Visualizing molecular weights differences in supramolecular polymers.

Issues of molecular weight determination have been central to the development of supramolecular polymer chemistry. Whereas relationships between concentration and optical features are established for well-behaved absorptive and emissive species, for most supramolecular polymeric systems no simple correlation exists between optical performance and number-average molecular weight (Mn). As such, the Mn of supramolecular polymers have to be inferred from various measurements. Herein, we report an anion-responsive supramolecular polymer [M1·Zn(OTf)2]n that exhibits monotonic changes in the fluorescence color as a function of Mn Based on theoretical estimates, the calculated average degree of polymerization (DPcal) increases from 16.9 to 84.5 as the monomer concentration increases from 0.08 mM to 2.00 mM. Meanwhile, the fluorescent colors of M1 + Zn(OTf)2 solutions were found to pass from green to yellow and to orange, corresponding to a red shift in the maximum emission band (λmax ). Therefore, a relationship between DPcal and λmax could be established. Additionally, the anion-responsive nature of the present system meant that the extent of supramolecular polymerization could be regulated by introducing anions, with the resulting change in Mn being readily monitored via changes in the fluorescent emission features.

pH/H2O2 Cascade-Responsive Nanoparticles of Lipid-Like Prodrugs through Dynamic-Covalent and Coordination Interactions for Chemotherapy.

Traditional lipid nanoparticles (LNPs) suffer from low drug loading capacity (DLC), weak stability, and lack of responsiveness. Conventional approaches to address these issues involve the synthesis of lipid-prodrug by incorporating responsive covalent linkers. However, such approaches often result in suboptimal sensitivity for drug release and undermine therapeutic effectiveness. Herein, the study reports a fundamentally different concept for designing lipid-like prodrugs through boron-nitrogen (B-N) coordination and dynamic covalent interaction. The 5-fluorouracil-based lipid-like prodrugs, featuring a borate ester consisting of a glycerophosphoryl choline head and a boronic acid-modified 5Fu/dodecanamine complex tail, are used to prepare pH/H2O2 cascade-responsive LNPs (5Fu-LNPs). The 5Fu-LNPs exhibit enhanced DLC and stability in a neutral physiological environment due to the B-N coordination and enhanced hydrophobicity. In tumors, acidic pH triggers the dissociation of B-N coordination to release prodrugs, which further responds to low H2O2 concentrations to release drugs, showcasing a potent pH/H2O2-cascade-responsive property. Importantly, 5Fu-LNPs demonstrate greater antitumor efficiency and lower toxicity compared to the commercial 5Fu. These results highlight 5Fu-LNPs as a safer and more effective alternative to chemotherapy. This work presents a unique LNP fabrication strategy that can overcome the limitations of conventional LNPs and broaden the range of intelligent nanomaterial preparation techniques.

Decoding the Pathway-Dependent Self-Assembly of Polymer-Grafted Nanoparticles by Ligand Crystallization.

Functional metamaterials can be constructed by assembling nanoparticles (NPs) into well-ordered structures, which show fascinating properties at different length scales. Using polymer-grafted NPs (PGNPs) as a building block, flexible composite metamaterials can be obtained, of which the structure is significantly affected by the property of polymer ligands. Here, it is demonstrated that the crystallization of polymer ligands determines the assembly behavior of NPs and reveal a pathway-dependent self-assembly of PGNPs into different metastructures in solution. By changing the crystallization degree of polymer ligands, the arrangement structure of NPs can be tailored. When the polymer ligands highly crystallize, the PGNPs assemble into diamond-shaped platelets, in which the NPs arrange disorderedly. When the polymer ligands lowly crystallize, the PGNPs assemble into highly ordered 3D superlattices, in which the NPs pack into a body-centered-cubic structure. The structure transformation of PGNP assemblies can be achieved by thermal annealing to regulate the crystallization of polymer ligands. Interestingly, the diamond-shaped platelets remain "living" for seeded epitaxial growth of newly added crystalline species. This work demonstrates the effects of ligand crystallization on the crystallization of NP, providing new insights into the structure regulation of metamaterials.

A-D-A Type Nonfullerene Acceptors Synthesized by Core Segmentation and Isomerization for Realizing Organic Solar Cells with Low Nonradiative Energy Loss.

