Adhesive bonding to diverse substances is vital to a great number of the established, cutting-edge and emerging applications. We have witnessed, in the last few years, the transformative progress in ...achieving robust adhesive bonding and tunable debonding behavior, which mostly employing the supramolecular forces. Among the diverse supramolecular forces, the contribution of hydrogen-bonds (H-bonds) to adhesives, on the modality of directionality, selectivity and sensitivity, can function as nano-scaled bonding agents for improved interfacial interactions, thus paved novel perspectives to the design and creation of glue materials with outstanding performance. On account of the dynamic and reversible feature, a characteristic principally determined for H-bonding (macro)molecules could be employed as adhesive platform for affording outstanding attaching, connecting and on demand disconnecting, arising from the combination of adhesion/cohesion process via H-bonding interactions and the responsive characteristics. Thus, H-bonded adhesives with abundant diverse molecular configuration furnish a rich toolbox that can fulfill universal yet specific needs with unique advantages, demonstrating great opportunities for fundamental researches and practical applications. Herein we outline and summarize the design and creation of H-bonded adhesives, responsive attaching/detaching, and applications in advanced materials. We propose the guidance for further designing H-bonded adhesives, in concert with biomedical science, physics, mechanical and electric, informatics or robotics of promising future.
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Recently,
in-situ
polymerization inside living cells has attracted much attention due to the efficient cellular internalization and elevated drug retention. However, the lack of tracking of the
...in-situ
polymerization process and the unclear effects of polymerization on cellular functions restrict its biomedical applications. Herein, we designed a Y-shaped diacetylene-containing lipidated peptide amphiphile (Y-DLPA1) with positive charges, which underwent
in-situ
polymerization initiated by reactive oxygen species in the intracellular microenvironment. In comparison, zwitterionic Y-DLPA2 and negatively charged Y-DLPA3 were polymerized in aqueous solution, but cannot polymerize in the intracellular microenvironment. The polymerized Y-DLPA1 with red fluorescence provides a platform to label cells for long-term tracking studies. This polymerization reaction induced tumor cell apoptosis, increased cell viscosity and decreased cell motility, which potentially inhibited tumor metastasis and served as a novel antitumor agent. This work provides a novel strategy to track
in-situ
polymerization process and modulate cell biofunctions.
The field of anticancer nanomedicine seeks to boost the arsenal’s exploitation with intelligent performance. One opportunistic choice comes from the fabrication of amphiphilic polymer micelles that ...are reversibly crosslinked. Here, hydrogen-bond (H-bond)-driven core-crosslinked supramolecular polymer micelles (FUS/ICG@PEDD) are constructed, co-loading α,ω-functionalized symmetrical H-bonding prodrug 5-fluorouracil-acetic acid–SS–5-fluorouracil-acetic acid (FUS) and a dual photothermal/photodynamic agent (indocyanine green, ICG). Such core-crosslinked nanomedicine is characterized by enhanced drug loading content, crosslinking-prompted stability, pH-responsive charge reversal, and smart drug release, which can facilitate the engineering of synergistic chemo/photothermal/photodynamic therapies (CT/PTT/PDT). To do so, an amphiphilic diblock copolymer, PEG-b-P(DAPA-co-DEAEMA) (denoted as PEDD), is developed to serve as a drug delivery vehicle, with hydrophilic PEG poly(ethylene glycol) and hydrophobic P(DAPA-co-DEAEMA) poly(diaminopyridine acrylamide-co-2-(diethylamino)ethyl methacrylate, bearing randomly dispersed dual functionalities: pH-responsive charge-reversal DEAEMA and H-bonding DAP motifs. Thanks to the specific DAP/FUS H-bonding interactions and two-terminal FU structure of the prodrug, core-crosslinked nanomedicine FUS/ICG@PEDD is thus enabled. In vitro and in vivo investigations indeed reveal remarkable antitumor efficacy. We believe that such H-bonded nanomedicines can fuel the development of intelligent nanomedicines with value in cancer 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). To do so, we design and synthesize an amphiphilic ABA-type triblock copolymer, bearing H-bonding moiety (barbiturate, Ba) within the middle hydrophobic B block. The presence of pendant Ba moieties within the hydrophobic core promotes the loading capability of methotrexate (MTX) and transportation stability, benefitting from the formation of specific Ba/MTX H-bonding interactions. IR780, a photothermal agent, concomitantly encapsulated via hydrophobic interactions, facilitates the development of a synergistic CT/PTT modalities, where MTX can be released on demand owing to the dissociation of Ba/MTX H-bonding interactions induced by elevated temperature. Such H-bonding nanomedicine possesses enhanced drug loading capacity and transport performance and can also trigger stimuli-responsive drug release in the tumor zone. We believe that H-bonded nanomedicines provide a fine toolbox that is conducive to attaining biomedical requirements with remarkable values in theranostics that are highly promising in clinical applications.
