, a family of multilevel hollow-structured particles (e.

Programmable Reconfiguration of Supramolecular Bottlebrush Block Copolymers: From Solution Self-Assembly to Co-Crystallization-Assistant Self-Assembly.

Achieving structural reconfiguration of supramolecular bottlebrush block copolymers toward topological engineering is of particular interest but challenging. Here, we address the creation of supramolecular architectures to discover how assembled topology influences the structured aggregates, combining hydrogen-bonded (H-bonded) bottlebrush block copolymers and electrostatic interaction induced polymer/inorganic eutectics. We first design H-bonding linear-brush block copolymer P(NBDAP-co-NBC)-b-P(NBPEO), bearing linear block P(NBDAP-co-NBC) (poly(norbornene-terminated diaminopyridine-co-norbornene-terminated hexane)) with pendant H-bonding DAP (diaminopyridine) motifs, and PEO (poly(ethylene oxide)) densely grafted P(NBPEO) brush block.

Deliver on a Promise: Hydrogen-Bonded Polymer Nanomedicine with a Precise Ratio of Chemodrug and Photosensitizer for Intelligent Cancer Therapy.

The outcomes of combined cancer therapy are largely related to loading content and contribution of each therapeutic agent; however, fine-tuning the ratio of two coloaded components toward precise cancer therapy is a great challenge and still remains in its infancy. We herein develop a supramolecular polymer scaffold to optimize the coloading ratio of chemotherapeutic agent and photosensitizer through hydrogen-bonding (H-bonding) interaction, for maximizing the efficacy of intelligent cancer chemo/photodynamic therapies (CT/PDT). To do so, we first synthesize a thymine (THY)-functionalized tetraphenylporphyrin photosensitizer (i.

Polyphenol-sodium alginate supramolecular injectable hydrogel with antibacterial and anti-inflammatory capabilities for infected wound healing.

Injectable hydrogel has attracted appealing attention for skin wound treatment. Although multifunctional injectable hydrogels can be prepared by introducing bioactive ingredients with antibacterial and anti-inflammatory capabilities, their preparation remains complicated. Herein, a polyphenol-based supramolecular injectable hydrogel (PBSIH) based on polyphenol gallic acid and biological macromolecule sodium alginate is developed as a wound dressing to accelerate wound healing.

Hydrogen-Bonded Polymer Nanomedicine with AIE Characteristic for Intelligent Cancer Therapy.

One of the major goals of biomedical science is to pioneer advanced strategies toward precise and smart medicine. Hydrogen-bonding (H-bonding) assembly incorporated with an aggregation-induced emission (AIE) capability can serve as a powerful tool for developing supramolecular nanomedicine with clear tumor imaging and smart therapeutic performance. We here report a H-bonded polymeric nanoformulation with an AIE characteristic toward smart antitumor therapy.

Large-Area Arrays of Polymer-Tethered Gold Nanorods with Controllable Orientation and Their Application in Nano-Floating-Gate Memory Devices.

In this work, it is reported that large-area (centimeter-scale) arrays of non-close-packed polystyrene-tethered gold nanorod (AuNR@PS) can be prepared through a liquid-liquid interfacial assembly method. Most importantly, the orientation of AuNRs in the arrays can be controlled by changing the intensity and direction of electric field applied in the solvent annealing process. The interparticle distance of AuNR can be tuned by varying the length of polymer ligands.

Monolayer LDH Nanosheets with Ultrahigh ICG Loading for Phototherapy and Ca-Induced Mitochondrial Membrane Potential Damage to Co-Enhance Cancer Immunotherapy.

Tumor recurrence and metastasis are the main causes of cancer mortality; traditional chemotherapeutic drugs have severe toxicity and side effects in cancer treatment. To overcome these issues, here, we present a pH-responsive, self-destructive intelligent nanoplatform for magnetic resonance/fluorescence dual-mode image-guided mitochondrial membrane potential damage (MMPD)/photodynamic (PDT)/photothermal (PTT)/immunotherapy for breast cancer treatment with external near infrared (NIR) light irradiation. To do so, we construct multifunctional monolayer-layered double hydroxide (LDH) nanosheets (MICaP), co-loading indocyanine green (ICG) with ultrahigh loading content realized via electrostatic interactions, and calcium phosphate (Ca(PO)) coating via biomineralization.

