Search Results (927)

Cardiolipin (CL), a dimeric phospholipid with four acyl chains and a small polar head group, is one of the most striking examples of evolutionary continuity in cell biology. Present in the plasma membrane of α-proteobacteria and retained without fundamental modification in the inner mitochondrial membrane (IMM) of every eukaryote examined, CL has persisted across roughly two billion years of evolution, a period over which the mitochondrion shed the great majority of its ancestral genes. This review develops, as an organizing hypothesis rather than an established fact, the proposal that CL acts as a programmable signaling hub: a lipid whose physical chemistry and membrane address allow it to nucleate distinct supramolecular platforms in response to discrete stress signals, each platform coupling a specific mitochondrial state to a defined cell fate outcome. Three CL-dependent platforms are examined, together with a fourth, emerging axis, and the evidence supporting each is explicitly graded. Platform 1, the catalytic peroxidase platform, converts the constitutive CL–cytochrome c (cyt c) structural complex into an enzymatic reaction under oxidative stress, generating oxidized CL (oxCL) species that contribute to cyt c release from the IMM; this platform is the best supported of the four. Platform 2, the receptor-like mitophagy platform, exploits NME4-dependent CL scramblase activity to translocate CL from the IMM to the outer mitochondrial membrane (OMM) surface upon membrane potential dissipation, creating an externalized “eat-me” signal recognized by LC3-II; the evidence here is moderate and largely cell-based. Platform 3, the caspase-8/BID activation platform, is proposed to assemble a CL microdomain scaffold at the OMM that recruits caspase-8, markedly accelerates BID cleavage, and couple extrinsic apoptotic signals to mitochondrial outer membrane permeabilization (MOMP); this model rests substantially on reconstituted systems and requires further validation in intact cells and in vivo. A fourth, still-debated axis links CL externalization to innate immune activation through NLRP3 recruitment, for which alternative membrane-recruitment models exist. The argument advanced here is that the conservation of CL is unlikely to be explained by its structural roles alone, although those roles are themselves sufficient to impose strong selection; disentangling structural from signaling contributions remains an open problem, and the comparative genomic work needed to do so has not yet been performed. Full article

Cyclodextrin (CD)-based supramolecular nanofibers (NFs) have emerged as an advanced class of multifunctional materials for active food packaging by integrating host–guest supramolecular chemistry with electrospun nanofibrous architectures. The unique hydrophobic cavity and hydrophilic exterior of CDs enable the encapsulation of a wide range of bioactive compounds, including essential oils, natural antioxidants, antimicrobials, and volatile active agents, thereby enhancing their solubility, stability, controlled release, and preservation efficacy. This review comprehensively discusses the molecular structure and inclusion complexation mechanisms of CDs, recent advances in polymer-assisted and polymer-free electrospinning strategies, and the design of CD-based supramolecular nanofibers for food preservation. Particular emphasis is placed on the relationship between fiber morphology, supramolecular interactions, and controlled release behavior, which collectively govern antimicrobial, antioxidant, moisture management, and barrier properties. Recent developments involving biodegradable polymers, hybrid nanofibrous systems, and cyclodextrin-based metal–organic frameworks (CD-MOFs) are critically summarized, highlighting their roles in improving encapsulation efficiency, mechanical stability, and multifunctional performance. The review further compares CD-based nanofibers with other advanced encapsulation technologies, including liposomes, solid lipid nanoparticles, nanostructured lipid carriers, nanoemulsions, polymeric nanoparticles, microspheres, and conventional MOFs, providing a comprehensive evaluation of their loading capacity, release kinetics, scalability, cost, and regulatory suitability for food-contact applications. Representative applications in the preservation of fruits, vegetables, meat, seafood, dairy products, and bakery products demonstrate significant improvements in microbial inhibition, oxidation resistance, ethylene and volatile organic compound adsorption, and shelf-life extension through sustained delivery of natural preservatives. Ultimately, the current challenges, including large-scale manufacturing, long-term stability, regulatory approval, and commercialization, are discussed together with future directions, focusing on smart packaging, stimuli-responsive delivery systems, intelligent sensing, biodegradable multifunctional materials, and sustainable industrial implementation. Full article

