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We use phototherapy rather than chemotherapy and radiotherapy for the first time before surgery to thoroughly remove the tumors with minimum wound area and few side effects. The phototoxicity under hypoxia conditions and targeting ability of photosensitizers were improved by camouflaging Chlorin e6 and chlorambucil assemblies with cancer cell membranes. This work provides a creative method for tumor clinical therapy. [Display omitted] Surgical risk and wound area can be reduced by diminishing tumor volume before surgery. The chemotherapy and radiotherapy currently used that can reduce the tumor volume generally cause severe systemic side effects. Phototherapy has recently emerged as an effective treatment modality for superficial cancers. However, phototherapy is limited by the low utilization of photosensitizer, the tumor hypoxia, and the low photothermal conversion efficiency. Herein, we report the cancer membrane biomimetic nanoparticles assembled by Chlorin e6 (Ce6) and chlorambucil (CRB). Ce6@CRB nanoparticles (CCNPs) show excellent photothermal conversion efficiency, which is 2 times higher than free Ce6. Meanwhile, CCNPs can produce singlet oxygen stably compared to free Ce6 thereby reducing the dependence on oxygen. Furthermore, the coating of 4 T1 cancer membrane on the surface of CCNPs endows them with the ability of homologous targeting, not only improving the utilization of Ce6, but also effectively activating the immune system in vivo when combined photodynamic therapy (PDT) and photothermal therapy (PTT). Intriguingly, surgical resection is performed after phototherapy in this treatment regimen, which can effectively reduce the wound area. Together, this work provided a feasible and creative method for tumor clinical therapy for its patient-centric and humanitarian focus. [ABSTRACT FROM AUTHOR]

The escalating utilization of nuclear energy and nuclear medicine raises concerns about the environmental impact of radioactive iodine, necessitating the development of effective iodine adsorbents, especially under a real-world scenario with extremely low iodine concentration and elevated temperature. Herein, we have presented the construction of a nitrogen-abundant two-dimensional (2D) halogen-bonded organic framework, XOF-TNP, characterized by exceptional crystallinity, thermal stability, and nitrogen-rich structures. XOF-TNP exhibits strong binding to iodine, thanks to the fact that iodine can be pre-enriched into the framework through N⋯I interactions. The nitrogen-rich framework and I+ synergistically have extremely high binding force to iodine, enabling the rapid and efficient capture of iodine in both vapor and solution phases, with significant recyclability. Further flow-through adsorption experiments using an XOF-TNP-packed column achieve 99% iodine removal from hexane and aqueous solutions, surpassing traditional activated carbon. This highlights its potential for environmental remediation. XOF-TNP enables the development of a novel rewritable security paper, utilizing its iodine adsorption properties to encrypt and decrypt QR codes. This research expands the application scope of halogen-bonded organic frameworks, providing insights into the design of materials for environmental remediation and security applications. [ABSTRACT FROM AUTHOR]

A novel aggregation‐induced emission (AIE)‐based artificial light‐harvesting system (LHS) is successfully assembled via the host‐guest interaction of bis‐naphthylacrylonitrile derivative (BND), water‐soluble pillar[5]arene (WP5), and sulforhodamine 101 (SR101). After host‐guest assembly, the formed WP5⊃BND complexes spontaneously self‐aggregated into WP5⊃BND nanoparticles (donors) and SR101 (acceptors) is introduced into WP5⊃BND to fabricate WP5⊃BND‐SR101 LHS. Through the investigation of energy transfer between donors and acceptors, the artificial light‐harvesting processes are certified in WP5⊃BND‐SR101 LHS and the absolute fluorescence quantum yields (Φf(abs)) are significantly improved from 8.9% (for WP5⊃BND) to 31.1% (for WP5⊃BND‐SR101), exhibiting the excellent light‐harvesting capabilities. Notably, by tuning the donor/acceptor (D:A) molar ratio to 250:1, a conspicuous white light emission (CIE coordinate is (0.32, 0.32)) is realized and the fluorescence quantum yield of white light emission (Φf(abs)WP5⊃BND‐SR101‐White) is 29.2%. Moreover, the antenna effect of white fluorescence emission (AEWP5⊃BND‐SR101‐White) can reach 36.2, which is higher than that of recent artificial LHSs in water environments, suggesting vast potential applications in aqueous LHSs. [ABSTRACT FROM AUTHOR]

Hepatitis C virus (HCV) is a major public health concern, and the development of an effective HCV vaccine plays an important role in the effort to prevent new infections. Supramolecular co-assembly and co-presentation of the HCV envelope E1E2 heterodimer complex and core protein presents an attractive vaccine design strategy for achieving effective humoral and cellular immunity. With this objective, the two antigens were non-covalently assembled with an immunostimulant (TLR 7/8 agonist) into virus-mimicking polymer nanocomplexes (VMPNs) using a biodegradable synthetic polyphosphazene delivery vehicle. The resulting assemblies were characterized using dynamic light scattering and asymmetric flow field-flow fractionation methods and directly visualized in their vitrified state by cryogenic electron microscopy. The in vivo superiority of VMPNs over the individual components and an Alum-formulated vaccine manifests in higher neutralizing antibody titers, the promotion of a balanced IgG response, and the induction of a cellular immunity—CD4+ T cell responses to core proteins. The aqueous-based spontaneous co-assembly of antigens and immunopotentiating molecules enabled by a synthetic biodegradable carrier offers a simple and effective pathway to the development of polymer-based supramolecular nanovaccine systems. [ABSTRACT FROM AUTHOR]