Starvation-assisted and photothermal-thriving combined chemo/chemodynamic cancer therapy with PT/MR bimodal imaging.

Chemodynamic therapy (CDT) reflects a novel reactive oxygen species (ROS)-related cancer therapeutic approach. However, CDT monotherapy is often limited by weak efficacy and insufficient endogenous HO. Herein, a multifunctional combined bioreactor (MnFe-LDH/MTX@GOx@Ta, MMGT) relying on MnFe-layered double hydroxide (MnFe-LDH) loaded with methotrexate (MTX) and coated with glucose oxidase (GOx)/tannin acid (Ta) is established for applications in HO self-supply and photothermal enhanced chemo/chemodynamic combined therapy along with photothermal (PT) /magnetic resonance (MR) dual-modality imaging ability for cancer treatment.

Electric, magnetic, and shear field-directed assembly of inorganic nanoparticles.

Ordered assemblies of inorganic nanoparticles (NPs) have shown tremendous potential for wide applications due to their unique collective properties, which differ from those of individual NPs. Various assembly methods, such as external field-directed assembly, interfacial assembly, template assembly, biomolecular recognition-mediated assembly, confined assembly, and others, have been employed to generate ordered inorganic NP assemblies with hierarchical structures. Among them, the external field-directed assembly method is particularly fascinating, as it can remotely assemble NPs into well-ordered superstructures.

Assembled Morphology of Copper-Thiourea Coordination-Mediated Metallo-Supramolecular Polymers.

Metallo-supramolecular polymers represent a powerful platform to construct self-assembled morphologies. Copper-thiourea (Cu-TU) coordination interactions, though have been extensively studied in small molecular system, the role of TU motifs in synthetic polymers using metal-ligand coordination to afford supramolecular aggregation and their morphology are often overlooked. Herein, an amphiphilic random copolymer, poly(oligo(ethylene glycol) ethyl acrylate-r-acylthiourea) (P(OEGEA-r-ATU)), bearing pendant TU motifs behaving as the ligand to coordinate Cu, a design characterized by core-coordinated metallo-supramolecular polymer is rationally synthesized.

Core-Coordinated Elliptic Polymer Nanoparticles Loading Copper(II) and Chlorambucil for Cooperative Chemodynamic/Chemotherapy.

Chemodynamic therapy (CDT) reflects an innovative cancer treatment modality; however, to enhance its relatively low therapeutic efficiency, rational combination with extra therapeutic modes is highly appreciated. Here, core-coordinated amphiphilic, elliptic polymer nanoparticles (Cu/CBL-POEGEA NPs) are constructed via the self-assembly of a glutathione (GSH)-responsive polymer-drug conjugate, bearing side-chain acylthiourea (ATU) motifs which behave as ligands capable of coordinating Cu(II), such a design is featured by combined chemo (CT)/CDT with dual GSH depletion collectively triggered by the Cu(II) reduction reaction and disulfide bond breakage. To do so, an amphiphilic random copolymer poly[oligo(ethylene glycol)ethyl acrylate--thiourea] [P(OEGEA--ATU)] is synthesized, followed by conjugation of chlorambucil (CBL) to ATU motifs linked via a disulfide bond, thus yielding the targeted P[OEGEA--(ATU--CBL)].

Hydrogen Bond-Mediated Supramolecular Polymeric Nanomedicine with pH/Light-Responsive Methotrexate Release and Synergistic Chemo-/Photothermal Therapy.

Complete cancer cure and healing are still difficult, owing to its complexity and heterogeneity. Integration of supramolecular forces, for example, hydrogen bonds (H-bonds), to anti-cancer nanomedicine affords new scaffolds for biomedical material decoration, featuring the advantages of dynamic property and easier processability. Here, we target the construction of H-bond-mediated supramolecular polymer micelles, loaded with a chemotherapeutic drug along with a photothermal agent for synergistic chemo-/photothermal therapies (CT/PTT).

Hydrogen-Bonds-Mediated Nanomedicine: Design, Synthesis, and Applications.

