Hydrogen bonds (H-bonds) are central in Nature, forming the “glue” of many biological materials and processes. Clustering and cooperativity of those bonds are functional principles in natural polymers such as proteins, cellulose, starch, and DNA, as well as synthetic polymers, among them polyamides or polyurethanes. The absence of mobile low-molecular-weight solvents in bulk polymers, combined with intrinsic anisotropy and restricted segmental motion of the surrounding polymer matrix, limits the diffusion of the H-bond motifs when covalently tethered onto a polymer skeleton, so inducing aggregates and higher-order assemblies of H-bonds then decisive for the final material properties. This review addresses fundamental aspects of H-bond association and the formation of supramolecular aggregates within different bulk polymers, discussing the influences of molecular proximity of the H-bonds and novel technical methods to extract dynamic information on their association state. There is a focus on specific sets of H-bond motifs, starting from “simple H-bonds” such as alcohol dimers (OHOH), carboxylic acid dimers (CA-CA), and amide dimers (Am-Am), to more complex assemblies, including ureidopyrimidinone dimers (UPy-UPy), hydroxyl‑pyridine complexes (OH-Pyr), thymine-diaminotriazine/diaminopyridine complex (Thy-DAT/DAP), and Hamilton-wedge-barbiturate/cyanurate complexes (HW-Ba/Cy). By providing a concise summary of literature (335 references) to illustrate the roles of H-bonds in polymers, this review identifies future strategies in the design of functional H-bonded materials, such as in self-healing elastomers, 3D-printing, or as reversible adhesives.

Despite significant advancements in robust adhesive materials, convenient monitoring adhesion strength under service conditions before adhesion failure is essential yet challenging. In this study, structurally novel silicone-based conductive adhesive from comb-shaped supramolecular elastomers is reported, featuring self-monitoring of adhesion state in real time manner via machine learning-assisted traffic light color-coding approach. Comb-shaped supramolecular ion-conducting polysiloxane P(Ba-co-Apy-co-DMS) are first constructed via effective hydrosilylation, yielding pendant H-bonding barbiturate (Ba) and ionic liquids (Apy) moieties. Adhesion-sensitive electrical properties and experimental database are therefore constructed from P(Ba-co-Apy-co-DMS) via digitally transforming of adhesion strength into capacitance signals. Such database is further used to train a hybrid deep learning architecture that integrates 1D convolutional neural networks (1D-CNN) with long short-term memory (LSTM) units. This model learns the capacitance-adhesion mapping and translates the encoded signal features into States 1, 2, and 3. Moreover, a traffic light color-coding approach on the perceptions of adhesion strength is developed, green, orange, and red LED light symbols are respectively associated with States 1, 2, and 3 leveraged from deep learning architecture, reflecting tight, stretched, and fractured adhesion. Our conductive adhesives illustrate the Internet of Things-empowered adhesion state and structural health monitoring, offering promising opportunity to boost intelligentization and informatization of classical materials.

The cross-cutting field of cancer immunotherapy triggered by immunogenic cell death (ICD) has made encouraging achievements; however, such a research field is often hampered by deficient ICD-inducing efficacy due to low tumor-targeting and insufficient drug concentration in tumor cells. With these issues in mind, an active tumor targeting hydrogen-bonded (H-bonded) intelligent supramolecular polymeric nanomedicine FT/FOF@PDOB is constructed, featuring synergetic sonodynamic and chemotherapy (SDT/CT), and amplified ICD-inducing efficacy with strengthened immunological potency. To do so, an active-targeting six-arm star-shaped amphiphilic random copolymer vehicle, PDOB, is developed, comprising a biotin-mediated active tumor targeting regime, and diaminopyridine (DAP) motifs bearing hetero-complementary H-bonding array towards 5-fluorouracil (FU) moieties. The high-fidelity of H-bonding modularity from privileged DAP/FU pair enables specific binding interaction and co-loading of both FU-functionalized tetraphenylporphyrin-based sonosensitizer FT, and α,ω-FU-functionalized oxaliplatin-based symmetrical fuplatin dual-prodrug FOF. Consequently, H-bonded active-targeting nanomedicine FT/FOF@PDOB is readily fabricated, characterized by enhanced cargo uploading content and pH-responsive drug release, therefore endowing the synergetic therapy via FT-induced SDT and FOF-based CT, also facilitating the enhanced ICD effect and stronger anti-tumor immunity. Both in vitro and in vivo therapeutic regimes with outstanding anti-tumor outcomes are truly accomplished. The privileged advantages offered by H-bond design constitute a rising arsenal towards multimodal combination immunotherapy.

