Three-dimensional supramolecular organic frameworks with precisely tunable pore sizes are highly demanded for a wide range of applications,e.g.,encapsulating enzymes to enhance their stability,activity,and reusability...Three-dimensional supramolecular organic frameworks with precisely tunable pore sizes are highly demanded for a wide range of applications,e.g.,encapsulating enzymes to enhance their stability,activity,and reusability.However,precise control and tune the pore size of such frameworks still remains a significant challenge to date.In this study,we constructed supramolecular polymer frameworks using rigid tetrahedral star polyisocyanides with tunable length and sufficiently narrow distribution as building block.First,a series of tetrahedral four-arm star polyisocyanides with controlled chain lengths and narrow molecular weight distributions was prepared via the Pd(Ⅱ)-catalyzed living isocyanide polymerization.Then 2-ureido-4[1H]-pyrimidinone(Upy) unit was installed onto each chain-end of polyisocyanide arms via post-polymerization functionalization.Leveraging the supramolecular hydrogen bonding interactions between the terminal Upy units,well-ordered supramolecular polymer frameworks were readily obtained.Notably,the pore size was dependent on the chain length of the polyisocyanide arms.Precisely control the chain length of polyisocyanide arms,supramolecular polymer frameworks with pore sizes ranging from 5.06 nm to 9.72 nm were achieved.These frameworks,with tunable and large pore apertures,demonstrated exceptional capabilities in encapsulating enzymes of different sizes,such as lipase(TL),horseradish peroxidase(HRP),and glucose oxidase(GOx).The encapsulated enzymes exhibited significantly enhanced catalytic activity and durability.Moreover,the frameworks' tunable and large pore apertures facilitated the co-encapsulation of multiple enzymes,enabling efficient dual-enzyme cascade reactions.展开更多
Supramolecular catalysis uses noncovalent interactions,such as hydrogen bonding,π-π stacking,and host-vip recognition,to control reactivity and selectivity in chemical reactions [1,2].Unlike traditional covalent c...Supramolecular catalysis uses noncovalent interactions,such as hydrogen bonding,π-π stacking,and host-vip recognition,to control reactivity and selectivity in chemical reactions [1,2].Unlike traditional covalent catalysis,supramolecular systems can create dynamic and adaptable microenvironments tailored to specific substrates,similar to how enzymes work.This strategy has shown great promise in asymmetric catalysis,cascade reactions,and green chemistry applications.Recent advances focus on leveraging less conventional noncovalent forces to expand the toolbox of supramolecular strategies in catalysis.展开更多
5,5'-dithiobis(2-nitrobenzoic acid)(H_(2)DTNB)was employed as the second ligand to react with cucurbit[6]uril(Q[6])and Cd(NO_(3))_(2),and it was deprotonated or transformed into HDTNB^(-),TNB^(2-)and NSB^(2-)(H_(2...5,5'-dithiobis(2-nitrobenzoic acid)(H_(2)DTNB)was employed as the second ligand to react with cucurbit[6]uril(Q[6])and Cd(NO_(3))_(2),and it was deprotonated or transformed into HDTNB^(-),TNB^(2-)and NSB^(2-)(H_(2)TNB=5,5'-thiobis(2-nitrobenzoic acid),H_(2)NSB=2-nitro-5-sulfobenzoic acid)under different conditions to afford three novel supramolecular assemblies with the formulas of[Cd(H_(2)O)_(4)(Q[6])](HDTNB)_(2)·3H_(2)O(1),[Cd(H_(2)O)_(6)]_(2)(TNB)_(2)·Q[6]·4H_(2)O(2)and[Cd(H_(2)O)_(5)(NSB)]_(2)·Q[6](3).Singe-crystal diffraction(SC-XRD)analysis revealed that assembly 1 is constructed from 2D[Cd(H_(2)O)_(4)(Q[6])]2+supramolecular layers and HDTNB^(-)supra molecular layers,the structure of assembly 2 is comprised of the 2D{[Cd(H_(2)O)_(6)]_(2)·Q[6]}^(4+)supramolecular layers and 1D TNB^(2-)supramolecular chains,while assembly 3 is built from the 3D Q[6]frameworks with[Cd(H_(2)O)_(5)(NSB)]supramolecular chains filled in the pores.Meanwhile,the noncovalent interactions between the ligands HDTNB^(-)/TNB^(2-)/NSB^(2-)and the outer-surface of Q[6]molecules contributed greatly to the formation of the supramolecular architecture of assemblies 1-3.CCDC:2522253,1;2522254,2;2522255,3.展开更多
We proposed a strategy using high-concentration tannic acid(TA) solutions to form robust and dense supramolecular networks in hydrogels,driven by the high osmotic pressure of the TA solution.The resulting hydrogels ar...We proposed a strategy using high-concentration tannic acid(TA) solutions to form robust and dense supramolecular networks in hydrogels,driven by the high osmotic pressure of the TA solution.The resulting hydrogels are both transparent and tough,with highly compacted networks.The hydrogels exhibit an ultimate tensile strength of approximately 4.55 MPa and a toughness of 160 MJ/m^(3).Additionally,the hydrogels adhere to a wide range of substrates,including metals,ceramics,glass,and even Teflon,with an adhesion strength of up to 42 kPa on Teflon plates.Given the biocompatibility and biodegradability of both PVA and TA,along with the hydrogels' toughness,transparency,and adhesiveness,we anticipated broad applications in the biomedical field,such as in articular cartilage restoration,electronic skin,and wound dressings.Additionally,these hydrogels hold significant potential for applications in wearable technology and optoelectronic devices.展开更多
Photo-responsive supramolecular assembly especially supramolecular hydrogels with tunable luminescence show a promising application potential in writable information recording and display materials.Herein,we report ph...Photo-responsive supramolecular assembly especially supramolecular hydrogels with tunable luminescence show a promising application potential in writable information recording and display materials.Herein,we report photo-responsive reversible multicolor supramolecular hydrogel with near-infrared emission,which is constructed by cucurbit[7]uril(CB[7]),cyanostilbene derivative(DAC)and Laponite XLG(LP)via supramolecular cascade assembly.Compared with the free vip molecule DAC,the confinement of macrocycle CB[7]achieve effective near-infrared fluorescence in the aqueous phase from scratch,and the subsequent cascade assembly with LP further restrict the molecular rotation of the DAC,which not only result in a substantial enhancement of the fluorescence intensity,but is also endowed with light-controlled fluorescence on/off both in the solution and hydrogel states.Further,8-hydroxy-1,3,6-pyrenetrisulfonic acid trisodium salt(HPTS)is introduced in the cascade assembly to fabricated photocontrollable reversible multicolor luminescence supramolecular hydrogel between red and green induced by Förster resonance energy transfer,which is successfully employed in reversible multiple information encryption.展开更多
Graphitic carbon nitride(g-CN)stands out as the most promising candidate for solar energy conversion owing to its easy preparation,metal-free nature,flexible molecular structure,moderate bandgap,and excellent thermal/...Graphitic carbon nitride(g-CN)stands out as the most promising candidate for solar energy conversion owing to its easy preparation,metal-free nature,flexible molecular structure,moderate bandgap,and excellent thermal/chemical stability.To enhance the performance of intrinsic g-CN,a supramolecular self-assembly strategy has been proposed to regulate the molecular structure of supramolecular precursors through non-covalent interactions across molecular building blocks,thereby optimizing the electronic structure of g-CN.This review provides a comprehensive overview of the recent progress in supramolecular self-assembly-derived graphitic carbon nitride(SM-CN)from both experimental and theoretical computational research in synthesis strategies,including synthesis methods and influencing factors,providing a theoretical foundation for the design of supramolecular assembly.It also discusses modification strategies,such as internal modification of the conjugated plane,interlayer optimization,and construction of heterointerfaces to improve the electronic structure of SM-CN owing to its unique layered structure.This review further summarizes the applications of SM-CN in environment and energy,including wastewater treatment,sterilization and disinfection/air purification,water splitting,H_(2)O_(2)production,organic synthesis/biomass conversion,CO_(2)reduction,photocatalytic coupling technology.Finally,perspectives and outlooks for the future development of SM-CN aim to inspire further innovation in the design and construction of high-performance SM-CN for broader applications.展开更多
