Interaction between chiral diols BDPDD, DMBDPD and BINOL with prochiral compounds was examined and some new supramolecular complexes were prepared. It was found that these chiral hosts could include prochiral vips,...Interaction between chiral diols BDPDD, DMBDPD and BINOL with prochiral compounds was examined and some new supramolecular complexes were prepared. It was found that these chiral hosts could include prochiral vips, a, b-unsaturated compounds or piper- azinedione derivatives to give inclusion crystals in different molar ratio. Formations of these supramolecular complexes were characterized by the data of IR and 1H NMR spectra.展开更多
The most simple method for solventless synthesis of supramolecular complex of CMCR·2BPY·BZP, [CMCR = C-methylcalix[4]resorcinarene, BPY = 4,4'-bipyridine, BZP = benzophenone], is proposed. Although CMCR ...The most simple method for solventless synthesis of supramolecular complex of CMCR·2BPY·BZP, [CMCR = C-methylcalix[4]resorcinarene, BPY = 4,4'-bipyridine, BZP = benzophenone], is proposed. Although CMCR by itself is high melting point compound (above 300°C), CMCR was found to be dissolved in melt mixture of BPY and BZPeven below 120°C. In the mixture of the three components, the reaction occurs to form CMCR·2BPY·BZP supramolecular complex.展开更多
MTBPyP (meso-tetrakis(4-N-benzylpyridyl)porphyrin, M=H-2, Zn) bearing positive charge has been shown to associate with SiW12O404- in water solution. The spectral evolution and Job's plots analyses reveal that the ...MTBPyP (meso-tetrakis(4-N-benzylpyridyl)porphyrin, M=H-2, Zn) bearing positive charge has been shown to associate with SiW12O404- in water solution. The spectral evolution and Job's plots analyses reveal that the relatively stable aggregates contain equal numbers of MTBPyP4(+) and SiW12O404-.展开更多
The chemistry of lanthanide supramolecular self-assembly has received much attention with many extraordinary structures discovered due to the unique photophysical properties such as the Laporte forbidden f–f transiti...The chemistry of lanthanide supramolecular self-assembly has received much attention with many extraordinary structures discovered due to the unique photophysical properties such as the Laporte forbidden f–f transition,large Stokes shift and long luminescence lifetime of lanthanides.Recent investigations have demonstrated the formation of architectures that are highly sensitive towards different stimuli,such as concentration,light,solvent and counter-anions.Various stimuli have been employed extensively for the preparation of desired supramolecular topologies with specific properties.Moreover,transformation from lower order- to higher order-supramolecular systems has also been observed by various stimuli due to the labile nature of lanthanide ions.This review summarizes recent research on the factors that govern the formation of self-assembled lanthanide supramolecules and aims to provide readers with the information required for designing functional lanthanide supramolecular systems.展开更多
Two supramolecular complexes [Zn（tacd）2]（C6H8O4）·6H2O（1） and [Cu（tacd）2]Cl2·4H2O（2） were synthesized and characterized by elemental analysis, IR spectra, TGA and single-crystal X-ray diffraction an...Two supramolecular complexes [Zn（tacd）2]（C6H8O4）·6H2O（1） and [Cu（tacd）2]Cl2·4H2O（2） were synthesized and characterized by elemental analysis, IR spectra, TGA and single-crystal X-ray diffraction analysis. The crystal structure showed that the metal ions in complexes 1 and 2 had similar coordination circumstance. But for the complex 2, it formed a novel two-dimensional supramolecular network with 12-membered rings and four-membered rings via hydrogen bond interaction. The thermal gravimetric analyses indicated that the two complexes had similar steps of weight-loss. On the basis of experiment, the two complexes were calculated by DFT-B3LYP/6-31G（d） in Gaussian 03. The results of calculation are in good agreement with the experiment.展开更多