Current strategies for metabolic regulation within the tumor microenvironment (TME) often rely on exogenous drugs, leading to transient benefits and necessitating repeated administrations that frequently cause detrimental side effects. To address this, we have developed a novel bacterial biocatalytic reactor, LDGM, which is fabricated by functionalizing Shewanella oneidensis MR-1 (MR-1) bacteria with DOX/GOx-loaded layered double hydroxide (LDH) nanosheets. This sophisticated biomaterial exhibits specific targeting towards hypoxic tumor areas, facilitating the controlled release of doxorubicin (DOX), glucose oxidase (GOx), and Fe3+. Crucially, MR-1 continuously metabolizes intratumoral lactate, thereby augmenting chemotherapy efficacy and combating tumor multidrug resistance. Moreover, with the hypoxic environment generated by GOx and lactate metabolism, MR-1 performs iron respiration, promoting the reduction of Fe3+ through electron transfer to simultaneously induce ferroptosis and apoptosis. Our investigations in murine tumor models showed that LDGM significantly suppresses tumor progression while simultaneously enhancing ferroptosis and apoptosis. Therefore, this living biomaterial presents a promising avenue for advancing cancer therapy by establishing continuous metabolic regulation of the intratumoral lactate/glucose microenvironment.

Polymer microneedles (MNs) have emerged as promising next-generation transdermal drug delivery platforms owing to their noninvasive nature and high delivery efficiency. Conventional fabrication strategies for polymer MNs mainly rely on mold-assisted vacuum casting or hot pressing. However, these approaches often fail to simultaneously achieve rapid fabrication and mild processing conditions, which are particularly critical for the fabrication of temperature-sensitive drug-loaded MNs. Herein, we report a vacuum-assisted pressing strategy for MN fabrication based on O-carboxymethyl chitosan (CMCA) and natural polyphenol protocatechuic acid (PCA) supramolecular composite slurries. This method enables MN production under significantly reduced processing times (<12 h) and mild thermal conditions (50 °C). Viscoelastic supramolecular composite slurries can be obtained by precisely tuning the polymer-to-polyphenol ratio, which is highly compatible with vacuum-assisted pressing in MNs molding. The resulting polymer-polyphenol supramolecular composites exhibit robust mechanical properties, with a fracture stress of 0.5 MPa and a toughness of 1.31 MJ·m−3. Notably, supramolecular MNs demonstrated a high fracture force of up to 1.08 N per needle, indicating sufficient mechanical integrity for transdermal insertion. This fabrication strategy offers a viable route for low-cost, scalable, and mild MN fabrication, highlighting its strong potential for practical and commercial applications.

Multilayer mesoporous vesosomes uniquely combine hollow multilayer shells with ordered mesopores, providing a basis for multilevel gating, controlled release, and programmed reaction cascades, yet robust construction remains challenging. Herein, we report a molecular engineering strategy based on 3D-confined self-assembly to produce multilayer vesosomes with nearly hexagonally ordered shell perforations. Selective association of pentadecylphenol (PDP) and 1,5-dibromopentane (DBP) with the poly(4-vinylpyridine) block precisely tunes block-copolymer volume fraction to stabilize an unconventional perforated lamellar morphology, while reversible hydrogen bonding enables region-selective pore generation. Experiments and simulations reveal cooperative roles of confinement and hydrogen bonding in directing morphological evolution, with DBP further refining assembly through electrostatic and cross-linking interactions. The resulting multilayer mesoporous vesosomes feature a pyridine-rich corona and show iodine capture (1.26 g g−1), good recyclability, and faster uptake than nonporous multilayer analogues. This work offers a versatile route to complex hollow architectures and clarifies key determinants governing their formation. The construction of multilayer mesoporous vesosomes that combine hollow multilayer shells with ordered mesopores remains a significant challenge. Here the authors report a molecular engineering strategy based on 3D-confined self-assembly to produce multilayer vesosomes with nearly hexagonally ordered shell perforations.