The preparation of ionic liquid gel electrolyte can reduce the occurrence of side effects and extend battery life.In the DMSO-ILZE electrolyte composed of DMSO,1-ethyl-3-methylimidazole tetrafluoroborate(EMIMBF_(4))an...The preparation of ionic liquid gel electrolyte can reduce the occurrence of side effects and extend battery life.In the DMSO-ILZE electrolyte composed of DMSO,1-ethyl-3-methylimidazole tetrafluoroborate(EMIMBF_(4))and Zn(BF_(4))_(2),the supramolecular gelatorβ-cyclodextrin(β-CD)was added,and then a gel electrolyte(CD-ILZE)for zinc-ion batteries was prepared through host-vip interaction betweenβ-CD and DMSO-ILZE electrolyte.The gel electrolyte has good conductivity between-30 and 80℃,which is found by fitting the Arrhenius equation that the gel electrolyte satisfies the liquid law within this temperature range.In addition,the supramolecular gel electrolyte can effectively decrease hydrogen evolution corrosion and the formation of zinc dendrites.Compared with the battery prepared by DMSO-ILZE electrolyte(about 1100 h),the prepared Zn||Zn battery exhibits a more stable cycle(over 2800 h)at a current density of 0.5 m A·cm^(-2).At 0.1 A·g^(-1),the prepared Zn||V_(2)O_(5)gel electrolyte cell has a capacity of 30 m Ah·g^(-1)and a capacity retention rate of 85.17%after more than 1500 cycles.The CD-ILZE supramolecular gel electrolyte can inhibit the formation of hydrogen evolution corrosion and zinc dendrites,and improve the cycling performance of the battery.展开更多
Constructing nanofibers with specific therapeutic effects against cancer is a challenge.Here,we present the synthesis approach and application prospects of supramolecular nanofibers,which are based on cucurbit[8]uril(...Constructing nanofibers with specific therapeutic effects against cancer is a challenge.Here,we present the synthesis approach and application prospects of supramolecular nanofibers,which are based on cucurbit[8]uril(CB[8])as the host and terpyridine lanthanum ions metal complex as the vip,constructed by layer-by-layer self-assembly through supramolecular interaction.Moreover,nanofibers with lanthanide luminescence properties exhibit surprising pH-responsive deformation properties and antibacterial behavior.In the tumor micro-environment,the dramatic reduction in the size of the nanofibers enables specific and hierarchical release of anticancer drugs in tumor cells to exert an advanced therapeutic effect.In addition,the synergistic therapeutic efficacy was achieved by reducing the excess of Gram-positive and Gram-negative bacteria surrounding tumor cells.The novel supramolecular nanofibers with sequential drug release and combined therapeutic mode provide new guidance for the synthesis of drug carrier materials and direction for the promotion of nanomaterial-mediated cancer therapy.展开更多
Two supramolecular organic frameworks(SOFs)have been constructed from the co-assembly of biimidazolium-derived octacationic components and cucurbit[8]uril in water.Dynamic light scattering and ^(1)H NMR experiments re...Two supramolecular organic frameworks(SOFs)have been constructed from the co-assembly of biimidazolium-derived octacationic components and cucurbit[8]uril in water.Dynamic light scattering and ^(1)H NMR experiments reveal that both SOFs can undergo reversible assembly and disassembly at room temperature.One of the SOFs displays unprecedently high maximum tolerated dose of 120 mg/kg with mice,which improves by 40%compared with the highest value of the reported SOFs.In vitro and in vivo tests show that the SOF can adsorb doxorubicin and overcome the resistance of multidrugresistant MDR A549/ADR tumor cells to realize intracellular delivery,leading to enhanced antitumor efficacy.Moreover,it can also completely inhibit the posttreatment phototoxicity of photofrin and fully neutralize the anticoagulation of both unfractionated heparin and low molecular weight heparins through efficient inclusion and elimination or sequestration mechanism.As the first examples that undergo roomtemperature reversible assembly and disassembly,the new SOFs in principle allow for quantitative analysis of the molecular components in the body that is prerequisite for preclinical evaluation in the future.展开更多
Improving the optoelectronic behavior and stress-deformation stability of conjugated materials is crucial for the realization of their potential applications in flexible optoelectronics.To tune the emission behavior a...Improving the optoelectronic behavior and stress-deformation stability of conjugated materials is crucial for the realization of their potential applications in flexible optoelectronics.To tune the emission behavior and mechanical property of molecular crystals simultaneously via supramolecular salt strategy is rarely reported,which is very important to improve their photophysical behavior and softness for the fabrication of flexible light-emitting device.Herein,supramolecular salt approach has been successfully applied to synthesize two elastic organic fluorescent crystals(CMOH-Py-Cl and CMOH-Py-Br)derived from non-emissive and brittle pyridine-substituted coumarin derivative(CMOH-Py).Their elastic properties can be attributed to the prevalent presence of numerous weak interactions introduced by halogen atoms,which are beneficial to the absorption and release of mechanical energy.Furthermore,density functional theory(DFT)calculations demonstrated a narrowing of the HOMO-LUMO energy gaps from CMOH-Py to CMOH-Py-Cl/CMOH-Py-Br via supramolecular salt approach.Finally,the application of flexible crystal materials in the field of optical waveguides has been investigated.The transformation of crystals in terms of photophysical and mechanical properties,achieved by the supramolecular salt approach,offers novel insights into the design and construction of flexible crystalline materials,providing a new path for the development of next-generation smart materials.展开更多
Supramolecular luminescent materials(SLMs)exhibit exceptional luminescence properties and the ability to be intelligently regulated through diverse assembly approaches,making them highly attractive in the field of lum...Supramolecular luminescent materials(SLMs)exhibit exceptional luminescence properties and the ability to be intelligently regulated through diverse assembly approaches,making them highly attractive in the field of luminescent materials.In recent years,the novel macrocyclic arenes characterized by unique electron-rich structures,ease of derivatization,tunable conformations and even inherent luminescence properties afford much opportunities to create such dynamic smart luminescent materials.The incorporation of macrocyclic arenes into SLMs leads to simple preparation process,diverse photophysical phenomena and sophisticated regulatory mechanisms,which is also currently one of the most frontier and hot topics in macrocyclic and supramolecular chemistry and even luminescent materials.In this review,the research advances in construction and applications of SLMs based on macrocyclic arenes in the last several years will be presented from the different assembly strategies,including host-vip complexes,supramolecular polymers,nanoparticles,and other assemblies.Moreover,some insights into future directions for this research area will also be offered.展开更多