Reducing non-radiative recombination energy loss (ΔEnonrad ) in organic solar cells (OSCs) has been considered an effective method to improve device efficiency. In this study, the backbone of PTBTT-4F/4Cl is divided into D1-D2-D3 segments and reconstructed. The isomerized TPBTT-4F/4Cl obtains stronger intramolecular charge transfer (ICT), thus leading to elevated highest occupied molecular orbital (HOMO) energy level and reduced bandgap (Eg ). According to ELoss  = Eg- qVOC , the reduced Eg and enhanced open circuit voltage (VOC ) result in lower ELoss , indicating that ELoss has been effectively suppressed in the TPBTT-4F/4Cl based devices. Furthermore, compared to PTBTT derivatives, the isomeric TPBTT derivatives exhibit more planar molecular structure and closer intermolecular stacking, thus affording higher crystallinity of the neat films. Therefore, the reduced energy disorder and corresponding lower Urbach energy (Eu ) of the TPBTT-4F/4Cl blend films lead to low ELoss and high charge-carrier mobility of the devices. As a result, benefitting from synergetic control of molecular stacking and energetic offsets, a maximum power conversion efficiency (PCE) of 15.72% is realized from TPBTT-4F based devices, along with a reduced ΔEnonrad of 0.276 eV. This work demonstrates a rational method of suppressing VOC loss and improving the device performance through molecular design engineering by core segmentation and isomerization.

Alkyl Chains Tune Molecular Orientations to Enable Dual Passivation in Inverted Perovskite Solar Cells.

Nonradiative recombination losses occurring at the interface pose a significant obstacle to achieve high-efficiency perovskite solar cells (PSCs), particularly in inverted PSCs. Passivating surface defects using molecules with different functional groups represents one of the key strategies for enhancing PSCs efficiency. However, a lack of insight into the passivation orientation of molecules on the surface is a challenge for rational molecular design. In this study, aminothiol hydrochlorides with different alkyl chains but identical electron-donating (-SH) and electron-withdrawing (-NH3 +) groups were employed to investigate the interplay between molecular structure, orientation, and interaction on perovskite surface. The 2-Aminoethane-1-thiol hydrochloride with shorter alkyl chains exhibited a preference of parallel orientations, which facilitating stronger interactions with the surface defects through strong coordination and hydrogen bonding. The resultant perovskite films following defect passivation demonstrate reduced ion migration, inhibition of nonradiative recombination, and more n-type characteristics for efficient electron transfer. Consequently, an impressive power conversion efficiency of 25 % was achieved, maintaining 95 % of its initial efficiency after 500 hours of continuous maximum power point tracking.

Reversible Emulsions from Polyoxometalate-Polymer: A Robust Strategy to Cyclic Emulsion Catalysis and High-Internal-Phase Emulsion Materials.

Reversible Pickering emulsions, achieved by switchable, interfacially active colloidal particles, that enable on-demand emulsification/demulsification or phase inversion, hold substantial promise for biphasic catalysis, emulsion polymerization, cutting fluids, and crude oil pipeline transportation. However, particles with such a responsive behavior usually require complex chemical syntheses and surface modifications, limiting their extensive use. Herein, we report a simple route to generate emulsions that can be controlled and reversibly undergo phase inversion. The emulsions are prepared and stabilized by the interfacial assembly of polyoxometalate (POM)-polymer, where their electrostatic interaction at the interface is dynamic. The wettability of the POMs that dictates the emulsion type can be readily regulated by tuning the number of polymer chains bound to POMs, which, in turn, can be controlled by varying the concentrations of both components and the water/oil ratio. In addition, the number of polymer chains anchored to the POMs can be varied by controlling the number of negative charges on the POMs through an in situ redox reaction. As such, a reversible inversion of the emulsions can be triggered by switching between exposure to ultraviolet light and the introduction of oxygen. Combining the functions of POM itself, a cyclic interfacial catalysis system was realized. Inversion of the emulsion also affords a pathway to high-internal-phase emulsions. The diversity of the POMs, the polymers, and the responsive switching groups open numerous new, simple strategies for designing a wide range of responsive soft matter for cargo loading, controlled release, and delivery in biomedical and engineering applications without time-consuming particle syntheses.