Imperfections in metal halide perovskites, such as those induced by light exposure or thermal stress, compromise device performance and stability. A key challenge is immobilizing volatile iodine produced by iodide oxidation and regenerating impurities like elemental lead and iodine. Here, we address this by integrating a redox‐active supramolecular assembly of nickel octaethylporphyrin into perovskite film, functioning as both an immobilizer and redox shuttle. Decorated ethyl groups in porphyrin distorts the π ring, increasing the axial ligand adsorption capacity of central metal ion, while reducing intermolecular interactions and promoting iodine adsorption achieving a maximum uptake of 3.83 mg mg−1 to iodine. Adsorbed iodine transfers more electrons to Ni ions, leading to a weakened interaction within I−I bond and facilitating the production of iodide ions. Such a situation further enables selective oxidation of metallic lead defects to Pb2+. Porphyrin supramolecule facilitates hole transport across perovskite grain boundaries, leading to a champion device efficiency of 25.37 % for a 0.10 cm2 active area, outperforms the value of control device being 23.96 %. Modified devices without encapsulation exhibit significantly enhanced stability, maintaining over 90 % of its initial performance after 1,000 hours of continuous 1‐sun illumination at maximum power point at 65 °C. [ABSTRACT FROM AUTHOR]

Chiral hybrid organic–inorganic metal halides (HOMHs) hold great promise in broad applications ranging from ferroelectrics, spintronics to nonlinear optics, owing to their broken inversion symmetry and tunable chiroptoelectronic properties. Typically, chiral HOMHs are constructed by chiral organic cations and metal anion polyhedra, with the latter regarded as optoelectronic active units. However, the primary design approaches are largely constrained to regulation of general components within structural formula. Herein, supramolecular approaches have been taken for the functionalization of chiral enantiomers by anchoring chiral cations with crown ether hosting molecules. Chiral HOMHs of R‐/S‐(18‐crown‐6@ClMBA)2MnBr4 have been thus obtained with boosted linear and nonlinear chiroptical properties. The self‐assembled cations lead to enhanced structural rigidity, which promote near‐unity green light emission and strong circularly polarized luminescence with a high asymmetry factor, along with high efficiency second‐order nonlinear optical responses. In particular, these chiral HOMH single crystals demonstrate a sensitive discrimination for circularly polarized laser in the near‐infrared region with the nonlinear optical asymmetry factor (gSHG‐CD) as high as 1.8. This work highlights the contribution of supramolecular assembly in improving chiroptical performances, offering valuable insights for the design of new chiral HOMH materials with promising application potentials as linear and nonlinear CPL emitters and detectors. [ABSTRACT FROM AUTHOR]

[Display omitted] Chemodynamic therapy (CDT) via Fenton-like reaction is greatly attractive owing to its capability to generate highly cytotoxic •OH radicals from tumoral hydrogen peroxide (H 2 O 2). However, the antitumor efficacy of CDT is often challenged by the relatively low radical generation efficiency and the high levels of antioxidative glutathione (GSH) in tumor microenvironment. Herein, an innovative photothermal Fenton-like catalyst, Fe-chelated polydopamine (PDA@Fe) nanoparticle, with excellent GSH-depleting capability is constructed via one-step molecular assembly strategy for dual-modal imaging-guided synergetic photothermal-enhanced chemodynamic therapy. Fe(III) ions in PDA@Fe nanoparticles can consume the GSH overexpressed in tumor microenvironment to avoid the potential •OH consumption, while the as-produced Fe(II) ions subsequently convert tumoral H 2 O 2 into cytotoxic •OH radicals through the Fenton reaction. Notably, PDA@Fe nanoparticles demonstrate excellent near-infrared light absorption that results in superior photothermal conversion ability, which further boosts above-mentioned cascade catalysis to yield more •OH radicals for enhanced CDT. Taken together with T 1 -weighted magnetic resonance imaging (MRI) contrast enhancement (r 1 = 8.13 mM−1 s−1) and strong photoacoustic (PA) imaging signal of PDA@Fe nanoparticles, this design finally realizes the synergistic photothermal-chemodynamic therapy. Overall, this work offers a new promising paradigm to effectively accommodate both imaging and therapy functions in one well-defined framework for personalized precision disease treatment. [ABSTRACT FROM AUTHOR]

Slow evaporation methods were employed to grow single crystals of 3-acetylpyridinium picrate (I), 4-acetylpyridinium picrate (II), and pyridin-4-ylmethanaminium 2,2-diphenylacetate hydrate (III). Crystal (I) and (III) crystallize triclinic crystal system with a centric (Pī) space group and (II) crystallize in a monoclinic system with a centric (P21/c) space group. Various types of non-covalent interactions take part successfully in the construction of 3D networks in the compounds. Optical reflectance measurements showed 2.57, 2.66, and 4.45 eV as band gaps for (I), (II) and (III) respectively. TG/DTA analysis reveals the thermal pattern of the compounds. Intermolecular interactions are quantified by Hirshfeld surface analysis. [ABSTRACT FROM AUTHOR]