A renewable fluorescent material(GСCP5L)has been constructed via supramolecular assembly between a new derivative of pillararene,namely leggero pillar[5]arene,as the host molecule(CP5L)and a tetraphenylethylene(TPE)-...A renewable fluorescent material(GСCP5L)has been constructed via supramolecular assembly between a new derivative of pillararene,namely leggero pillar[5]arene,as the host molecule(CP5L)and a tetraphenylethylene(TPE)-based ditopic vip(G).This new material can simultaneously perform efficient detection and separation of silver(I)from aqueous environments.Possessing an electron-rich cavity and two cytosine groups modified on both rims,CP5L functions as the host-vip binding site for G and offers exclusive coordination sites for further interaction with Ag+.Adding Ag+to the system undergoes dramatic fluorescence enhancement due to the mechanism of supramolecular assembly-induced enhanced emission(SAIEE).This fluorescence enhancement allows for efficient and visualized detection following a“light-up”pattern,achieving a limit of detection(LOD)of 1.3×10^(-7)mol/L,which is fully in line with the World Health Organization's drinking water standard of 9×10^(-7)mol/L.In addition,GСCP5L also shows strong anti-interference capability against other cationic species.For the separation of Ag+from aqueous systems,GСCP5L displays exceptional adsorption efficiency(97%)and reliable recovery performance,demonstrating excellent recyclability after five experimental cycles without compromising its adsorption activity.展开更多
The ring has been a romantic fascination throughout the ages,embodying not only beauty and order but also harboring numerous undisclosed properties awaiting discovery.In the realm of supramolecular chemistry,macrocycl...The ring has been a romantic fascination throughout the ages,embodying not only beauty and order but also harboring numerous undisclosed properties awaiting discovery.In the realm of supramolecular chemistry,macrocycles,with a cyclic structure and a central cavity like a doughnut,captivate the attention of scientists[1].In 1967,Pedersen's groundbreaking revelation that alkali metal ions could"fall into"the cavities of a cyclic ether named crown ether,even in organic solvents,unveiled a novel universe of macrocycle chemistry.Since then,numerous macrocyclic structures in nature have been discovered,isolated,and scrutinized.Drawing inspiration from nature,chemists endeavor to explore the vast potential of macrocyclic compounds by designing and synthesizing artificial macrocycles with diverse structural features and recognition properties.展开更多
Circularly polarized luminescence(CPL)-active materials have a wide range of technological applications.Traditionally,creating CPL-active materials relies on the use of chiral luminophores.In contrast,supramolecular a...Circularly polarized luminescence(CPL)-active materials have a wide range of technological applications.Traditionally,creating CPL-active materials relies on the use of chiral luminophores.In contrast,supramolecular assembly introduces an innovative and promising strategy for developing CPL-active materials not only from chiral luminophores but also from achiral species.This approach significantly enriches the diversity of CPL-active materials.It also offers an effective means to optimize the performance of CPL-active materials,such as enhancing the asymmetry factor|glum|.Compared to polymers,the assembly of small molecules is generally easier to control.This review systematically summarizes the recent progress and developments in CPL from small-molecule assemblies,particularly focusing on differences,merits,and demerits of three typical assembly modes.The aim is to provide valuable insights for the future development of chiroptical materials.展开更多
The convergence of materials science and biotechnology has catalyzed the development of innovative platforms,including nanotechnology,smart sensors,and supramolecular materials,significantly advancing the progress in ...The convergence of materials science and biotechnology has catalyzed the development of innovative platforms,including nanotechnology,smart sensors,and supramolecular materials,significantly advancing the progress in the field of life sciences[1−7].Among them,supramolecular materials have garnered increasing attention in life sciences owing to their distinctive self-assembly capabilities and intelligent responsiveness[8−12].展开更多
Surface-adhering biofilms contribute significantly to irreversible biofouling and corrosion,presenting a multi-trillion-dollar annual problem in public health and industry.Strategies employing antibacterial elements a...Surface-adhering biofilms contribute significantly to irreversible biofouling and corrosion,presenting a multi-trillion-dollar annual problem in public health and industry.Strategies employing antibacterial elements are emerging to fabricate multifunctional coatings that effectively combat such microbially produced damage.However,rapid,reliable,and robust surface engineering remains challenging due to stability limitations and intricate anti-biofilm additive dynamics.Herein,a silver-capsule-conjugated polyurethane coating with high stability and antimicrobial efficacy in a cooperative manner is developed through controlled supramolecular self-assembly.Polyvinylpyrrolidone(PVP)-mediated molecule entanglement breaks through the incompatibility between polymeric components and nanomaterials,strengthening the dispersion and fixation of encapsulated silver nanoparticles.The facilitation and control of the nanoscale interfacial binding significantly suppresses the aggregation of inorganic nanoparticles and consequent microcracks development,giving rise to mechanical robustness and thermal stability of the hybrid coating under extreme conditions.A synergistic combination of exposed residues,electrostatic,and coordination interactions could readily integrate the resultant coating on virtually arbitrary material sur-faces.This composite coating exhibits broad-spectrum and high bactericidal efficiencies of 99.99% against Staphylococcus aureus and Escherichia coli,as well as excellent biofilm formation suppression.Moreover,our coating has robust resistance to microbial-influenced corrosion(MIC)and can even endure 720 h of salt spray.This study deciphers a general code for creating stable and durable nanohybrid coatings to mitigate microbially related risks.展开更多
Sustained inflammatory responses are closely related to various severe diseases,and inhibiting the excessive activation of inflammasomes and pyroptosis has significant implications for clinical treatment.Natural produ...Sustained inflammatory responses are closely related to various severe diseases,and inhibiting the excessive activation of inflammasomes and pyroptosis has significant implications for clinical treatment.Natural products have garnered considerable concern for the treatment of inflammation.Huanglian-Wumei decoction(HLWMD)is a classic prescription used for treating inflammatory diseases,but the necessity of their combination and the exact underlying anti-inflammatory mechanism have not yet been elucidated.Inspired by the supramolecular self-assembly strategy and natural drug compatibility theory,we successfully obtained berberine(BBR)-chlorogenic acid(CGA)supramolecular(BCS),which is an herbal pair from HLWMD.Using a series of characterization methods,we confirmed the self-assembly mechanism of BCS.BBR and CGA were self-assembled and stacked into amphiphilic spherical supramolecules in a 2:1 molar ratio,driven by electrostatic interactions,hydrophobic interactions,andπ–πstacking;the hydrophilic fragments of CGA were outside,and the hydrophobic fragments of BBR were inside.This stacking pattern significantly improved the anti-inflammatory performance of BCS compared with that of single free molecules.Compared with free molecules,BCS significantly attenuated the release of multiple inflammatory mediators and lipopolysaccharide(LPS)-induced pyroptosis.Its anti-inflammatory mechanism is closely related to the inhibition of intracellular nuclear factor-kappaB(NF-κB)p65 phosphorylation and the noncanonical pyroptosis signalling pathway mediated by caspase-11.展开更多