Photothermal therapy (PTT) integrated with nanotechnology reflects an essential modality towards cancer treatment, however, this strategy often encounters considerable issues such as low therapeutic efficiency and excessive heat that need to be addressed. In this context, a structurally novel intelligent polymeric antitumor nanobomb (GEM806@PETU(CO)) is highlighted, featuring hydrogen-bonds (H-bonds) linked gemcitabine (GEM)-IR780 conjugate (GEM806), along with metal-chelation locked carbon monoxide (CO) reservoir, towards synergistic low-temperature photothermal/chemo/gas therapy (LTPTT/CT/GT). To do so, an amphiphilic diblock copolymer vehicle PETU(CO) is firstly constructed, bearing hydrophilic and biocompatible polyethylene glycol (PEG) block, importantly, rationally designed hydrophobic block reflects triple functionalities, i.e., pH responsive charge-reversal, stable CO-storage scaffold, and H-bonding ureidoimidazole (UIM) motifs towards GEM. Meanwhile, chemotherapeutic GEM is tethered onto photothermal agent IR780, endowing multifunctional prodrug GEM806 that combines H-bonding site, chemotherapeutic drug, photothermal and NIR fluorescence imaging in single formulation. Thanks to H-bonding UIM/GEM association mediated self-assembly, GEM806 is uploaded and supramolecular intelligent nanobomb GEM806@PETU(CO) is thus created, featuring spatiotemporally controlled activation and synergistic therapeutics, including: 1) pH/thermal responsive GEM806-release towards CT/PTT modalities, 2) H2O2/thermal responsive CO-release for boosting LTPTT/GT, 3) CO-enhanced chemotherapy sensitivity by ferroptosis pathway. Such modular allies of nanobomb render advanced paradigm towards precision cancer therapy and potential clinical impact.

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. Herein, a detailed discussion on the latest advancements is provided in ILs-based adhesive design, including strategies such as IL monomer decoration/polymerization and the creation of ionogels, etc. Leveraging abundant toolbox of ILs structure and obtained rich (macro)molecular configuration, these adhesives can address both general and specific requirements, offering distinctive advantages and great potential for practical industrial applications. From this perspective, it outlines and summarizes the recent research including rational design and manufacturing technique toward advanced ILs-based adhesives such as sensory, underwater, electric-controlled and biomedical applications, particularly proposing the guidance for construction toward tailor-made glues.

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-co-NBPEO) (i.e., P1, poly(norbornene-terminated diaminopyridine-co-norbornene-terminated poly(ethylene oxide)), featuring randomly dispersed dual functionalities: H-bonding DAP (diaminopyridine) motifs and hydrophilic PEO (poly(ethylene oxide)) content. On the other hand, by tethering the chemotherapeutic 5-fluorouracil (FU) onto the photothermal agent IR780, "two-in-one" multifunctional prodrug, FU-IR780, is fabricated, integrating an H-bonding site, chemodrug, photothermal, and fluorescence imaging in single formulation. Thanks to the H-bonding DAP/FU association-mediated self-assembly, supramolecular FU-IR780@P1 nanomedicine is thus created, where FU-IR780 can be released on demand via pH/thermal-responsive rupture of the DAP/FU H-bonding interaction, thus enabling intelligent and synergistic CT/PTT. Such H-bonded bottlebrush polymers contribute a fine toolbox that is conducive to attain biomedical requirements for intelligent antitumor treatments.