Amino acid‐based biomolecular glasses represent an emerging material to meet the demand for sustainable development. However, most amino acids are difficult to vitrify due to their strong crystallization tendency, limiting further advancements of this field. In this study, we demonstrate that the introduction of counterions effectively suppresses crystallization, as hydrogen bonds within the system stabilize the disordered structures. Based on this, we propose a counterion co‐assembly strategy to synthesize a wide range of amino acid‐based glasses. This strategy enables the facile fabrication of glass with customizable shapes, high mechanical rigidity, and tunable multicolor fluorescence, ranging from blue to red depending on the excitation wavelength. Furthermore, this strategy allows the integration and enhancement of counterion properties within the glass matrix. Through the co‐assembly of phosphorescent counterions, we synthesized a series of long‐persistent luminescent glasses with significantly extended afterglow lifetimes. This work presents an effective approach for the synthesis of amino acid‐based glasses and provides insights into the development of supramolecular glasses with tailored functionalities. [ABSTRACT FROM AUTHOR]

The reaction of p-methylbenzaldehyde and 5,5-dimethyl-1,3-cyclohexanedione with the addition of HCl yielded 3,3,6,6-tetramethyl-9-(p-tolyl)-3,4,5,6,7,9-hexahydro-1H-xanthene-1,8(2H)-dione (TTHD). X-ray diffraction method was used for verification of the crystal structure. Supramolecular assembly was studied via various intermolecular interactions and explored via Hirshfeld surface analysis. The contact-making ability of the pairs of atoms is determined by enrichment ratios. The stability of the present compound is determined through interaction energies. Electronic structure calculations are conducted at the wb97xd/def2tzvp theoretical level. Charge transfer and reactivity are estimated through natural bonding orbital (NBO) charge analysis. Global reactivity parameters are calculated and compared with the reported molecule. Quantum theory of atoms in molecules (QTAIM) is exploited to unveil the bonding’s nature and van der Waals interactions (vdW). Electron localizing function (ELF), and localized orbital locator (LOL) are also employed to investigate electronic properties. The optical and nonlinear optical (NLO) properties of the present compound are examined using the density functional theory (DFT) method. [ABSTRACT FROM AUTHOR]

Molecular spherical nucleic acids (m‐SNAs) are a second generation of spherical nucleic acids (SNAs), which are of significance in potential application of targeted delivery of nucleic acids or gene regulation due to their defined molecular structures. Nevertheless, m‐SNAs typically involve a single DNA sequence which greatly limits its functions as either targeting purpose or gene regulation. In response, we proposed here a third generation, supramolecular spherical nucleic acids (Supra‐SNAs) with two different sequences to achieve both above‐mentioned functions. Specifically, we constructed a series of supramolecular self‐assembly structures by coupling a cell membrane receptor (i.e., nucleolin)‐recognizing aptamer (AS1411)‐modified adamantine as targeting probe and human epithelial growth factor receptor 2 (HER2) antisense‐functionalized β‐cyclodextrin to specifically inhibit the overexpression of HER2 proteins for gene regulations. In comparison to the m‐SNA precursors, such Supra‐SNA structures exhibited enhanced levels of resistance to nuclease degradation, cellular uptake, gene regulation capabilities and tumor retention capacity. We demonstrated that Supra‐SNAs exhibited optimal cell suppression rates and cell apoptosis via a phosphatidylinositol 3‐kinase/protein kinase B signaling pathway. The well‐defined molecular structures provide an attractive platform for investigating interrelationship between structure and property at the molecular level. [ABSTRACT FROM AUTHOR]

Curved π‐electron systems show unique properties and assembly feature that enable the specific applications in materials science and supramolecular chemistry. Herein, fullerene, carbon nanohoop and π‐bowl are integrated by the coupling of covalent and supramolecular tactics. Firstly, π‐bowl trichalcogenasumanenes (TCSs) are fused with a carbon nanohoop [10]CPP via covalent joint to form molecular crowns 4a/4b, which show structural and electronic complementarity and accordingly strong binding affinity to C60/C70. Secondly, the supramolecular assemblies of 4a/4b with fullerenes afford the host‐guest complexes 4a/4b⊃C60/C70 in solution (molar ratio, 2:1) and solid state (molar ratio, 1:1). In the crystals of host–guest complexes, the intra‐cluster and inter‐cluster interactions are respectively dominated by the [10]CPP and TCSs moieties of 4a/4b. Additionally, it is found that 4a/4b are good photosensitizers for generating 1O2 and show structural adaptability in accordance to assembly conditions. 4a/4b take an endo‐conformation in their own crystals with TCSs and [10]CPP moieties being bowl‐shaped and elliptical, respectively. In contrast, the [10]CPP on 4a/4b changes into circular and the TCSs moiety becomes flat (for 4b) or shows bowl inversion to be exo‐conformation (for 4a) in 4a/4b⊃C60/C70. [ABSTRACT FROM AUTHOR]

In cellular environments, certain synthetic molecules can form nanostructures via self-assembly, impacting molecular imaging, and biomedical applications. Control over the formation of these self-assembled nanostructures in subcellular organelle is challenging. By the action of stimuli, either present in the cellular environment or applied externally, in situ generation of molecular precursors can lead to accumulation and supramolecular nanostructure formation, resulting in efficient bioimaging. Here, we summarize smart fluorophore-based ordered nanostructure preparation at specific organelles for efficient bioimaging and therapeutic application towards cancer theranostics. We also present challenges and an outlook regarding intercellular self-assembly for theranostics application. Altogether, smart nanostructured materials with fluorescence read-outs at specific subcellular compartments would be beneficial in synthetic biology and precision therapeutics. [ABSTRACT FROM AUTHOR]