Osteoarthritis(OA)is the most prevalent joint disease and icariin is a promising drug for its treatment.However,the clinical use of icariin is hindered by poor water solubility,low bioavailability,and nonspecific rele...Osteoarthritis(OA)is the most prevalent joint disease and icariin is a promising drug for its treatment.However,the clinical use of icariin is hindered by poor water solubility,low bioavailability,and nonspecific release and biological distribution.Herein,sulfonated azocalix[4]arene(SAC4A)with enhanced water solubility,recognition capacity,and designed responsiveness was used to improve the efficiency of icariin for OA therapy.SAC4A,a macrocycle with well-defined molecular weight and structure,could encapsulate and enhance water solubility of various drugs.In addition,SAC4A enables hypoxia-responsive release of loaded drug.Compared with icariin treatment,supramolecular complex icariin@SAC4A significantly relieved OA symptoms of rats,including more regular bone morphology and structure,and lower degree of cartilage damage.Moreover,the supramolecular formulation demonstrated various advantages,including easy preparation,hypoxia-triggered release,and small size that conducive to drug penetration.展开更多
Background:Enzyme fragility remains a major challenge in research and applications.Free enzymes are highly unstable,inactivated by heat,acid,alkali,or organic solvents,and often lose activity even under optimal storag...Background:Enzyme fragility remains a major challenge in research and applications.Free enzymes are highly unstable,inactivated by heat,acid,alkali,or organic solvents,and often lose activity even under optimal storage conditions.Limiting their use in cosmetics.Few commercial products combine acids and enzymes effectively.Objective:To investigate the physicochemical properties,in vitro exfoliation efficacy,and effects on facial skin parameters of a supramolecular acid-enzyme complex(SAE)composed of mandelic acid(MAN),betaine(BET),and composite enzymes(CE;papain and bromelain),thereby establishing a theoretical foundation for cosmetic applications.Methods:The supramolecular structure was characterized using Fourier transform infrared(FTIR)spectroscopy and proton nuclear magnetic resonance(1H NMR)spectroscopy.Dissolution experiments were conducted to compare the solubility of SAE and CE in aqueous solutions.Enzymatic activity assays evaluated the stabilizing effect of supramolecular deep eutectic technology on enzymes.In vitro exfoliation tests assessed acid-enzyme synergy in keratin removal.A 4-week clinical trial evaluated the efficacy of a 2%SAE essence aqueous solution on facial skin parameters.Results:Dissolution experiments confirmed that supramolecular deep eutectic technology significantly improved enzyme solubility.Enzymatic activity tests demonstrated that this technology effectively preserved protease activity,substantially enhancing its practical applicability.Furthermore,in vitro exfoliation efficacy tests revealed that this technology strengthened the synergistic interaction between acids and enzymes and exhibited superior stratum corneum-removing capability of the SAE.In clinical evaluations of efficacy,after 7 days of using the essence containing SAE,the formulation significantly enhanced cheek gloss(+8.08%),while reducing comedones volume(-16.25%).after 28 days,significantly enhanced cheek hydration(+25.0%,SCH),gloss(+15.93%),and smoothness(−7.78%SEsm),while reducing TEWL(−6.86%),sebum(−15.54%),roughness(+16.24%SEr),and pore metrics(volume:−39.98%;count:−30.64%),and decreased comedones(blackheads:−70.33%;Whiteheads:−52.42%;all p<0.05).Conclusion:The supramolecular acid-enzyme complex demonstrates enhanced stability,improved solubility,and superior exfoliation efficacy compared to free enzymes.Clinical results further confirm its multifunctional benefits,including enhancing skin hydration,sebum regulation,barrier repair,pore refinement,and comedolytic effects.This study provides both theoretical and practical foundations for developing stable acid-enzyme combinations in dermatological applications.展开更多
A supramolecular system of active pharmaceutical ingredients(APIs)can modify the physicochemical properties and enhance the synergistic efficacy of their components;however,the relevant underlying mechanisms in vivo r...A supramolecular system of active pharmaceutical ingredients(APIs)can modify the physicochemical properties and enhance the synergistic efficacy of their components;however,the relevant underlying mechanisms in vivo remain unclear.This study employed a metabolomics-driven approach,combined with biological validation,to investigate the synergistic mechanisms of API-based supramolecular systems.Metabolic dysfunction exacerbates insulin resistance and obesity,contributing to hepatic steatosis and cardiac hypertrophy.A novel sodium-dependent glucose transporter 2(SGLT-2)/peroxisome proliferator-activated receptor-γ(PPAR-γ)dual receptor(dapagliflozin-pioglitazone(DAP-PIO))supramolecular system was selected as the model to explore the synergistic mechanism involved in the treatment of metabolic dysfunctions,diabetes and obesity.First,metabolomics analyses were performed to compare the effects of a simple physical mixture(PM)of DAP and PIO with the DAP-PIO supramolecular system after absorption into the bloodstream.The results demonstrated significant differences,with the supramolecular system activating the phosphatidylinositol 3-kinase(PI3K)/protein kinase B(AKT)and adenosine monophosphate-activated protein kinase(AMPK)signaling pathways.Ceramide(Cer),a key metabolite in sphingolipid metabolism,emerged as a critical mediator.Subsequently,the mechanisms underlying the DAP-PIO supramolecular system’s hypoglycemic effects and its ability to ameliorate hepatic steatosis and myocardial hypertrophy by reducing insulin resistance were evaluated and confirmed.These findings provide an innovative strategy for developing SGLT-2/PPAR-γdual-receptor supramolecular systems to enhance the therapeutic outcomes for diabetes and obesity.展开更多
基金The National Natural Science Foundation of China (NSFC,Nos.92256201,52273006,22071041,92356302,and 21971052)Natural Science Foundation of Jilin Province (No.20240101181JC) are gratefully appreciated for financial the supportssupported by the User Experiment Assist System of Shanghai Synchrotron Radiation Facility (SSRF)。
文摘Three-dimensional supramolecular organic frameworks with precisely tunable pore sizes are highly demanded for a wide range of applications,e.g.,encapsulating enzymes to enhance their stability,activity,and reusability.However,precise control and tune the pore size of such frameworks still remains a significant challenge to date.In this study,we constructed supramolecular polymer frameworks using rigid tetrahedral star polyisocyanides with tunable length and sufficiently narrow distribution as building block.First,a series of tetrahedral four-arm star polyisocyanides with controlled chain lengths and narrow molecular weight distributions was prepared via the Pd(Ⅱ)-catalyzed living isocyanide polymerization.Then 2-ureido-4[1H]-pyrimidinone(Upy) unit was installed onto each chain-end of polyisocyanide arms via post-polymerization functionalization.Leveraging the supramolecular hydrogen bonding interactions between the terminal Upy units,well-ordered supramolecular polymer frameworks were readily obtained.Notably,the pore size was dependent on the chain length of the polyisocyanide arms.Precisely control the chain length of polyisocyanide arms,supramolecular polymer frameworks with pore sizes ranging from 5.06 nm to 9.72 nm were achieved.These frameworks,with tunable and large pore apertures,demonstrated exceptional capabilities in encapsulating enzymes of different sizes,such as lipase(TL),horseradish peroxidase(HRP),and glucose oxidase(GOx).The encapsulated enzymes exhibited significantly enhanced catalytic activity and durability.Moreover,the frameworks' tunable and large pore apertures facilitated the co-encapsulation of multiple enzymes,enabling efficient dual-enzyme cascade reactions.