Combined chemotherapy (CT) and gene therapy (GT) represent a reliable modality toward drug-resistant tumor treatment. Yet, physical-chemical differences between chemodrugs and nucleic acids often hinder the construction of feasible delivery systems with synergistic activity. Herein, a smart supramolecular polymeric scaffold is reported to co-load chemodrug paclitaxel (PTX) and Bcl-2 small interfering RNA (siRNA), respectively via Hydrogen-bonding (H-bonding) association and electrostatic interaction, toward efficiently reversing drug resistance and significantly inhibiting tumor growth in a synergistic manner via GT-enhanced CT. Therefore, a cationic copolymer carrier, P(OEGA-co-DMAEA)-b-P(HFA-co-TU) (e.g., PODHT), serves as a structurally distinct drug-delivery platform. The hydrophobic section, P(HFA-co-TU) (poly((heptafluorobutyl acrylate)-co-acylthiourea)), incorporates pendant thiourea (TU) moieties that can selectively recognize hydrophobic PTX. Such molecular recognition and co-assembly are governed by TU/PTX double H-bonding association in concert with hydrophobic interactions. Moreover, the cationic shell consisting of P(OEGA-co-DMAEA) (poly(oligo(ethylene glycol) monomethyl ether acrylate-co-2-dimethylaminoethyl acrylate)) from resulting PTX-loaded micelles can steadily bind the negative siRNA via electrostatic interaction, finally to afford the targeted supramolecular micelleplexes PTX@PODHT/siRNA. Such nanoplatform not only possesses the enhanced co-loading capacity and transportation stability of distinct PTX and siRNA, but also can induce pH-responsive cargos release within the tumor zone, ultimately effectively inhibiting tumor growth via synergistic CT/GT.

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). The high‐fidelity of H‐bonding modularity from privileged heterocomplementary diaminopyridine/5‐fluorouracil (DAP/FU) and Hamilton wedge/barbiturate (HW/Ba) pairs, respectively enable the precise spatial control of binding interactions toward FPtF and BPeB, in turn allowing the self‐sorting process and specific “mix‐and‐match” capability. To directly stimulate phototherapy from BPeB via near‐infrared (NIR) light, spectral matched upconversion nanoparticles (UCNPs, β‐NaYF 4 :Yb,Er) are encapsulated simultaneously. As a result, supramolecular polymeric nanomicelles, i.e., F/B/U@PHDO, are readily fabricated. Moreover, distinct H‐bonding association constant (Ka) of DAP/FU (≈10 2 M −1 ) and HW/Ba (≈10 4‐5 M −1 ) pairs reflect different strengths and stabilities of H‐bonds, thus endowing the programmable H‐bonding dissociation, accompanied with the chemo‐prodrug release through pH/thermal‐stimuli. Therapeutic regime with appreciated anti‐tumor outcomes is ultimately accomplished via combined CT/PT. The privileged opportunities offered by self‐sorting design are anticipated to point to new paradigm toward precise nanomedicine for cancer therapy.

Dissolving microneedles (DMNs) are emerging transdermal delivery platforms but rely on water-soluble polymers as carriers that inherently limit drug-loading capacity and slow release due to dissolution/diffusion barriers. Formulating drugs directly into robust DMNs is further challenged by crystallization tendencies. Here, a supramolecular engineering strategy enabling carrier-free antibiotic glass microneedles (GMNs) is presented, leveraging synergistic drug-sulfate-water interactions that suppress crystallization and form mechanically stable amorphous networks. Using tobramycin sulfate, monolithic GMNs are achieved with 100%-drug payload, exceptional strength (Young's modulus 5.1 GPa), and instant transdermal delivery (threefold faster than polymer DMNs). Eliminating polymeric carriers accelerates drug diffusion by 2.6-fold, enabling deep tissue penetration for efficient biofilm eradication. In vivo evaluation demonstrates that the antibiotic GMNs effectively promote the healing of biofilm-infected skin wounds in mice and exhibit potent therapeutic efficacy against subcutaneous abscesses. This strategy extends broadly to aminoglycoside antibiotics. By replacing the polymer matrix with supramolecular-engineered amorphous networks, a next-generation DMN platform is pioneered that bridges critical gaps in drug-loading efficiency, dissolution kinetics, and clinical translation for urgent therapeutic applications.