Hypertrophic scar (HS) remains a major challenge for clinicians due to unsatisfactory therapeutic performance. Although inducing apoptosis of HS fibroblasts (HSFs) has proved to be an effective nonsurgical treatment strategy, potential chemotherapy resistance to apoptosis of HSFs makes the development of new and efficient strategies highly demanding. Herein, a ferroptosis‐apoptosis combined therapeutic strategy for the treatment of HS is developed through supramolecular self‐assembly between cucurbit[7]uril (CB[7]) and two bioactive agents, dihydroartemisinin (DHA) and gold nanoclusters (AuNCs). The resulting self‐assembled supramolecular nanoparticles, named CAD NPs, showed high guest loading efficiency and prominent pH‐responsive degradability in the acidic lysosomes of HSFs. Importantly, both DHA and AuNCs act synergistically to generate excessive reactive oxygen species and lipid peroxidation, leading to mitochondrial damage, and ultimately inducing concurrent ferroptosis and apoptosis on HSFs. Upon further loading into hydrogel microneedles to facilitate their transdermal delivery, these CAD NPs showed superior antiscar therapeutic effects in shortening the treatment span to 3 weeks and improving the HS appearance, as demonstrated at a rabbit ear model of HS. The present supramolecular assembly‐based ferroptosis‐apoptosis strategy provides an innovative guideline for efficiently treating HS as well as other diseases. [ABSTRACT FROM AUTHOR]

The polymorphic behavior of conjugated polymers enables tunable optoelectronic properties, but their transport mechanism remains elusive due to the inherent complexity and uncontrollability of polymorphic self‐assembly behaviors and electronic processes at various length scales, alongside the ambiguous relationship between solution and solid states. Herein, precise control of multi‐level supramolecular self‐assembly of a polymorphic conjugated polymer, N‐PDPP4T‐HD with two distinct semi‐crystalline aggregated phases (β1 and β2) via solvent engineering is demonstrated. β1 forms 1D worm‐like nanostructures in solution, whereas β2 generates 2D nanoscale lamellar configuration, confirmed by experimental observation and molecular dynamic simulation. Such solution‐state features are inherited in the solid state (1D nanofibers for β1 and 2D granular‐like structures for β2). X‐ray characterizations reveal larger crystalline domains on the nanometer scale, reduced π‐stacking distance on the Ångstrom scale, and diminished paracrystallinity disorder for solid‐state β2. Going beyond conventional DC transistor characterizations, contact‐free ultrafast terahertz spectroscopy to unveil AC short‐range, intrinsic transport properties is employed. Longer charge carrier scattering time and thus intrinsic mobility of β2 result in threefold higher short‐range photoconductivity than β1. This work establishes the "solution structure – solid structure – local transport" relation in polymorphic conjugated polymers and provides new opportunities for high‐performance plastic electronic devices. [ABSTRACT FROM AUTHOR]

Developing nanophotosensitizer (nanoPS) for synergistic phototherapy by leveraging the aggregation of small‐molecule dyes is compelling frontier in precision medicine, but challenges remain due to the limited understanding of the interactions between molecular structure, assembly behavior, and theranostic function. Here, the concept of “spin‐orbit charge‐transfer intersystem crossing (SOCT‐ISC) in crystalline aggregates” is introduced, which significantly enhances photodynamic (PD) and photothermal (PT) properties of small‐molecule‐based nanoPS. Specifically, a cationic pyridine (Py) group is incorporated at the meso‐position of a tricyanofuran (TCF)‐containing anionic heptamethine cyanine (TCF‐Cy7‐TCF) dye to construct an orthogonal charge‐transfer dyad (TCF‐Cy7(Py)‐TCF), boosting triplet state formation through SOCT‐ISC mechanism to enhance the PD properties. Remarkably, the zwitterion moieties impart TCF‐Cy7(Py)‐TCF with high crystallinity even at ultralow concentrations, dictating its stacking behavior within aggregates and enhancing both PT and PD properties. The TCF‐Cy7(Py)‐TCF nanoaggregates exhibit superior singlet oxygen quantum yield (0.8% vs 0.2%) and photothermal conversion efficiency (55.06% vs 7.78%) compared to TCF‐Cy7‐TCF. Impressively, TCF‐Cy7(Py)‐TCF preferentially accumulates at tumor sites, yielding high signal‐to‐background ratios for tumor imaging in NIR‐I and NIR‐II windows, with minimal nonspecific binding. Finally, in vivo experiments confirm TCF‐Cy7(Py)‐TCF nanoaggregates function as nanoPS for synergistic phototherapy, offering a simple yet effective strategy to design single‐component PS for clinical translation. [ABSTRACT FROM AUTHOR]