文摘Supramolecular catalysis uses noncovalent interactions,such as hydrogen bonding,π-π stacking,and host-vip recognition,to control reactivity and selectivity in chemical reactions [1,2].Unlike traditional covalent catalysis,supramolecular systems can create dynamic and adaptable microenvironments tailored to specific substrates,similar to how enzymes work.This strategy has shown great promise in asymmetric catalysis,cascade reactions,and green chemistry applications.Recent advances focus on leveraging less conventional noncovalent forces to expand the toolbox of supramolecular strategies in catalysis.
文摘5,5'-dithiobis(2-nitrobenzoic acid)(H_(2)DTNB)was employed as the second ligand to react with cucurbit[6]uril(Q[6])and Cd(NO_(3))_(2),and it was deprotonated or transformed into HDTNB^(-),TNB^(2-)and NSB^(2-)(H_(2)TNB=5,5'-thiobis(2-nitrobenzoic acid),H_(2)NSB=2-nitro-5-sulfobenzoic acid)under different conditions to afford three novel supramolecular assemblies with the formulas of[Cd(H_(2)O)_(4)(Q[6])](HDTNB)_(2)·3H_(2)O(1),[Cd(H_(2)O)_(6)]_(2)(TNB)_(2)·Q[6]·4H_(2)O(2)and[Cd(H_(2)O)_(5)(NSB)]_(2)·Q[6](3).Singe-crystal diffraction(SC-XRD)analysis revealed that assembly 1 is constructed from 2D[Cd(H_(2)O)_(4)(Q[6])]2+supramolecular layers and HDTNB^(-)supra molecular layers,the structure of assembly 2 is comprised of the 2D{[Cd(H_(2)O)_(6)]_(2)·Q[6]}^(4+)supramolecular layers and 1D TNB^(2-)supramolecular chains,while assembly 3 is built from the 3D Q[6]frameworks with[Cd(H_(2)O)_(5)(NSB)]supramolecular chains filled in the pores.Meanwhile,the noncovalent interactions between the ligands HDTNB^(-)/TNB^(2-)/NSB^(2-)and the outer-surface of Q[6]molecules contributed greatly to the formation of the supramolecular architecture of assemblies 1-3.CCDC:2522253,1;2522254,2;2522255,3.
基金Funded by the Guangdong Major Project of Basic and Applied Basic Research(No.2021B0301030001)the National Key Research and Development Program of China(No. 2021YFB3802300)the National Natural Science Foundation of China(Nos. 52403153 and 52203169)。
文摘We proposed a strategy using high-concentration tannic acid(TA) solutions to form robust and dense supramolecular networks in hydrogels,driven by the high osmotic pressure of the TA solution.The resulting hydrogels are both transparent and tough,with highly compacted networks.The hydrogels exhibit an ultimate tensile strength of approximately 4.55 MPa and a toughness of 160 MJ/m^(3).Additionally,the hydrogels adhere to a wide range of substrates,including metals,ceramics,glass,and even Teflon,with an adhesion strength of up to 42 kPa on Teflon plates.Given the biocompatibility and biodegradability of both PVA and TA,along with the hydrogels' toughness,transparency,and adhesiveness,we anticipated broad applications in the biomedical field,such as in articular cartilage restoration,electronic skin,and wound dressings.Additionally,these hydrogels hold significant potential for applications in wearable technology and optoelectronic devices.
基金National Natural Science Foundation of China (NSFC) (No.22131008)the Haihe Laboratory of Sustainable Chemical Transformations for financial support。
文摘Photo-responsive supramolecular assembly especially supramolecular hydrogels with tunable luminescence show a promising application potential in writable information recording and display materials.Herein,we report photo-responsive reversible multicolor supramolecular hydrogel with near-infrared emission,which is constructed by cucurbit[7]uril(CB[7]),cyanostilbene derivative(DAC)and Laponite XLG(LP)via supramolecular cascade assembly.Compared with the free vip molecule DAC,the confinement of macrocycle CB[7]achieve effective near-infrared fluorescence in the aqueous phase from scratch,and the subsequent cascade assembly with LP further restrict the molecular rotation of the DAC,which not only result in a substantial enhancement of the fluorescence intensity,but is also endowed with light-controlled fluorescence on/off both in the solution and hydrogel states.Further,8-hydroxy-1,3,6-pyrenetrisulfonic acid trisodium salt(HPTS)is introduced in the cascade assembly to fabricated photocontrollable reversible multicolor luminescence supramolecular hydrogel between red and green induced by Förster resonance energy transfer,which is successfully employed in reversible multiple information encryption.