Over the past two decades, triphenylamine (TPA)-based supramolecular coordination metallacycles, constructed by incorporating TPA and its derivatives as key building blocks into two-dimensional (2D) coordination-driven assemblies, have gradually received considerable attention and emerged as an important research topic within the field of discrete supramolecular coordination complexes (SCCs). Leveraging the synthetic accessibility and outstanding optoelectronic properties of TPA units, the resulting TPA-based metallacycles exhibit well-defined topological structures, excellent emission characteristics, and unique functions. In this review, we systematically and comprehensively discuss the design strategies, synthetic methodologies, and practical applications for TPA-based supramolecular metallacycles, with an emphasis on five key aspects: (i) coordination-driven self-assembly, (ii) hierarchical self-assembly, (iii) supramolecular polymers, (iv) tunable fluorescence, and (v) diverse applications. Finally, future perspectives and challenges in this rapidly evolving field are presented. Full article

Developing lead-free organic-inorganic hybrid metal halides with strong light-harvesting capabilities and superior stability, while precisely tuning their crystalline phases and electronic structures, remains a key challenge in optoelectronics. Herein, we report a neutral iodine-induced structural transition from a 1D chain-like (C₆H₁₁NH₃)₂SbI₅ architecture to a 0D dimeric (C₆H₁₁NH₃)₃[Sb₂I₉]·I₂ supramolecular host-guest complex. This transformation is achieved via a controlled solution-cooling crystallization process, yielding high-quality bulk single crystals. Crystallographic analysis reveals that N–H···I hydrogen-bonding networks stabilize the organic cations, while halogen bonding interactions anchor the I₂ guests within the lattice cavities of the [Sb₂I₉]³⁻ dimeric host. Experimental characterizations, including XRD, TGA, and XPS, confirm the high phase purity and thermal stability of the (C₆H₁₁NH₃)₃[Sb₂I₉]·I₂ hybrid and determine its electronic band structure. To further elucidate the underlying mechanisms, theoretical calculations were performed, revealing that strong sp-orbital hybridization yields a high absorption coefficient. The associated dimensional transition narrows the direct optical bandgap to 1.46 eV, approaching the Shockley-Queisser limit and demonstrating strong potential for visible-light harvesting. This work elucidates the role of supramolecular host-guest interactions in modulating the lattice evolution of lead-free antimony-based materials, presenting halogen guest engineering as an effective approach for optoelectronic material design. Full article

Background: Depression is a severe disorder associated with hypothalamic–pituitary–adrenal (HPA) axis dysregulation and neuroinflammation, and which restrains the efficacy of conventional antidepressants. Vortioxetine is a multimodal antidepressant with potential immunomodulatory properties. Glycyrrhizic acid (GA) is a natural compound derived from licorice root that exhibits anti-inflammatory activity and modulates glucocorticoid signaling. We hypothesized that a supramolecular complex of vortioxetine with GA (Vort:Na₂GA) would exert synergistic effects on inflammatory and glucocorticoid pathways. Methods: Vortioxetine compositions with Na₂GA were prepared using a mechanochemical method. Cytotoxicity, anti-inflammatory property, and glucocorticoid receptor (GR) signaling pathway modulation of the complex were evaluated in vitro using SIM-A9 microglial cells. Additionally, a 7-day oral administration study in intact female C57BL/6 mice was conducted to evaluate the effects on peripheral blood cells. Results: The Vort:Na₂GA complex improves the solubility of the parent drug while increasing its stability and permeability. Furthermore, the resulting complex exhibits reduced cytotoxicity, particularly under glucocorticoid challenge. In SIM-A9 microglial cells, the Vort:Na₂GA complex upregulated expression of Nr3c1 and Nr1d1 genes without activating canonical GR target genes (Fkbp5 and Gilz) and partially reversed dexamethasone-induced glucocorticoid resistance. In vivo, the complex reduced the percentage of inflammatory Ly6C^high monocytes and preserved dexamethasone-induced Gilz expression in peripheral blood cells, indicating protection against stress-induced glucocorticoid resistance. Conclusions: The Vort:Na₂GA supramolecular complex enhances the physicochemical and pharmacological profile of vortioxetine, reduces inflammation-associated myeloid cell populations, and preserves glucocorticoid sensitivity. These findings support its further evaluation as a potential therapeutic agent for depressive disorders with inflammatory and HPA axis-related components. Full article