A series of unprecedented supramolecular complexes of covalently modified Anderson‐type polyoxometalates (POMs) and α‐cyclodextrins (α‐CDs) have been obtained and characterized in solid state by single‐crystal X‐ray diffraction, and in aqueous solution using various techniques including 1H DOSY NMR, 2D NOESY 1H NMR, isothermal titration calorimetry (ITC), and electrospray ionization time‐of‐flight mass spectroscopy (ESI‐TOF‐MS). It has been demonstrated that the supramolecular assembly process could be modulated by different covalent modification modes of the Anderson POMs, giving rise to a new type of POM/α‐CD complexes featuring organic‐inorganic pseudo‐rotaxane structures, which are in good contrast to those of POM/γ‐CD complexes of poly‐rotaxane structures. Moreover, it is delighted to find that these pseudo‐rotaxanes of POM/α‐CD complexes exhibit stable chirality in aqueous solution, which has not been accomplished in previously reported POM/CD assemblies. [ABSTRACT FROM AUTHOR]

Herein, we reported a biofuel‐driven recyclable chiral supramolecular transfer container based on hexacationic triphenylamine cage and nucleotides. Possessing rotatable paddle rigid backbones, the artificial receptor effectively encapsulated nucleotides with a high binding constant up to 5.37×105 M−1 in water, displaying guest‐induced efficient fluorescence enhancement with quantum yield increased from 6.5 % to 16.6 %. Especially, the achiral cage could effectively bind with adenosine triphosphate to activate chirality transfer from substrates to the single molecular container, giving circularly polarized luminescence at 575 nm and positive Cotton effect peaks with significant asymmetric factor (gabs=+6.4×10−4). Meanwhile, the adaptive chiral supramolecule not only has reversible thermal responsiveness but also could stepwise regulate chirality transfer by the catalysis of hexokinase and apyrase in tandem, showing recovery adaptive chirality after refueled, achieving dynamically regulated programmable multistate chiral luminescent supramolecules. Therefore, the biofuel‐driven chiral supramolecular transfer container could be successfully applied in chiral logic gates and multilevel information encryption, providing new insight into intelligent chiral materials. [ABSTRACT FROM AUTHOR]

We construct a compartmentalized nanoarchitecture to regulate bioenergy level. Glucose dehydrogenase, urease and nicotinamide adenine dinucleotide are encapsulated inside through liquid‐liquid phase separation. ATPase and glucose transporter embedded in hybrid liposomes are attached at the surface. Glucose is transported and converted to gluconic acid catalyzed by glucose dehydrogenase, resulting in an outward proton gradient to drive ATPase for ATP synthesis. In parallel, urease catalyzes hydrolysis of urea to generate ammonia, which leads to an inward proton gradient to drive ATPase for ATP hydrolysis. These processes lead to a change of the direction of proton gradient, thus achieving artificial ATP oscillation. Importantly, the frequency and the amplitude of the oscillation can be programmed. The work explores nanoarchitectonics integrating multiple components to realize artificial and precise oscillation of bioenergy level. [ABSTRACT FROM AUTHOR]

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Herein, corannulene‐based quintuple [6]helicenes (Q[6]H‐1 and Q[6]H‐2) and [7]helicene (Q[7]H) were synthesized via penta‐fold Heck and Mallory reaction. Notably, Q[7]H represents the highest reported helicene based on corannulene. X‐ray crystallography reveals that Q[6]H‐2 adopts a propeller‐shaped conformation with a well‐preserved corannulene core, while Q[6]H‐1 and Q[7]H exhibit quasi‐propeller‐shaped conformations. Upon heating, conformer Q[6]H‐1 undergoes conversion to the thermodynamically more stable conformer Q[6]H‐2, whereas conformer Q[7]H remains unchanged due to larger steric congestion. Racemization of the enantiomer of Q[6]H‐1 and conformational conversion were observed simultaneously at elevated temperature, with DFT studies indicating a racemization barrier of 32.06 kcal ⋅ mol−1. In contrast, the racemization barrier for Q[6]H‐2 was calculated to be 45.46 kcal ⋅ mol−1, indicating exceptional chiral stability. Surprisingly, the bowl inversions of Q[6]H‐1 and Q[6]H‐2 conformers are somewhat inhibited by the helical blades, whereas this was not observed for other possible conformers of Q[6]H. These results first demonstrated that subtle conformational variations can lead to significant changes in chiral stability and bowl inversions of multiple helicenes. Due to the well‐preserved corannulene core, propeller‐shaped conformation and electron complementarity, Q[6]H‐2 can recognize fullerenes in both solution and solid state, which is a rare instance of co‐crystallization assembly between multiple helicenes and fullerenes. [ABSTRACT FROM AUTHOR]

This study identifies and characterizes a second polymorph (Poly‐II) of quinoline‐4‐carbaldoxime (HQ), isolated from an acetone‐acetonitrile mixture. Poly‐II was compared to the previously known Poly‐I using PXRD, DSC, IR, and Raman spectroscopy. Poly‐I forms a 1D supramolecular assembly, whereas Poly‐II exhibits a 2D assembly with additional hydrogen bonds. Hirshfeld surface analysis reveals the presence of different non‐covalent interactions in Poly‐I and Poly‐II, and atom‐in‐molecule (AIM) analysis identifies their strength. AIM analysis, along with Espinosa's relation, was used to calculate the strength of O─H···N and C─H···N interactions in Poly‐I and Poly‐II. The values are −30.0 and −6.17 kJ/mol for Poly‐I, whereas the values for Poly‐II are −36.18 and −3.66 kJ/mol. The plane wave periodic DFT calculations determined the lattice energies of Poly‐I and Poly‐II to be −1.52 and −1.53 eV, respectively, indicating that both polymorphs have comparable stability. The crystal parameters of Poly‐I and Poly‐II obtained from theoretical simulations and the experiment are comparable, indicating the similar stability of Poly‐I and Poly‐II. Computational simulations confirmed experimental data, showing both polymorphs have similar stability and melting points despite different unit cell volumes. [ABSTRACT FROM AUTHOR]