基金supported by the National Natural Science Foundation of China(NSFC No.52271228)the Natural Science Foundation of Shaanxi Province(No.2023-JC-ZD-21)the Doctoral Dissertation Innovation Fund of Xi'an University of Technology(No.101-252072301)。
文摘Graphitic carbon nitride(g-CN)stands out as the most promising candidate for solar energy conversion owing to its easy preparation,metal-free nature,flexible molecular structure,moderate bandgap,and excellent thermal/chemical stability.To enhance the performance of intrinsic g-CN,a supramolecular self-assembly strategy has been proposed to regulate the molecular structure of supramolecular precursors through non-covalent interactions across molecular building blocks,thereby optimizing the electronic structure of g-CN.This review provides a comprehensive overview of the recent progress in supramolecular self-assembly-derived graphitic carbon nitride(SM-CN)from both experimental and theoretical computational research in synthesis strategies,including synthesis methods and influencing factors,providing a theoretical foundation for the design of supramolecular assembly.It also discusses modification strategies,such as internal modification of the conjugated plane,interlayer optimization,and construction of heterointerfaces to improve the electronic structure of SM-CN owing to its unique layered structure.This review further summarizes the applications of SM-CN in environment and energy,including wastewater treatment,sterilization and disinfection/air purification,water splitting,H_(2)O_(2)production,organic synthesis/biomass conversion,CO_(2)reduction,photocatalytic coupling technology.Finally,perspectives and outlooks for the future development of SM-CN aim to inspire further innovation in the design and construction of high-performance SM-CN for broader applications.
文摘The preparation of ionic liquid gel electrolyte can reduce the occurrence of side effects and extend battery life.In the DMSO-ILZE electrolyte composed of DMSO,1-ethyl-3-methylimidazole tetrafluoroborate(EMIMBF_(4))and Zn(BF_(4))_(2),the supramolecular gelatorβ-cyclodextrin(β-CD)was added,and then a gel electrolyte(CD-ILZE)for zinc-ion batteries was prepared through host-vip interaction betweenβ-CD and DMSO-ILZE electrolyte.The gel electrolyte has good conductivity between-30 and 80℃,which is found by fitting the Arrhenius equation that the gel electrolyte satisfies the liquid law within this temperature range.In addition,the supramolecular gel electrolyte can effectively decrease hydrogen evolution corrosion and the formation of zinc dendrites.Compared with the battery prepared by DMSO-ILZE electrolyte(about 1100 h),the prepared Zn||Zn battery exhibits a more stable cycle(over 2800 h)at a current density of 0.5 m A·cm^(-2).At 0.1 A·g^(-1),the prepared Zn||V_(2)O_(5)gel electrolyte cell has a capacity of 30 m Ah·g^(-1)and a capacity retention rate of 85.17%after more than 1500 cycles.The CD-ILZE supramolecular gel electrolyte can inhibit the formation of hydrogen evolution corrosion and zinc dendrites,and improve the cycling performance of the battery.
基金supported by the National Natural Science Foundation of China(No.82273919)Natural Science Foundation of Heilongjiang Province(No.LH2024H013)China Postdoctoral Science Foundation(No.2022MD723781).
文摘Constructing nanofibers with specific therapeutic effects against cancer is a challenge.Here,we present the synthesis approach and application prospects of supramolecular nanofibers,which are based on cucurbit[8]uril(CB[8])as the host and terpyridine lanthanum ions metal complex as the vip,constructed by layer-by-layer self-assembly through supramolecular interaction.Moreover,nanofibers with lanthanide luminescence properties exhibit surprising pH-responsive deformation properties and antibacterial behavior.In the tumor micro-environment,the dramatic reduction in the size of the nanofibers enables specific and hierarchical release of anticancer drugs in tumor cells to exert an advanced therapeutic effect.In addition,the synergistic therapeutic efficacy was achieved by reducing the excess of Gram-positive and Gram-negative bacteria surrounding tumor cells.The novel supramolecular nanofibers with sequential drug release and combined therapeutic mode provide new guidance for the synthesis of drug carrier materials and direction for the promotion of nanomaterial-mediated cancer therapy.
基金the National Natural Science Foundation of China(No.21921003 for Z.T.L.and 22201293 for S.B.Y.)Shanghai Sailing Program(No.22YF1458300 for S.B.Y.)for financial support。
文摘Two supramolecular organic frameworks(SOFs)have been constructed from the co-assembly of biimidazolium-derived octacationic components and cucurbit[8]uril in water.Dynamic light scattering and ^(1)H NMR experiments reveal that both SOFs can undergo reversible assembly and disassembly at room temperature.One of the SOFs displays unprecedently high maximum tolerated dose of 120 mg/kg with mice,which improves by 40%compared with the highest value of the reported SOFs.In vitro and in vivo tests show that the SOF can adsorb doxorubicin and overcome the resistance of multidrugresistant MDR A549/ADR tumor cells to realize intracellular delivery,leading to enhanced antitumor efficacy.Moreover,it can also completely inhibit the posttreatment phototoxicity of photofrin and fully neutralize the anticoagulation of both unfractionated heparin and low molecular weight heparins through efficient inclusion and elimination or sequestration mechanism.As the first examples that undergo roomtemperature reversible assembly and disassembly,the new SOFs in principle allow for quantitative analysis of the molecular components in the body that is prerequisite for preclinical evaluation in the future.
基金supported by the National Natural Science Foundation of China(Nos.22205105,61874053,22075136)National Key Basic Research Program of China(No.2020YFA0709900)Jiangsu Provincial Postgraduate Scientific Research Innovation Program(No.KYCX24_1649).
文摘Improving the optoelectronic behavior and stress-deformation stability of conjugated materials is crucial for the realization of their potential applications in flexible optoelectronics.To tune the emission behavior and mechanical property of molecular crystals simultaneously via supramolecular salt strategy is rarely reported,which is very important to improve their photophysical behavior and softness for the fabrication of flexible light-emitting device.Herein,supramolecular salt approach has been successfully applied to synthesize two elastic organic fluorescent crystals(CMOH-Py-Cl and CMOH-Py-Br)derived from non-emissive and brittle pyridine-substituted coumarin derivative(CMOH-Py).Their elastic properties can be attributed to the prevalent presence of numerous weak interactions introduced by halogen atoms,which are beneficial to the absorption and release of mechanical energy.Furthermore,density functional theory(DFT)calculations demonstrated a narrowing of the HOMO-LUMO energy gaps from CMOH-Py to CMOH-Py-Cl/CMOH-Py-Br via supramolecular salt approach.Finally,the application of flexible crystal materials in the field of optical waveguides has been investigated.The transformation of crystals in terms of photophysical and mechanical properties,achieved by the supramolecular salt approach,offers novel insights into the design and construction of flexible crystalline materials,providing a new path for the development of next-generation smart materials.
基金the National Natural Science Foundation of China(Nos.22171272,22031010)the Strategic Priority Research Program of the Chinese Academy of Sciences(No.XDB0520302)the Youth Innovation Promotion Association CAS(No.2021035)for financial support。
文摘Supramolecular luminescent materials(SLMs)exhibit exceptional luminescence properties and the ability to be intelligently regulated through diverse assembly approaches,making them highly attractive in the field of luminescent materials.In recent years,the novel macrocyclic arenes characterized by unique electron-rich structures,ease of derivatization,tunable conformations and even inherent luminescence properties afford much opportunities to create such dynamic smart luminescent materials.The incorporation of macrocyclic arenes into SLMs leads to simple preparation process,diverse photophysical phenomena and sophisticated regulatory mechanisms,which is also currently one of the most frontier and hot topics in macrocyclic and supramolecular chemistry and even luminescent materials.In this review,the research advances in construction and applications of SLMs based on macrocyclic arenes in the last several years will be presented from the different assembly strategies,including host-vip complexes,supramolecular polymers,nanoparticles,and other assemblies.Moreover,some insights into future directions for this research area will also be offered.