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. Moreover, the AuNR@PS with short PS ligand are favorited to form orientated arrays with the assistance of electric field, while long PS ligands make the orientation of AuNRs difficult. The orientated AuNR@PS arrays are employed as the nano-floating gate of field-effect transistor memory device. Tunable charge trapping and retention characteristics in the device can be realized by electrical pulse with visible light illumination. The memory device with orientated AuNR@PS array required less illumination time (1 s) at the same onset voltage in programming operation, compared to the control device with disordered AuNR@PS array (illumination time: 3 s). Moreover, the orientated AuNR@PS array-based memory device can maintain the stored data for more than 9000 s, and exhibits stable endurance characteristic without significant degradation in 50 programming/reading/erasing/reading cycles.

In Situ Self-Assembly of Nanoscale Particles into Macroscale Ordered Monolayers with Enhanced Memory Performance.

In situ fabrication of macroscale ordered monolayers of nanoparticles (NPs) on targeted substrates is highly desirable for precision electronic and optical devices, while it remains a great challenge. In this study, a solution is provided to address this challenge by developing a colloidal ink formulation and employing the direct-ink-writing (DIW) technique, where on-demand delivery of ink at a targeted location and directional evaporation with controllable rate are leveraged to precisely guide the deposition of polystyrene-grafted gold NPs (Au@PS NPs) into a macroscale monolayer with an ordered Au NP array embedded in a PS thin film. A 2D steady-state diffusion-controlled evaporation model, which explains the parameter dependence of the experimental results and gives semiquantitative agreement with the experimental evaporation kinetics is proposed. The ordered monolayer is used as both nanocrystal floating gates and the tunneling layer for nonvolatile memory devices. It shows significantly enhanced performance compared with a disordered NP film prepared by spin coating. This approach allows for fine control of NP self-assembly to print macroscaleordered monolayers directly onto substrates, which has great promise for application in broad fields, including microelectronic and photoelectronic devices, sensors, and functional coatings.

Trace Explosive Detection Based on Photonic Crystal Amplified Fluorescence.

With increasing demand for public security and environmental protection, it is highly desirable to develop strategies to identify trace explosives (e. g., 2,4,6-trinitrotoluene (TNT)). Herein, we report novel photonic crystal (PC)-based sensor chips for trace TNT detection by using amplification effect of PCs on fluorescence (FL) signals. The sensor chips are constructed by integrating silica nanoparticles (NPs) modified with (3-aminopropyl)triethoxysilane (APTES) and fluorescein isothiocyanate isomer (FITC) and PC substrates. The amino groups on FITC-APTES-silica NPs can specifically bind with TNT molecules to form Meisenheimer complexes and strongly quench the FL signal of neighboring fluorophores FITC through Förster resonance energy transfer. PCs with matched PBG can amplify the FL signal of FITC-APTES-silica NPs about 24.4-fold and significantly improve sensitivity and resolution of trace TNT detection with the limit of detection of 0.23 nM. The PC-based sensor chips are stable, sensitive, and reliable TNT sensing platforms, showing great potential in homeland safety and environmental protection.

Effect of Polymeric Ligand Grafting Region on Confined Assembly of Gold Nanorods in cylindrical nanopores.

The grafting region of polymeric ligands exhibit a significant influence on the assembly behavior of polymer tethered gold nanorods (AuNRs) in confined space. In this work, the effect of core size, molecular weight and grafting region of ligands on the assembly structure in cylindrical nanopores was investigated. It is found that polystyrene end-tethered AuNR (AuNR@End-PS) exhibits a dumbbell-like shape, while the AuNR with PS tethered on the entire surface (AuNR@Full-PS) shows a rod-like morphology that gradually transforms into a spherical shape as the molecular weight increases. AuNR@End-PS is affected by the special steric hindrance at both ends, and prefers to form special structures such as inclination arrangement, whereas AuNR@Full-PS prefers to be arranged shoulder-to-shoulder in a chain-like assembly. The confinement effect was studied as well by varying the diameter of pores. The results show that the nanoparticles prefer to arrange into a regular and ordered assembly structure in the strong confinement spaces. Under the synergy of confined spaces and ligands at both ends, the AuNRs@End-PS are more likely to form a tilted order-assembly structure. The results of this work could provide new ideas and guidance for the preparation of ordered assembly of AuNRs with novel structures.