Amino acids (AAs), serving as the primary monomer of peptides and proteins, are widely present in nature. Benefiting from their inherent advantages, such as chemical diversity, low cost, ease of modification, chirality, biosafety, and bio-absorbability, AAs have been extensively exploited to create self-assembled nanostructures and supramolecular soft materials. In this review article, we systematically describe the recent progress regarding amino acid-derived assembly and functional soft materials. A brief background and several classified assemblies of AAs and their derivatives (chemically modified AAs) are summarized. The key non-covalent interactions to drive the assembly of AAs are emphasized based on the reported systems of self-assembled and co-assembled AAs. We discuss the molecular design of AAs and the general rules behind the hierarchical nanostructures. The resulting soft materials with interesting properties and potential applications are demonstrated. The conclusion and remarks on AA-based supramolecular assemblies are also presented from the viewpoint of chemistry, materials, and bio-applications. [ABSTRACT FROM AUTHOR]

Pesticide residues pose significant risks to human health and the environment, emphasizing the need for sensitive detection and analysis methods. Fluorescence-based sensors, particularly those utilizing aggregation-induced emission (AIE) fluorophores (AIEgens), have demonstrated exceptional performance in this area. This review summarizes key advancements in pesticide detection sensors based on AIEgens, detailing their luminescence mechanisms and fluorescence sensing principles. It explores various applications of AIEgens in fluorescence sensors, including organic small-molecule sensors, nanocomposite sensors, metal-organic framework sensors, supramolecular sensors, fluorescent porous organic polymer sensors, and lateral flow immunoassay sensors, with specific examples illustrating their detection mechanisms and performance. This review also discusses current challenges and future perspectives for the development of these sensors. We anticipate that this review will serve as a valuable and timely resource for researchers working to advance the development and application of AIEgens-based sensors in pesticide detection. [ABSTRACT FROM AUTHOR]

Photosynthesis is a complex multi‐step process in which light collection is the initial step of photosynthesis and plays an important role in the utilization of solar energy. In order to improve the utilization of sunlight, researchers have developed a variety of artificial light‐harvesting systems to simulate photosynthesis in nature. Here, we report a supramolecular artificial light‐harvesting system in aqueous solution. Since β‐cyclodextrin (β‐CD) has a hydrophobic cavity and a hydrophilic outer surface, we adopt β‐cyclodextrin (β‐CD) as the host molecule and use adamantane as the guest molecule. At the same time, we modified β‐CD with the donor molecule naphthalimide and adamantane with the tetraphenylethylene molecule which has aggregation‐induced emission (AIE) effects. By using fluorescent molecules with AIE, the self‐quenching effect caused by aggregation in aqueous solution can be effectively avoided. Due to the host‐guest interaction of β‐CD and adamantane, nanoparticles with stable structure and uniform size can be spontaneously assembled in water. Because of the close distance and strong spectral overlap between naphthalimide and tetraphenylethylene, Förster resonance energy transfer (FRET) was realized, and artificial light‐harvesting system was successfully constructed in aqueous solution. Therefore, this study provides a new strategy for constructing artificial light‐harvesting system, and the artificial light‐harvesting system shows broad application prospects in aqueous solutions. [ABSTRACT FROM AUTHOR]

Supramolecular assembly allows multiple chemical/bio‐components integrated as one system for cascade biochemical reactions. Herein the graphitic carbon nitrides (g‐C3N4) as photocatalyst trapped in a dipeptide hydrogel covering adenosine triphosphate (ATP) synthase accelerates the photophosphorylation through ATP synthesis. Self‐assembled N‐fluorenylmethoxycarbonyl diphenylalanine (Fmoc‐FF) as nanofibrils to allow g‐C3N4 nanosheets are embedded as a complex Fmoc‐FF/g‐C3N4 hydrogel. Fmoc‐FF gel exhibits good electronic coupling with g‐C3N4, which enables a photo‐induced proton generation. The transmembrane proton gradient can be established by ATP synthase‐lipid reconstituted on the surface of the Fmoc‐FF/g‐C3N4 hydrogel to enhance the ATP synthesis. It indicates that the Fmoc‐FF/g‐C3N4/ATP synthase‐lipid film can possess a longer‐term ATP production capability and allow repeated immersion for sustained ATP production. Such a hydrogel‐supported ATP synthesis platform is achieved by a procedure at a larger scale. [ABSTRACT FROM AUTHOR]