基金the Natural Science Foundation of Jilin Province(No.20230101052JC)the National Natural Science Foundation of China(No.52173200)Hangzhou Jingshi Technology Co.,Ltd.,and Hangzhou Xuhui Technology Co.,Ltd.for financial support。
文摘A renewable fluorescent material(GСCP5L)has been constructed via supramolecular assembly between a new derivative of pillararene,namely leggero pillar[5]arene,as the host molecule(CP5L)and a tetraphenylethylene(TPE)-based ditopic vip(G).This new material can simultaneously perform efficient detection and separation of silver(I)from aqueous environments.Possessing an electron-rich cavity and two cytosine groups modified on both rims,CP5L functions as the host-vip binding site for G and offers exclusive coordination sites for further interaction with Ag+.Adding Ag+to the system undergoes dramatic fluorescence enhancement due to the mechanism of supramolecular assembly-induced enhanced emission(SAIEE).This fluorescence enhancement allows for efficient and visualized detection following a“light-up”pattern,achieving a limit of detection(LOD)of 1.3×10^(-7)mol/L,which is fully in line with the World Health Organization's drinking water standard of 9×10^(-7)mol/L.In addition,GСCP5L also shows strong anti-interference capability against other cationic species.For the separation of Ag+from aqueous systems,GСCP5L displays exceptional adsorption efficiency(97%)and reliable recovery performance,demonstrating excellent recyclability after five experimental cycles without compromising its adsorption activity.
文摘The ring has been a romantic fascination throughout the ages,embodying not only beauty and order but also harboring numerous undisclosed properties awaiting discovery.In the realm of supramolecular chemistry,macrocycles,with a cyclic structure and a central cavity like a doughnut,captivate the attention of scientists[1].In 1967,Pedersen's groundbreaking revelation that alkali metal ions could"fall into"the cavities of a cyclic ether named crown ether,even in organic solvents,unveiled a novel universe of macrocycle chemistry.Since then,numerous macrocyclic structures in nature have been discovered,isolated,and scrutinized.Drawing inspiration from nature,chemists endeavor to explore the vast potential of macrocyclic compounds by designing and synthesizing artificial macrocycles with diverse structural features and recognition properties.
基金support from the National Natural Science Foundation of China(52473192)。
文摘Circularly polarized luminescence(CPL)-active materials have a wide range of technological applications.Traditionally,creating CPL-active materials relies on the use of chiral luminophores.In contrast,supramolecular assembly introduces an innovative and promising strategy for developing CPL-active materials not only from chiral luminophores but also from achiral species.This approach significantly enriches the diversity of CPL-active materials.It also offers an effective means to optimize the performance of CPL-active materials,such as enhancing the asymmetry factor|glum|.Compared to polymers,the assembly of small molecules is generally easier to control.This review systematically summarizes the recent progress and developments in CPL from small-molecule assemblies,particularly focusing on differences,merits,and demerits of three typical assembly modes.The aim is to provide valuable insights for the future development of chiroptical materials.
基金supported by the National Natural Science Foundation of China(22101043)the Fundamental Research Funds for the Central Universities(N2205013,N232410019,N2405013)+3 种基金Natural Science Foundation of Liaoning Province(2023-MSBA-068)the Opening Fund of State Key Laboratory of Heavy Oil Processing(SKLHOP202203006)the Key Laboratory of Functional Molecular Solids,Ministry of Education(FMS2023005)Northeastern University。
文摘The convergence of materials science and biotechnology has catalyzed the development of innovative platforms,including nanotechnology,smart sensors,and supramolecular materials,significantly advancing the progress in the field of life sciences[1−7].Among them,supramolecular materials have garnered increasing attention in life sciences owing to their distinctive self-assembly capabilities and intelligent responsiveness[8−12].
基金supported by the National Key Research and Development Program of China(Grant No.2022YFB3808800,Dake Xu)the National Natural Science Foundation of China(Grant Nos.U2006219(Dake Xu),52301081(Xiangyu Li))+4 种基金the National Postdoctoral Program for Innovative Talents(Grant No.BX20220059,Xiangyu Li)the China Postdoctoral Science Foundation(Grant No.2022M720677,Xiangyu Li)the Liaoning Provincial Natural Science Foundation of China(Grant No.2023-BS-052,Xiangyu Li)the Fundamental Research Funds for the Central Universities(Grant No.N2302015,Xiangyu Li)the State Key Laboratory of Marine Coatings Funded Project(Grant No.2024020800027,Xiangyu Li).
文摘Surface-adhering biofilms contribute significantly to irreversible biofouling and corrosion,presenting a multi-trillion-dollar annual problem in public health and industry.Strategies employing antibacterial elements are emerging to fabricate multifunctional coatings that effectively combat such microbially produced damage.However,rapid,reliable,and robust surface engineering remains challenging due to stability limitations and intricate anti-biofilm additive dynamics.Herein,a silver-capsule-conjugated polyurethane coating with high stability and antimicrobial efficacy in a cooperative manner is developed through controlled supramolecular self-assembly.Polyvinylpyrrolidone(PVP)-mediated molecule entanglement breaks through the incompatibility between polymeric components and nanomaterials,strengthening the dispersion and fixation of encapsulated silver nanoparticles.The facilitation and control of the nanoscale interfacial binding significantly suppresses the aggregation of inorganic nanoparticles and consequent microcracks development,giving rise to mechanical robustness and thermal stability of the hybrid coating under extreme conditions.A synergistic combination of exposed residues,electrostatic,and coordination interactions could readily integrate the resultant coating on virtually arbitrary material sur-faces.This composite coating exhibits broad-spectrum and high bactericidal efficiencies of 99.99% against Staphylococcus aureus and Escherichia coli,as well as excellent biofilm formation suppression.Moreover,our coating has robust resistance to microbial-influenced corrosion(MIC)and can even endure 720 h of salt spray.This study deciphers a general code for creating stable and durable nanohybrid coatings to mitigate microbially related risks.
基金supported by the Project of National Natural Science Foundation of China(Grant No.:82274219 and 81930117)the Key Project of Traditional Chinese Medicine Technology Development Plan of Jiangsu Province,China(Grant No.:ZD202201)Jiangsu Province Postgraduate Scientific Research Practice and Innovation Plan Project,China(Grant Nos.:KYCX21_1735 and SJCX21_0679).