Among the various challenges in medicine, diagnosis, complete cure, and healing of cancers remain difficult given the heterogeneity and complexity of such a disease. Differing from conventional platforms with often unsatisfactory theranostic capabilities, the contribution of supramolecular interactions, such as hydrogen-bonds (H-bonds), to cancer nanotheranostics opens new perspectives for the design of biomedical materials, exhibiting remarkable properties and easier processability. Thanks to their dynamic characteristics, a feature generally observed for noncovalent interactions, H-bonding (macro)molecules can be used as supramolecular motifs for yielding drug- and diagnostic carriers that possess attractive features, arising from the combination of assembled nanoplatforms and the responsiveness of H-bonds.

Hydrogen-Bonded Supramolecular Polymer Adhesives: Straightforward Synthesis and Strong Substrate Interaction.

High-performance adhesives are of great interest in view of industrial demand. We herein identify a straightforward synthetic strategy towards universal hydrogen-bonded (H-bonded) polymeric adhesives, using a side-chain barbiturate (Ba) and Hamilton wedge (HW) functionalized copolymer. Starting from a rubbery copolymer containing thiolactone derivatives, Ba and HW moieties are tethered as pendant groups via an efficient one-pot two-step amine-thiol-bromo conjugation.

MnO coated nanotheranostic LDH for synergistic cascade chemo/chemodynamic cancer therapy under the guidance of MRI-targeted diagnosis.

Integrating magnetic resonance imaging (MRI)-targeted diagnosis with synergistic cascade treatments, such as chemo/chemodynamic therapy (CT/CDT), is highly desired for promoting the antitumor performance; however, the rational design of such "all-in-one" nanomedicine is still in its infancy. In this report, using MnO coated layered dihydroxide (LDH) as a carrier to load chemotherapy molecule 5-flurouracil (5-FU), a novel tumor microenvironment (TME) regulating nanodrug is formed: LDH/5-FU@MnO. Combined guidance of CT/CDT and MRI is used to realize synergistic diagnosis and enhanced anti-tumor efficacy.

Structure Regulation of Block Copolymer Assemblies in Emulsion Droplets by Adding a Selective Solvent.

Generally, nanostructured polymer particles are prepared by 3D confined self-assembly (3D-CSA) of block copolymers (BCPs), while micelles are obtained through self-assembly of BCPs in dilute solutions. Herein, a facile yet robust strategy is developed to regulate the assembled structures of BCP, poly(styrene-block-4-vinylpyridine) (PS-b-P4VP), from nanostructured particles to micelles. The assemblies are prepared by an emulsion-solvent diffusion-induced self-assembly route, which is conducted by dialysis.

Halogen-Bond Mediated 3D Confined Assembly of AB Diblock Copolymer and C Homopolymer Blends.

Halogen-bond driven assembly, a world parallel to hydrogen-bond, has emerged as an attractive tool for constructing (macro)molecular arrangement. However, knowledge about halogen-bond mediated confined-assembly in emulsion droplets is limited so far. An I N bond mediated confined-assembly pathway to enable order-order phase transitions is reported here.

Tunable Photonic Microspheres of Comb-Like Supramolecules.

Photonic crystals (PCs) are ideal candidates for reflective color pigments with high color purity and brightness due to tunable optical stop band. Herein, the generation of PC microspheres through 3D confined supramolecular assembly of block copolymers (polystyrene-block-poly(2-vinylpyridine), PS-b-P2VP) and small molecules (3-n-pentadecylphenol, PDP) in emulsion droplets is demonstrated. The intrinsic structural colors of the PC microspheres are effectively regulated by tuning hydrogen-bonding interaction between P2VP blocks and PDP, where reflected color can be readily tuned across the whole visible spectrum range.

Segmental Janus nanoparticles of polymer composites.

We demonstrate a facile yet robust "plasma etching and grafting" strategy to prepare Janus nanoparticles (NPs) coated with binary polymer brushes on two different sides. The ratio of the two types of polymer ligands can be tailored by tuning the plasma etching power.

Opposing Phase-Segregation and Hydrogen-Bonding Forces in Supramolecular Polymers.

Phase segregation between different macromolecules and specific weak interactions are the basis of molecular organization in many biological systems, which are held together by attractive hydrogen bonds (H-bonds) and dissociated by phase segregation. We report significant changes in the association behavior of covalent H-bonds by the phase of attached polymer chains. Depending on the aggregation state, we observed either intact H-bonds despite segregation of the phases, or macrophase separation with a larger amount of H-bonding dissociation.