The management of dysfunctional intestinal epithelium by promoting mucosal healing and modulating the gut microbiota represents a novel therapeutic strategy for inflammatory bowel disease (IBD). As a convenient and well‐tolerated method of drug delivery, intrarectal administration may represent a viable alternative to oral administration for the treatment of IBD. Here, a biomimetic supramolecular assembly of hyaluronic acid (HA) and β‐cyclodextrin (HA‐β‐CD) for the delivery of the C domain peptide of insulin‐like growth factor‐1 (IGF‐1C), which gradually releases IGF‐1C, is developed. It is identified that the supramolecular assembly of HA‐β‐CD enhances the stability and prolongs the release of IGF‐1C. Furthermore, this biomimetic supramolecular assembly potently inhibits the inflammatory response, thereby restoring intestinal barrier integrity. Following HA‐β‐CD‐IGF‐1C administration, 16S rDNA sequencing reveals a significant increase in the abundance of the probiotic Akkermansia, suggesting enhanced intestinal microbiome homeostasis. In conclusion, the findings demonstrate the promise of the HA‐based mimicking peptide delivery platform as a therapeutic approach for IBD. This biomimetic supramolecular assembly effectively ameliorates intestinal barrier function and intestinal microbiome homeostasis, suggesting its potential for treating IBD. [ABSTRACT FROM AUTHOR]

The recognition of the importance of nanostructures is mainly due to the development of nanotechnology. For further developments in materials sciences, a concept that integrates nanotechnology with material chemistry to fabricate functional materials has to be proposed. Nanoarchitectonics will carry out this task. In nanoarchitectonics, we architect functional material systems from nano-units (atoms, molecules, nanomaterials). The methodology is not specific to any particular material or application. It covers a wide range. Therefore, nanoarchitectonics can be thought of as the method for everything in materials science. As typical demonstrations for usages of nanoarchitectonics, this review paper presents our work on nanoarchitectonics for supercapacitors. We divide it into two categories with different approaches. The first is the development of carbon materials as supercapacitor electrode materials from biomass. The second category is preparing carbon materials using structures created by supramolecular assembly of fullerenes such as C60 and C70. By presenting examples using opposite starting materials, a complex natural material, and an ultimately simple molecule, we will demonstrate the versatility and breadth of possibilities of this approach. [ABSTRACT FROM AUTHOR]

The iron‐armored chain horse is a military strategy in ancient China to enhance the combat force of the entire army, especially when individual fighters are vulnerable to being picked off one by one. Herein, this strategy is adopted to generate highly efficient metal‐free blue room temperature phosphorescence (RTP) using the world's largest production of dicarboxylate acid. By encapsulating the commercially available chemical disodium terephthalate (DTPA) within the iron armor of α‐cyclodextrin (α‐CD), and subsequently linking the iron‐armored DTPA@α‐CD horses into a crystalline array mediated by hydrogen bonds and Na+ coordination, a highly confined and segregated arrangement of DTPA is achieved, leading to heavy atom‐free deep‐blue phosphorescence with a maximum efficiency of 83.3%. Since the crystalline array of the iron‐armored chain horse DTPA@α‐CD can be facilely obtained through water evaporation, the current phosphorescent material allows for rapid, high‐throughput solution processing of deep‐blue afterglow display, offering an economic and environmentally benign approach for deep‐blue RTP materials and facilitating their application. [ABSTRACT FROM AUTHOR]

Molecular motor amphiphiles have already been widely attempted for dynamic nanosystems across multiple length‐scale for developments of small functional materials, including controlling macroscopic foam properties, amplifying motion as artificial molecular muscles, and serving as extracellular matrix mimicking cell scaffolds. However, limiting examples of bola‐type molecular motor amphiphiles are considered for constructing macroscopic biomaterials. Herein, this work presents the designed two second generation molecular motor amphiphiles, motor bola‐amphiphiles (MBAs). Aside from the photoinduced motor rotation of MBAs achieved in both organic and aqueous media, the rate of recovering thermal helix inversion step can be controlled by the rotor part with different steric hindrances. Dynamic assembled structures of MBAs are observed under (cryo)‐transmission electron microscopy (TEM). This dynamicity assists MBAs in further assembling as macroscopic soft scaffolds by applying a shear‐flow method. Upon photoirradiation, the phototropic bending function of MBA scaffolds is observed, demonstrating the amplification of molecular motion into macroscopic phototropic bending functions at the macroscopic length‐scale. Since MBAs are confirmed with low cytotoxicity, human bone marrow‐derived mesenchymal stem cells (hBM‐MSCs) can grow on the surface of MBA scaffolds. These results clearly demonstrate the concept of designing MBAs for developing photoresponsive dynamic functional materials to create new‐generation soft robotic systems and cell‐material interfaces. [ABSTRACT FROM AUTHOR]

Many stimuli‐responsive materials harness the reversible association of supramolecular binding motifs to enable advanced functionalities such as self‐healing, switchable adhesion, or mechanical adaptation. Despite extensive research into the structure–property relationships of these materials, direct correlations between molecular‐level changes in supramolecular binding and macroscopic material behaviors have mostly remained elusive. Here, we show that this challenge can be overcome with supramolecular binding motifs featuring integrated binding indicators. We demonstrate this using a novel motif that combines a hydrogen‐bonding ureido‐4‐pyrimidinone (UPy) with two strategically placed pyrene fluorophores. Dimerization of this motif promotes pyrene excimer formation, facilitating the straightforward optical quantification of supramolecular assembly under various conditions. We exploit the new motif as a supramolecular cross‐linker in poly(methyl acrylate)s to probe the extent of (dis)assembly as a function of cross‐linker content, processing history, and applied stimuli. We demonstrate that the stimuli‐induced dissociation of hydrogen‐bonding linkages strongly depends on the initial cross‐link density, which also dictates whether the force‐induced dissociation in polymer films correlates with the applied stress or strain. Thus, beyond introducing a robust tool for the in situ study of dynamic (dis)assembly mechanisms in supramolecular systems, our findings provide new insights into the mechanoresponsive behavior of such materials. [ABSTRACT FROM AUTHOR]