文摘Sustained inflammatory responses are closely related to various severe diseases,and inhibiting the excessive activation of inflammasomes and pyroptosis has significant implications for clinical treatment.Natural products have garnered considerable concern for the treatment of inflammation.Huanglian-Wumei decoction(HLWMD)is a classic prescription used for treating inflammatory diseases,but the necessity of their combination and the exact underlying anti-inflammatory mechanism have not yet been elucidated.Inspired by the supramolecular self-assembly strategy and natural drug compatibility theory,we successfully obtained berberine(BBR)-chlorogenic acid(CGA)supramolecular(BCS),which is an herbal pair from HLWMD.Using a series of characterization methods,we confirmed the self-assembly mechanism of BCS.BBR and CGA were self-assembled and stacked into amphiphilic spherical supramolecules in a 2:1 molar ratio,driven by electrostatic interactions,hydrophobic interactions,andπ–πstacking;the hydrophilic fragments of CGA were outside,and the hydrophobic fragments of BBR were inside.This stacking pattern significantly improved the anti-inflammatory performance of BCS compared with that of single free molecules.Compared with free molecules,BCS significantly attenuated the release of multiple inflammatory mediators and lipopolysaccharide(LPS)-induced pyroptosis.Its anti-inflammatory mechanism is closely related to the inhibition of intracellular nuclear factor-kappaB(NF-κB)p65 phosphorylation and the noncanonical pyroptosis signalling pathway mediated by caspase-11.
基金supported by grants from the National Natural Science Foundation of China(Nos.82374489,U20A20259 and 22201299)the Scientific Research Program of the Tianjin Municipal Education Commission(No.2021ZD013)。
文摘Osteoarthritis(OA)is the most prevalent joint disease and icariin is a promising drug for its treatment.However,the clinical use of icariin is hindered by poor water solubility,low bioavailability,and nonspecific release and biological distribution.Herein,sulfonated azocalix[4]arene(SAC4A)with enhanced water solubility,recognition capacity,and designed responsiveness was used to improve the efficiency of icariin for OA therapy.SAC4A,a macrocycle with well-defined molecular weight and structure,could encapsulate and enhance water solubility of various drugs.In addition,SAC4A enables hypoxia-responsive release of loaded drug.Compared with icariin treatment,supramolecular complex icariin@SAC4A significantly relieved OA symptoms of rats,including more regular bone morphology and structure,and lower degree of cartilage damage.Moreover,the supramolecular formulation demonstrated various advantages,including easy preparation,hypoxia-triggered release,and small size that conducive to drug penetration.
文摘Background:Enzyme fragility remains a major challenge in research and applications.Free enzymes are highly unstable,inactivated by heat,acid,alkali,or organic solvents,and often lose activity even under optimal storage conditions.Limiting their use in cosmetics.Few commercial products combine acids and enzymes effectively.Objective:To investigate the physicochemical properties,in vitro exfoliation efficacy,and effects on facial skin parameters of a supramolecular acid-enzyme complex(SAE)composed of mandelic acid(MAN),betaine(BET),and composite enzymes(CE;papain and bromelain),thereby establishing a theoretical foundation for cosmetic applications.Methods:The supramolecular structure was characterized using Fourier transform infrared(FTIR)spectroscopy and proton nuclear magnetic resonance(1H NMR)spectroscopy.Dissolution experiments were conducted to compare the solubility of SAE and CE in aqueous solutions.Enzymatic activity assays evaluated the stabilizing effect of supramolecular deep eutectic technology on enzymes.In vitro exfoliation tests assessed acid-enzyme synergy in keratin removal.A 4-week clinical trial evaluated the efficacy of a 2%SAE essence aqueous solution on facial skin parameters.Results:Dissolution experiments confirmed that supramolecular deep eutectic technology significantly improved enzyme solubility.Enzymatic activity tests demonstrated that this technology effectively preserved protease activity,substantially enhancing its practical applicability.Furthermore,in vitro exfoliation efficacy tests revealed that this technology strengthened the synergistic interaction between acids and enzymes and exhibited superior stratum corneum-removing capability of the SAE.In clinical evaluations of efficacy,after 7 days of using the essence containing SAE,the formulation significantly enhanced cheek gloss(+8.08%),while reducing comedones volume(-16.25%).after 28 days,significantly enhanced cheek hydration(+25.0%,SCH),gloss(+15.93%),and smoothness(−7.78%SEsm),while reducing TEWL(−6.86%),sebum(−15.54%),roughness(+16.24%SEr),and pore metrics(volume:−39.98%;count:−30.64%),and decreased comedones(blackheads:−70.33%;Whiteheads:−52.42%;all p<0.05).Conclusion:The supramolecular acid-enzyme complex demonstrates enhanced stability,improved solubility,and superior exfoliation efficacy compared to free enzymes.Clinical results further confirm its multifunctional benefits,including enhancing skin hydration,sebum regulation,barrier repair,pore refinement,and comedolytic effects.This study provides both theoretical and practical foundations for developing stable acid-enzyme combinations in dermatological applications.
基金supported by the National Natural Science Foundation of China(Grant No.:22301060)the Central Guidance on Local Science and Technology Development Fund of Hebei Province(Grant No.:246Z2601G)+1 种基金Post-graduate’s Innovation Fund Project of Hebei Province(Grant No.:CXZZBS2024118)the Scientific Research Project of Hebei Administration of Traditional Chinese Medicine(Project No.:2022391).
文摘A supramolecular system of active pharmaceutical ingredients(APIs)can modify the physicochemical properties and enhance the synergistic efficacy of their components;however,the relevant underlying mechanisms in vivo remain unclear.This study employed a metabolomics-driven approach,combined with biological validation,to investigate the synergistic mechanisms of API-based supramolecular systems.Metabolic dysfunction exacerbates insulin resistance and obesity,contributing to hepatic steatosis and cardiac hypertrophy.A novel sodium-dependent glucose transporter 2(SGLT-2)/peroxisome proliferator-activated receptor-γ(PPAR-γ)dual receptor(dapagliflozin-pioglitazone(DAP-PIO))supramolecular system was selected as the model to explore the synergistic mechanism involved in the treatment of metabolic dysfunctions,diabetes and obesity.First,metabolomics analyses were performed to compare the effects of a simple physical mixture(PM)of DAP and PIO with the DAP-PIO supramolecular system after absorption into the bloodstream.The results demonstrated significant differences,with the supramolecular system activating the phosphatidylinositol 3-kinase(PI3K)/protein kinase B(AKT)and adenosine monophosphate-activated protein kinase(AMPK)signaling pathways.Ceramide(Cer),a key metabolite in sphingolipid metabolism,emerged as a critical mediator.Subsequently,the mechanisms underlying the DAP-PIO supramolecular system’s hypoglycemic effects and its ability to ameliorate hepatic steatosis and myocardial hypertrophy by reducing insulin resistance were evaluated and confirmed.These findings provide an innovative strategy for developing SGLT-2/PPAR-γdual-receptor supramolecular systems to enhance the therapeutic outcomes for diabetes and obesity.