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. Indeed, rod-like nano-objects are successfully generated via the self-assembly and coordination interaction between P(OEGEA-r-ATU) and Cu. The spatial distribution of TU moieties in polymer chain, along with their Cu chelating capability, featuring the interchain coordination interaction, is tightly related to metallo-supramolecular polymer organization. The specific Cu-TU coordination interactions enable the prompted robustness and stability of soft P(OEGEA-r-ATU), induce the polymer chain configuration, which eventually furnish efficient fabrication of rod-like nano-objects via straightforward nanoprecipitation procedure. These structural motifs of copper-coordinated, rod-like nano-objects from such metallo-supramolecular polymers endow the potential therapeutic properties, such as anti-inflammatory and antitumor effects.

Controlled synthesis of Fe3O4/MnO2 (3 1 0)/ZIF-67 composite with enhanced synergetic effects for the highly selective and efficient adsorption of Cu (II) from simulated copperplating effluents.

This study designed a composite material with internal synergistic effects among multiple components to achieve highly selective adsorption of Cu (II). Through controlled synthesis, the Fe3O4/MnO2(3 1 0)/ZIF-67 composite was successfully fabricated, leading to significant improvement in adsorption selectivity, capacity, and adsorption rate. The experimental results showed that the composite is of outstanding selectivity in the adsorption of Cu (II), with a partition coefficient K of Cu (II) that was 2.2-5.3 times higher than that of other coexisting ions. Moreover, the composite exhibited a remarkable adsorption capacity of 1261.0 mg g-1 and a fast adsorption rate of 840.7 mg g-1 h-1 at 298 K. Additionally, its magnetic property facilitated easy separation from wastewater, thereby enhancing its potential for commercial applications. The synergetic effect mechanism was analyzed through characterizations and DFT calculations. Furthermore, the recyclability of the composite was investigated, which showed that after seven cycles, the adsorption efficiency remained at 85% of its initial efficiency. It can be concluded that Fe3O4/MnO2(3 1 0)/ZIF-67 has potential to address challenges posed by heavy metal pollution in copperplating effluents.

Fabrication of Oriented Colloidal Crystals from Capillary Assembly of Polymer-Tethered Gold Nanoparticles.

Self-assembled colloidal crystals (CCs) or nanoparticle (NPs) superlattices have attracted significant attention due to their potential applications in many fields. However, due to the complex interactions that govern the self-assembly, it is difficult to predict and control the superstructure organization of CCs. Herein, a facile yet effective way is demonstrated to fabricate oriented CCs from capillary assembly of polymer-tethered gold NPs (AuNPs). Assembly mechanism of polymer-tethered AuNPs and their superlattice structures are systematically studied by in situ small-angle X-ray scattering (SAXS) technology. The results show that the oriented CCs of polymer-tethered AuNPs can be obtained upon solvent evaporation in a capillary tube and the oriented structure is mainly determined by the chain length of polymer ligands and size of AuNPs. Assembly of AuNPs tethered by short-chain ligand can result in oriented face-centered cubic (fcc) superlattice, whereas AuNPs tethered by long-chain ligand can assemble into an oriented body-centered tetragonal (bct) superlattice structure. Interestingly, in situ SAXS study shows that for the sample of bct superlattice structure, a transformation from fcc to bct superlattice upon solvent evaporation is observed, which strongly depends on chain length of ligands. This work provides a useful guide for polymer-tethered AuNPs to prepare orientation colloidal crystals.

Size-Transformable Bicomponent Peptide Nanoparticles for Deep Tumor Penetration and Photo-Chemo Combined Antitumor Therapy.