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. Thanks to H-bonding association between DAP and thymine (Thy), incorporation of Thy-functionalized polystyrene (Thy-PS65) enables solution self-assembly and formation of H-bonded bottlebrush block copolymers, generating augmented nanospheres with increasing Thy-PS65 amount. Noteworthy that integration of inorganic cluster silicotungstic acid (STA) to P(NBC-co-NBDAP)-b-P(NBPEO), endows the formation of PEO/STA eutectic core. Therefore, co-crystallization-assistant self-assembly at the interfaces of polymeric, inorganic and supramolecular chemistry is realized, reflecting multi-stage morphology transformation from hexagonal platelets, needle-like, curved rod-like micelles, finally to end-to-end closed rings, by gradually increasing Thy-PS65 while fixing STA content. Interestingly, such solution self-assembly to co-crystallization-assistant self-assembly strategy not only endows unique nanostructure transition, also induce in-to-out reconfiguration of PS domains. These findings clearly provide unique methodology towards programmable fabrication of geometrical objects promising in smart materials.

Injectable hydrogel has attracted appealing attention for skin wound treatment. Although multifunctional injectable hydrogels can be prepared by introducing bioactive ingredients with antibacterial and antiinflammatory 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. We show that such PBSIH can be rapidly formed within 15 s by mixing the sodium alginate and gallic acid solutions based on the hydrogen bonding and hydrophobic interactions. The PBSIH shows excellent cytocompatibility, antibacterial, and antioxidant properties, which enhance infected wound healing by inhibiting bacterial infection and alleviating inflammation after treatment of 11 days. Moreover, we show that the preparative strategies of injectable supramolecular hydrogels can be extended to other polyphenols, including protocatechuic and tannic acids. This study provides a facile yet highly effective method to design injectable polyphenol- sodium alginate hydrogel for wound dressing based on naturally bioactive ingredients.

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.

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. H-bonding association and electrostatic interaction play orthogonal yet synergistic roles in the strong supramolecular adhesive formation, serving as the leveraging forces for opposing both cohesion and adhesion energy. To do so, six-arm star-shaped random copolymers P1, and P2 are strategically designed, bearing H-bonding PDAP (poly(diaminopyridine acrylamide)) and PThy (poly(thymine)) segments, which can form hetero-complementary DAP/Thy H-bonding association, along with ionic conductive poly(ionic liquid)s segment: PMBT, (poly(1-[2-methacryloylethyl]-3-methylimidazolium bis(trifluoromethane)-sulfonamide)). DAP/Thy H-bonding association, along with electrostatic ionic interaction, can yield dual supramolecular forces crosslinked polymeric networks with robust cohesion energy. Moreover, coexistence of poly(ionic liquid)s can impact and interfere the configuration of H-bonding association, liberate more free DAP and Thy motifs to form H-bonds towards substrate, affording strong surface adhesion in a synergistic manner. This work demonstrates a significant forward step towards potential adhesives devoted to hybrid electronic devices.