Indocyanine green (ICG), the only near-infrared (NIR) dye approved for clinical use, has received increasing attention as a theranostic agent wherein diagnosis (fluorescence) is combined with therapy (phototherapy), but suffers rapid hepatic clearance, poor photostability, and limited accumulation at tumor sites. Here we report that dimerized ICG can self-assemble to form zwitterionic nanoparticles (ZN-dICG), which generate fluorescence self-quenching but exhibit superior photothermal and photodynamic properties over ICG. The zwitterionic moieties confer ZN-dICG an ultralow critical micelle concentration and high colloidal stability with low non-specific binding in vivo. In addition, ZN-dICG can respond to the over-generated reactive oxygen species (ROSs) and dissociate to restore NIR fluorescence of ICG, amplifying the sensitivity via albumin binding for low-background imaging of tumors. Following systemic administration, ZN-dICG accumulated in tumors of xenograft-bearing mice for imaging primary and metastatic tumors, and induced tumor ablation under laser irradiation. The discovery of ZN-dICG would contribute to the design of translational phototheranostic platform with high biocompatibility. Indocyanine green (ICG) has been extensively studied as a phototheranostic agent that combines imaging with phototherapies, but it suffers from rapid hepatic clearance, poor photostability, and limited accumulation at tumor sites. Here, we report a strategy to construct ICG dimers (ICG-tk-ICG) by conjugating two ICG molecules via a thioketal bond, which can self-assemble into zwitterionic nanoparticles (ZN-dICG) at ultralow critical micelle concentrations, exhibiting superior photothermal and photodynamic properties over ICG. ZN-dICG responds to the over-generated ROS in tumors and dissociates to restore the NIR fluorescence of ICG, enhancing the sensitivity via albumin binding for low-background imaging of tumors. This study offers a supramolecular strategy that may potentiate the clinical translation of ICG in imaging-guided cancer phototherapy. [Display omitted] [ABSTRACT FROM AUTHOR]

The photochemical and photophysical properties of near-infrared (NIR) dyes are significantly influenced by their aggregation state and mesoscopic morphology. However, beyond chemical synthesis, the regulation mechanisms for the properties of NIR dyes, particularly with respect to photothermal properties of the aggregates, are not yet fully understood. Here, we investigate the photothermal behaviors of croconaine-based (CroA) NIR dyes containing dipeptide or amino acids moieties. The introduction of hydrogen bonding promotes π–π stacking of croconaine center, which can efficiently regulate aggregation states and assembly structures in isopropanol. Under laser irradiation, CroA aggregates undergo aggregation-dissociation transition, the in-situ monomer generation process regulates two parameters of photothermal performance: heating rates and plateau photothermal temperatures. This study reveals the regulation effect of non-covalent bonding interactions on CroA aggregates, highlighting supramolecular assembly strategy not only facilitates to construct of photothermal nanomaterials with well-defined structures, but also provides an alternative and effective method for regulating photothermal performance of NIR dyes. [ABSTRACT FROM AUTHOR]

Stabilizing liquids based on supramolecular assembly (non-covalent intermolecular interactions) has attracted significant interest, due to the increasing demand for soft, liquid-based devices where the shape of the liquid is far from the equilibrium spherical shape. The components comprising these interfacial assemblies must have sufficient binding energies to the interface to prevent their ejection from the interface when the assemblies are compressed. Here, we highlight recent advances in structuring liquids based on non-covalent intermolecular interactions. We describe some of the progress made that reveals structure-property relationships. In addition to treating advances, we discuss some of the limitations and provide a perspective on future directions to inspire further studies on structured liquids based on supramolecular assembly.

Abstract Owing to their attractive antitumor effects, aminated fullerene derivatives are emerging as promising therapeutic drugs for cancer. However, their in vivo applications are severely limited due to cation toxicity. To address this problem, human heavy chain ferritin (HFn), possessing natural biocompatibility is utilized, to develop a novel supramolecular assembly drug delivery system. Specifically, tetra[4‐(amino)piperidin‐1‐yl]‐C60 (TAPC) is selected as the representative aminated fullerene, and a layer‐by‐layer assembly strategy is designed to controllably assemble TAPC with the negatively charged HFn into a hierarchical coassembly (H@T@H) via electrostatic interactions and hydrogen bonds. In this ordered multilayer structure, the surface displayed HFn endows the inner TAPC with biocompatibility, tumor‐targeting and blood‐brain barrier crossing ability. Additionally, the electrostatic assembly mode enables the acid‐responsive disassembly of H@T@H to release TAPC in lysosomes. In the orthotopic glioma mouse model, the HFn‐assembled TAPC (H@T@H) shows higher brain accumulation and a stronger inhibitory effect on glioma than polyethylene glycol (PEG)‐coated TAPC. Moreover, in an experimental metastasis mouse model, H@T@H have significant preventive and therapeutic effects on tumor metastasis. Encouragingly, the ferritin‐based supramolecular assembly strategy has been proven to have broad applicability for various aminated fullerene derivatives, showing promising potential for tackling the in vivo delivery challenges of cationic drugs.