The suitable size of multifunctional nanomedicines strongly influences their physicochemical properties and actions in biological systems, for example, prolonged blood circulation time, efficient tumor accumulation, and deep tumor penetration. However, it is still a great challenge to construct size-transformable nanoparticles (NPs) for both efficient accumulation and penetration throughout tumor tissue. Herein, a size-transformed multifunctional NP is developed through a simple bicomponent assembling strategy for enhanced tumor penetration and efficient photo-chemo combined antitumor therapy, due to the acidic tumor microenvironment and near infrared-laser irradiation induced size-shrink. This multifunctional bicomponent NP (PP NP) driven by electrostatic interaction is composed of negatively charged peptide amphiphile (PA1) and positively charged peptide prodrug (PA2). PP NPs (≈170 nm) have been proven to improve blood circulation time and stability in biological environments. Interestingly, PP NPs can reassemble small NPs (<30 nm) by responding to acidic tumor microenvironment and near-infrared laser irradiation, which facilitates deep tumor penetration and improves cellular internalization. By integrating fluorescence imaging, tumor targeting, deep tumor penetration, and combined photo-chemotherapy, PP NPs exhibit excellent in vivo antitumor efficacy. This study might provide an insight for developing a bicomponent assembling system with efficient tumor penetration and multimode for antitumor therapy.

Morphological Transformation and In Situ Polymerization of Caspase-3 Responsive Diacetylene-Containing Lipidated Peptide Amphiphile for Self-Amplified Cooperative Antitumor Therapy.

In order to artificially regulate cell behaviors, intracellular polymerization as an emerging chemical technique has attracted much attention. Yet, it is still a challenge to achieve effective intracellular polymerization to conquer tumors in the complex cellular environment. Herein, this work develops a tumor-targeting and caspase-3 responsive nanoparticle composed of a diacetylene-containing lipidated peptide amphiphile and mitochondria-targeting photosensitizer (C3), which undergoes nanoparticle-to-nanofiber transformation and efficient in situ polymerization triggered by photodynamic treatment and activation of caspase-3. The locational nanofibers on the mitochondria membranes lead to mitochondrial reactive oxygen species (mtROS) burst and self-amplified circulation, offering persistent high oxidative stress to induce cell apoptosis. This study provides a strategy for greatly enhanced antitumor therapeutic efficacy through mtROS burst and self-amplified circulation induced by intracellular transformation and in situ polymerization.

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). 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.

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-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 P[OEGEA-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.

MolMiner: You Only Look Once for Chemical Structure Recognition.

Molecular structures are commonly depicted in 2D printed forms in scientific documents such as journal papers and patents. However, these 2D depictions are not machine readable. Due to a backlog of decades and an increasing amount of printed literatures, there is a high demand for translating printed depictions into machine-readable formats, which is known as Optical Chemical Structure Recognition (OCSR). Most OCSR systems developed over the last three decades use a rule-based approach, which vectorizes the depiction based on the interpretation of vectors and nodes as bonds and atoms. Here, we present a practical software called MolMiner, which is primarily built using deep neural networks originally developed for semantic segmentation and object detection to recognize atom and bond elements from documents. These recognized elements can be easily connected as a molecular graph with a distance-based construction algorithm. MolMiner gave state-of-the-art performance on four benchmark data sets and a self-collected external data set from scientific papers. As MolMiner performed similarly well in real-world OCSR tasks with a user-friendly interface, it is a useful and valuable tool for daily applications. The free download links of Mac and Windows versions are available at https://github.com/iipharma/pharmamind-molminer.

Bioinspired Supramolecular Photonic Composites: Construction and Emerging Applications.

Living organisms have evolved fascinating structural colors to survive in complex natural environments. Artificial photonic composites developed by imitating the structural colors of organisms are applied in displaying, sensing, biomedicine, and many other fields. As emerging materials, photonic composites mediated by supramolecular chemistry, namely, supramolecular photonic composites, are designed and constructed to meet emerging application needs and challenges. This review mainly introduces the constructive strategies, properties, and applications of supramolecular photonic composites. First, constructive strategies of supramolecular photonic composites are summarized, including the introduction of supramolecular polymers into colloidal photonic array templates, coassembly of colloidal particles (CPs) with supramolecular polymers, self-assembly of soft CPs, and compounding photonic elastomers with functional substances via supramolecular interactions. Supramolecular interactions endow photonic composites with attractive properties, such as stimuli-responsiveness and healability. Subsequently, the unique optical and mechanical properties of supramolecular photonic composites are summarized, and their applications in emerging fields, such as colorful coatings, real-time and visual motion monitoring, and biochemical sensors, are introduced. Finally, challenges and perspectives in supramolecular photonic composites are discussed. This article provides general strategies and considerations for the design of photonic materials based on supramolecular chemistry.

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. 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.