Cucurbiturils (CB[n]) are rigid glycoluril-based macrocycles possessing well-defined hydrophobic cavities capable of forming stable host–guest complexes in water. Owing to these properties, CB[n]-containing supramolecular polymer gels have attracted increasing attention as functional composite materials in modern materials science. This review summarizes recent progress in the development of cucurbituril-based supramolecular gels, with particular attention to synthetic approaches, network design, and emerging applications. Both conventional acid-catalyzed methods and more sustainable synthetic strategies for cucurbituril preparation and functionalization are discussed. We further consider the role of CB[n] macrocycles as reversible crosslinking units in polymer networks and analyze how host–guest interactions influence the mechanical properties, self-healing behavior, and stimuli responsiveness of the resulting materials. Recent applications in biomedical engineering, soft electronics, and environmental remediation are also highlighted, demonstrating how molecular-level supramolecular interactions can determine the macroscopic performance of these composite systems. The review concludes with perspectives on scalable synthesis, processing integration, and future directions in supramolecular composite materials. Full article

In this study, a novel and sensitive fluorescent sensing platform was rationally developed for the rapid and specific detection of dopamine. The proposed strategy ingeniously integrates the superior adsorption behavior and extraordinary fluorescence quenching effect of oxidized single-walled carbon nanohorns toward FAM-modified aptamers, as well as the highly efficient cleavage property of the cryonase enzyme. Specifically, the fluorescently labeled aptamer is efficiently adsorbed and shielded by oxidized single-walled carbon nanohorns through strong supramolecular interactions, thereby triggering an evident fluorescence quenching response. Upon the introduction of target dopamine, the specific recognition event between dopamine and its corresponding aptamer takes place, accompanied by the formation of stable aptamer–dopamine complexes. Subsequently, these complexes are selectively hydrolyzed under the catalytic action of the cryonase enzyme, which contributes to the distinct release of fluorophores and the obvious recovery of fluorescence signals. Under the optimized experimental conditions, the aptamer exhibits good linearity toward dopamine in the concentration range of 50–400 ng/mL, with a correlation coefficient of 0.9957 and a low detection limit of 26.12 ng/mL. Therefore, the established analytical method offers a rapid, convenient, and reliable tool for the accurate determination of dopamine in complex human serum samples. Full article

Melanin pigments protect human tissues from ultraviolet and visible radiation, yet their phototoxic potential increases with oxidative degradation. This computational study investigates how the oxidation state influences the first excited states of eu- and pheomelanin using molecular models of varying complexity (monomers to tetramers, both covalently and non-covalently bonded). First, vertical and adiabatic electronic transitions were computed, and supramolecular interactions were characterized with the ETS-NOCV method. In eumelanin, oxidation drastically lowers the first triplet-state (T₁) energies (from above 230 kJ/mol) to levels comparable to retinal carotenoids (≤66 kJ/mol), emphasizing its role in triplet quenching rather than singlet oxygen generation. Pheomelanin showed greater heterogeneity in the values of the first triplet state, staying mostly above the eumelanin T₁ energies. However, selected pheomelanin structures also exhibited relatively low triplet energies, particularly oxidized benzothiazole (BZox) and trichochromes, and although their T₁ energetics remained higher than those calculated for oxidized eumelanin, they were still sufficiently low to suggest a potential ability to quench singlet oxygen. Furthermore, supramolecular analysis reveals that eumelanin aggregates are moderately stabilized by both π-π stacking and hydrogen bonding, whereas pheomelanin aggregates are dominated by dense hydrogen-bond networks. Full article

This study investigated the effect of brief mechanical homogenization using a household blender on the properties of nopal mucilage and its performance in removing potentially toxic elements (PTEs), specifically Pb, Ni, As, Cd, and Zn, from a real cyanidation barren solution. An aqueous extract from Opuntia ficus-indica cladodes was homogenized for 0, 30, or 60 s before spray drying, yielding powders designated as CA, CB, and CC. The powders and water-reconstituted dispersions were characterized and evaluated in coagulation–flocculation assays. Homogenization reduced water activity and average hydrodynamic diameter and significantly modified the ζ potential, although the effects were not proportional to processing time. At 10% w·v⁻¹, the reconstituted mucilages showed frequency-dependent viscoelastic behavior consistent with a transient gel-like organization. All treatments removed more than 98% of Pb, Ni, and As at doses of 200–800 mg·L⁻¹. Cd removal was more variable and significantly affected by mucilage type, whereas Zn showed lower, non-monotonic removal. ESEM–EDS detected PTE-bearing inorganic domains within the recovered flocs, corroborating transfer from the liquid to the solid phase. Overall, mechanical homogenization modified the colloidal, supramolecular, and gel-related properties of spray-dried nopal mucilage, which showed potential as a multifunctional hydrocolloid for treating chemically complex cyanidation process streams. Full article