The structural rigidity of thiourea (TU) motifs has made them useful in supramolecular (bio)materials. However, the role of the TU motif in a single system endowing dual noncovalent interactions, i.e., Hydrogen-bonding (H-bonding) association and metal-coordination interaction, to afford nanomedicine is still unexplored. Herein a smart supramolecular polymeric nanomedicine constructed via TU motifs privileged dual noncovalent interactions, toward synergistic chemo/chemodynamic (CT/CDT) cancer therapy is reported. The study first synthesized a six-arm star-shaped amphiphilic polymer vehicle containing pendant TU motifs, poly(acylthiourea-co-oligo(ethylene glycol) ethyl acrylate)6 (P(TU-co-OEGEA)6), followed by addressing both H-bonding association and metal-coordination to fabricate supramolecular nanomedicine (e.g., Dox/Cu@P(TU-co-OEGEA)6). Structural privilege and functional diversity of TU motifs constitute an outstanding scaffold, not only offering an H-bonding site to associate doxorubicin (Dox) but also acting as a ligand to coordinate copper (Cu). Thereby, one TU motif can enable dual noncovalent binding modes, triggering multiple curative outcomes. TU/Dox and TU/Cu noncovalent interactions can induce intermolecular configuration, yielding prompted cargo loading and in vivo stability. Moreover, benefiting from pH-responsive Dox release and Fenton-like copper redox chemistry, accompanied by Dox-induced intratumoral H2O2 elevation and prompted center dot OH generation, synergistic CT/CDT with extraordinary anti-tumor efficacy is indeed accomplished. This work provides a new paradigm using TU motifs regulated dual supramolecular forces to meet therapeutic goals. By rational designing of both TU/Dox H-bonding association and TU/Cu coordination interactions within one nanoplatform, The study has constructed a smart supramolecular Dox/Cu@P(TU-co-OEGEA)6 micelles toward synergistic CT/CDT cancer therapy. Indeed, pH-responsive Dox release and Fenton-like copper redox chemistry, along with Dox-activated H2O2 elevation and more efficient center dot OH generation in cancer cells, eventually trigger the synergistic CT/CDT with remarkable anti-tumor efficacy. image

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.g., fully porous, multi-chamber, multi-shell, and concentric multi-layer architectures) is reported via halogen-bond regulated 3D confined-assembly of amphiphilic polymer networks. To do so, polystyrene-b-poly(2-vinyl pyridine)-b-poly(ethylene oxide) (PS-b-P2VP-b-PEO) amphiphilic triblock copolymer is selected, where P2VP blocks act as halogen acceptor. Meanwhile, poly(3-(2,3,5,6-tetrafluoro-4-iodophenoxy) propyl acrylate) (PTFIPA) is employed as halogen donor. Halogen-bond driven donor-acceptor linking between PTFIPA and P2VP block presented in PS-b-P2VP-b-PEO, can lead to the formation of supramolecular polymeric networks, along with the increased P2VP domain and tunable hydrophobic volume. Therefore, an adjustable packing parameter (p) is thus anticipated, which can enable the morphology transformation sequence until an equilibrium state is reached. Moreover, computer simulations are further utilized as the tool to interpret such morphologies transition and identify the precise distribution of each component. Benefiting from the tunable hollow structure and a substantial surface for transporting purpose, these structurally novel particles open perspectives toward promising applications including encapsulation, nanoreactor, and catalyst support.

Constitutional dynamic chemistry (CDC), as defined by Lehn (), covers both supramolecular science and dynamic covalent chemistry to process components recombination toward the chemistry of complex matter. While CDC has increasingly guided active research decisions during the past decades, undergraduate chemistry curricula do not reflect the prevalence of such concepts and knowledge; this article seeks to introduce such ideas to laboratory practice. Incorporation of CDC and its characterization techniques, such as 1H NMR and mass spectrometry (MS), into chemistry education is warranted to support CDC-relevant learning experiences, understanding of spectroscopy instrumentation, and student motivation to pursue a professional career. Herein, we develop an experimental design by combining supramolecular forces, i.e., H-bonding interaction, and dynamic covalent linkage, i.e., borate ester bond, toward orthogonal linking of the chemotherapeutic agent gemcitabine (GEM) by the antiviral drug acyclovir (ACV) and proteasome inhibitor bortezomib (BTZ). Such design enables a "double dynamic" process, which leverages both noncovalent and covalent dynamics. Moreover, this laboratory program outlines how NMR and MS technologies are employed to characterize H-bonding association and boronic ester bonds. Such a lab experiment provides the prospect for instructors to illustrate to undergraduates with a basic background in chemistry and medical science the state-of-the-art H-bonding interaction and boronic ester bond, modern characterization instruments, and broad impacts of CDC.

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.