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.e., TTPP), featuring the same molecular configuration of H-bonding array with chemotherapeutic carmofur (e.g., 1-hexylcarbamoyl-5-fluorouracil, HCFU). Meanwhile, a six-arm star-shaped amphiphilic polymer vehicle P(DAPA-co-DPMA-co-OEGMA)6 (poly(diaminopyridine acrylamide-co-2-(diisopropylamino)ethyl methacrylate-co-oligo(ethylene glycol) monomethyl ether methacrylate)6) is prepared, bearing hydrophilic and biocompatible POEGMA segment, along with hydrophobic PDAPA and PDPMA segments, characterizing the randomly dispersed dual functionalities, i.e., heterocomplementary H-bonding DAP motifs and pH-responsive protonation DPMA content. Thanks to the identical DAP/HCFU and DAP/TTPP H-bonding association capability, the incorporation of both HCFU and TTPP to six-arm star-shaped P(DAPA-co-DPMA-co-OEGMA)6 vehicle, with an optimized coloading ratio, can be straightforwardly realized by adjusting the feeding concentrations, thus yielding the hydrogen-bonded supramolecular nanoparticles (i.e., HCFU-TTPP-SPNs), demonstrating the codelivery of two components with the promise to optimize the combined CT/PDT efficacy.
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. Hetero‐complementary Ba/HW interactions thus yield H‐bonded supramolecular polymeric networks. In addition to an enhanced polymeric network integrity induced by specific Ba/HW association, the presence of individual Ba or HW moieties enables strong binding to a range of substrates, outstanding compared to commercial glues and reported adhesives.
A straightforward synthetic strategy towards strong supramolecular adhesives is reported, based on a side‐chain barbiturate (Ba) and Hamilton wedge (HW) functionalized polymer. Specific Ba/HW interactions serve as cohesive domains to maintain polymeric network integrity, while molecular configuration of individual Ba or HW moieties linked onto substrates via diverse H‐bonding interactions, form adhesive domains and endow strong adherence.
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 polyoligo(ethylene glycol)ethyl acrylate-co-thiourea P(OEGEA-co-ATU) is synthesized, followed by conjugation of chlorambucil (CBL) to ATU motifs linked via a disulfide bond, thus yielding the targeted POEGEA-co-(ATU-g-CBL). In such a system, hydrophilic POEGEA serves as the biocompatible section and ATU motifs coordinate Cu(II), resulting in core-coordinated elliptic Cu/CBL–POEGEA NPs. Benefitting from the GSH-induced reduction reaction, Cu(II) is converted into Cu(I) and subsequently react with endogenous H2O2 to create •OH, realizing GSH-depletion-promoted CDT. Additionally, the disulfide bond endows GSH-responsive CBL release and provokes further GSH decline, finally realizing combined CDT/CT toward enhancing antitumor outcomes, and in vitro as well as in vivo studies indeed reveal remarkable efficacy. Such a system can provide valuable advantages to create novel nanomedicines toward cascade antitumor therapy.
Front Cover: Article 2200168 by Senbin Chen, Jintao Zhu, and co‐workers summarizes the design and synthetic routes towards Hydrogenbonded nanomedicines, focuses on the growing understanding of the ...structure‐function relationship for efficient cancer treatment. A guidance for designing new Hydrogen‐bonded intelligent theranostic agents is proposed, to inspire more successful explorations of cancer nanotheranostics and finally to promote potential clinical translations.
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. Thus, H‐bonded nanomedicine provides a rich toolbox that is useful to fulfill biomedical needs with unique advantages in early‐stage diagnosis and therapy, demonstrating the promising potential in clinical translations and applications. Here the design and synthetic routes toward H‐bonded nanomedicines, focus on the growing understanding of the structure‐function relationship for efficient cancer treatment are summarized. A guidance for designing new H‐bonded intelligent theranostic agents is proposed, to inspire more successful explorations of cancer nanotheranostics and finally to promote potential clinical translations.
Hydrogen‐bonds (H‐bonds) bridge artificial and biological sciences, implementing dynamic properties into materials and (macro)molecules, which cannot be achieved via purely covalent bonds. In this review, the current state‐of‐the‐art for designing novel H‐bonded nanomedicines for precise diagnosis, and targeted therapeutic drugs delivery are highlighted.