Skin aging is a central focus of skin health. Supramolecular chemistry has emerged as a powerful strategy for enhancing the performance of cosmetic active ingredients. Adenosine is a promising anti-aging ingredient in skincare products, but its cosmetic application is limited by poor water solubility and low skin penetration. This study developed a supramolecular complex combining adenosine with ectoine through cocrystallization. The supramolecular assembly was characterized by differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA). Powder X-ray diffraction (PXRD), Fourier-transform infrared spectroscopy (FTIR) and density functional theory (DFT) calculations revealed extensive hydrogen-bonding networks between the components. The optimal supramolecular composition (1:1.5 molar ratio) achieved a 5.5-fold increase in water solubility. The supramolecular organization enhanced skin permeability by 3.1-fold in ex vivo porcine skin models. In fibroblast cell models, the supramolecular system exhibited superior antioxidant activity with 30.3% greater reactive oxygen species (ROS) reduction and restored cellular adenosine triphosphate (ATP) levels by 2.1-fold under H₂O₂-induced oxidative stress compared to individual components. These findings demonstrate that the adenosine–ectoine supramolecular complex represents an innovative multifunctional ingredient for basic anti-aging cosmetics, offering enhanced delivery, improved safety, and superior biological efficacy through supramolecular engineering. Full article

The adsorption of aromatic hydrocarbons from liquid paraffin is essential because of their harmful nature, long-lasting presence, and detrimental effects on the quality of the product. In this study, we investigated the adsorption of naphthalene from liquid paraffin by using a nanoclay-based adsorbent prepared from boron enrichment process waste. The characterization of the prepared adsorbent was carried out by using X-ray Diffraction (XRD), Scanning Electron Microscopy (SEM), X-ray Photoelectron Spectroscopy (XPS) and N₂ adsorption–desorption techniques, which confirmed the development of a layered nanostructure containing boron that possesses a porous and high-surface-area format appropriate for the adsorption. The hydrothermal treatment significantly increased the BET surface area from 35.42 to 112.15 m²/g, indicating the successful formation of a porous nanostructure. The kinetic and isotherm parameters of the adsorption process were calculated from experimental data. The adsorption of naphthalene followed pseudo-second-order kinetics and the isotherm fit well to the Langmuir model. Adsorption experiments revealed that the optimum adsorption performance was achieved at pH 4.0, and equilibrium was reached within 90 min. The adsorption kinetics were best described by the pseudo-second-order model (R² > 0.99), while the equilibrium data showed excellent agreement with the Langmuir isotherm model (R² = 0.995), suggesting monolayer adsorption. The maximum adsorption capacity of BNC was determined as 365.20 mg/g, which was more than twice that of the raw BEW (247.59 mg/g). Thermodynamic analysis indicated that the adsorption process was spontaneous at lower temperatures and exothermic, with a ΔH° value of −15.42 kJ/mol for BNC. The results suggest that the adsorption occurs through a multi-step process, beginning with external film diffusion, followed by pore diffusion and surface interaction. Based on the kinetic, isotherm, and spectroscopic data, a supramolecular adsorption mechanism is suggested, which encompasses π-π interactions, van der Waals forces, and surface complexation between naphthalene and the nanoclay structure. These results indicate that boron enrichment process waste-derived nanoclay is a sustainable, economical, and efficient adsorbent for removing naphthalene from liquid paraffin. Full article

Programmable peptide hydrogels represent advanced supramolecular biomaterials featured with customizable molecular sequences and tunable self-assembly behaviors, which can biomimetically reconstruct the structural and microenvironmental complexity of native extracellular matrix. This review systematically elaborates the molecular engineering advances of programmable peptide hydrogels following a hierarchical logic from fundamental mechanisms to translational applications. We first interpret the intrinsic self-assembly mechanisms driven by non-covalent interactions and the regulatory effects of typical external microenvironmental stimuli. On this basis, we summarize core rational design principles, covering stimuli-responsive structural optimization, biofunctional modification, and the tunable regulation of physical properties, degradability and immunogenicity. Furthermore, we correlate multi-scale structural features (nanostructures, porous architecture and mechanical properties) with their versatile biomedical functions, and comprehensively discuss their cutting-edge applications in tissue regeneration, targeted drug and gene delivery, cell-mediated therapy, immunomodulation, and anti-infective treatment. Finally, we identify critical translational barriers including batch-to-batch inconsistency, immunogenic risks, and in vivo performance instability, and highlight future directions involving multi-stimuli-responsive systems, artificial intelligence-assisted design, computational modeling, and hybrid material construction. This work systematically clarifies the structure–property–function relationship of peptide hydrogels, and underscores their great potential as next-generation platforms for precision regenerative medicine and targeted disease intervention. Full article

Whey protein isolate (WPI) can assemble into supramolecular complexes with flavonoids via non-covalent interactions, although the underlying binding mechanisms remain not fully understood. In this work, the formation mechanism of the WPI–phloridzin (PHL) complex was systematically investigated using an integrated experimental and computational approach. High-performance liquid chromatography quantified the binding content of PHL as 1.3% (w/w). Isothermal titration calorimetry indicated that the process was entropy-driven and governed predominantly by hydrophobic and electrostatic interactions. Complementary circular dichroism spectroscopy and molecular dynamics simulations revealed that complexation induces modest conformational adjustments in the protein’s secondary structure. Collectively, this multi-scale analysis provides mechanistic insights into the dynamic formation of the WPI–PHL complex, offering theoretical insights into protein–flavonoid recognition. Full article

Aliphatic diamines possess two amino functional groups and exhibit diverse chemical properties and tunable molecular structures. By selecting the guest [(C₂H_2n+4N₂), n = 2–6] and host 18-crown-6, and controlling the design and assembly processes via modulation by thiocyanate and a manganese salt, a series of dumbbell-shaped crown ether complexes, (C₂H_2n+6N₂)²⁺(18-crown-6)₂[Mn(NCS)₄]²⁻·(δ_n,₂C₂H₃N), n = 2–6, (1)–(5), was synthesized and analyzed by single-crystal X-ray diffraction (SCXRD) at 100 K and 293 K. Variable-temperature infrared and XRD analyses confirmed that compounds 3 and 5 underwent a phase transition. As the length of the carbon chain increases and alternates between odd and even, the interplanar dihedral angle of the crown ether exhibits a distinct pattern: Even-number chains arrange in parallel, whereas odd-number chains form a pronounced angle. This structural pattern influences macroscopic deformation of the crystal and induces corresponding periodic variations in the dielectric and electrochemical properties. The wide-bandgap insulators and magnetic properties are primarily governed by the inorganic components of the system and are less influenced by the organic portion. This study reveals principles for regulating supramolecular conformation and functional properties through the parity of the organic chain lengths, providing a strategy for the molecular-level design of supramolecular crystal materials with ordered structures and tunable properties. Full article

Background: Retinol is a mainstay of dermatological care due to its central role in epidermal differentiation, skin barrier repair, and tissue regeneration. However, its clinical use is limited by poor physicochemical stability, rapid photodegradation, and frequent skin intolerance, particularly in individuals with impaired skin barrier function. Supramolecular biovectorization strategies could overcome these limitations. Objectives: This study aimed to evaluate the impact of third-generation dendritic poly-L-lysine (PLL_G3; 22 kDa, ~7 nm) on retinol stability, skin tolerance, and skin functional performance. Methods: A supramolecular retinol-poly-L-lysine complex was characterized in terms of encapsulation efficiency and physicochemical stability using HPLC and UV spectroscopy under oxidative, thermal, and photochemical stress. The stability of the formulation was evaluated as hydrophilic emulsion over a three-month period. Skin functional efficacy was evaluated by corneometric analysis of stratum corneum hydration after topical application, as well as by clinical assessment of tolerance and efficacy after repeated daily use over 28 days in subjects presenting xerosis, defined as dry to very dry skin. Results: Retinol remained structurally intact in the PLL_G3 matrix, confirming a reversible, non-covalent encapsulation mechanism. The formulation exhibited high physicochemical stability, with only minimal changes after prolonged UV exposure. Corneometric measurements showed a rapid and sustained increase in skin hydration, reaching +61.5% two hours after application. After 28 days of repeated use, the formulation was well tolerated, with no signs of irritation or sensitization, and demonstrated significant improvements in skin dryness, suppleness, and comfort. Conclusions: PLL_G3-based supramolecular vectorization significantly improves stability, tolerance, and functional hydration of the skin by retinol. By enabling controlled release while preserving the integrity of the epidermal barrier, poly-L-lysine dendrimers represent a clinically relevant strategy for safer and more effective topical use of retinol, particularly on sensitive, xerotic, inflammatory, and photoaged skin. Full article