Two novel supramolecular complexes [Cu（bpapa）（dhbd）]·CHaOH （1） and [Cu（bpapa）（ma）]·ma （2） （bpapa= bis[6-（2-pyridylamino）pyrid-2-yl]amine, dhbd=2,3-dihydroxybutanedioate dianion, ma=a-methacryl...Two novel supramolecular complexes [Cu（bpapa）（dhbd）]·CHaOH （1） and [Cu（bpapa）（ma）]·ma （2） （bpapa= bis[6-（2-pyridylamino）pyrid-2-yl]amine, dhbd=2,3-dihydroxybutanedioate dianion, ma=a-methacrylate） were rationally designed, synthesized and characterized by single crystal X-ray diffraction, IR, electronic spectroscopy and thermogravimetric analyses. Complex 1 was the first oligo-a-pyfidylamino complex based on hydroxypolycarboxylate and self-assembled into a 3D honeycomb configuration network with open channels and tubes containing 1D ladder-shaped double chains formed by hydrogen bonds and aromatic π-π stacking interactions. Complex 2 constructed a 2D supramolecular network extended by 1D chains from dimeric supramolecular synthon through noncovalent supramolecular interactions. In the two complexes, the chelating monohelical ligand adopted all-anti configuration. Density functional theory calculations were applied to 1 and 2.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
Parkinson's disease(PD)is a debilitating and progressive neurodegenerative disorder with complex pathology and multiple membrane barriers that hinder drug delivery,resulting in the absence of ideal therapeutic dru...Parkinson's disease(PD)is a debilitating and progressive neurodegenerative disorder with complex pathology and multiple membrane barriers that hinder drug delivery,resulting in the absence of ideal therapeutic drugs with minimal side effects[1].Recently,natural medicine has garnered significant attention due to its remarkable efficacy and limited side effects.Icariin,a naturally occurring flavonoid,exhibits excellent potential as a therapeutic agent for neurodegenerative disease[2].However,its clinical application is limited by poor water solubility,low bioavailability,and high clearance rates.Here,an aqueous formulation of icariin/hydroxypropyl-β-cyclodextrin(HP-β-CD)supramolecular inclusion complex was obtained to optimize icariin properties.Furthermore,icariin cyclodextrin supramolecular inclusion complex based thermosensitive(icariin gels)was innovated.At lower temperatures,it remained in a liquid phase with high fluidity.Upon reaching the gelation temperature,it underwent a transition to a gel phase with significantly reduced fluidity,which may be suitable for the design of an intranasal delivery system for PD treatment.The innovative approach capitalizes on the exceptional characteristics of HP-β-CD,which was utilized to synergize with nasal delivery for targeted brain delivery and with icariin for PD treatment[3,4].展开更多
The catalytic epoxidation of olefin was investigated on two copper complex-modified molybdenum oxides with a 3D supramolecular structure, [Cu（bipy）]4[Mo15O47].2H2O （1） and [Cu1（bix）][（Cu1bix） （δ-MoVl8O26）0....The catalytic epoxidation of olefin was investigated on two copper complex-modified molybdenum oxides with a 3D supramolecular structure, [Cu（bipy）]4[Mo15O47].2H2O （1） and [Cu1（bix）][（Cu1bix） （δ-MoVl8O26）0.5] （2） （bipy = 4,4＇-bipyridine, bix = 1,4-bis（imidazole-1-ylmethyl）benzene）. Both compounds were catalytically active and stable for the epoxidation of cyclooctene, 1-octene, and styrene with tert-butyl hydroperoxide （t-BuOOH） as oxidant. The excellent catalytic performance was attributed to the presence of stable coordination bonds between the molybdenum oxide and copper complex, which resulted in the formation of easily accessible Mo species with high electropositivity. In addition, the copper complex also acted as an active site for the activation of t-BuOOH, thus im- proving these copper complex-modified polyoxometalates.展开更多
Three novel rare-earth,nitrogen-rich and oxygen heterocyclic supramolecular complexes,namely[Nd(BTF)_(2)(H_(2)O)_(5)]_(n),[Sm(BTF)_(2)(H_(2)O)_(5)]_(n),and[Eu(BTF)_(2)(H_(2)O)_(5)]_(n),were synthesized.A single crysta...Three novel rare-earth,nitrogen-rich and oxygen heterocyclic supramolecular complexes,namely[Nd(BTF)_(2)(H_(2)O)_(5)]_(n),[Sm(BTF)_(2)(H_(2)O)_(5)]_(n),and[Eu(BTF)_(2)(H_(2)O)_(5)]_(n),were synthesized.A single crystal was obtained by the solvent evaporation method,and the structure and coordination mode of metal complexes were determined by single crystal X-ray diffraction.Results show that the supramolecular complexes contain many hydrogen bonds and thus have good thermal stability(T_(dec)>540 K).The thermal decomposition of ammonium perchlorate(AP)catalyzed by the complexes was investigated by differential thermal analysis,which reveals a pre-eminent catalytic effect on AP.The high temperature decomposition peak of AP can be advanced by nearly 90 K at the amount of added complexes of 10 wt%,and the activation energy of AP descent range is from 70 to 150 kJ/mol.The other properties were fully characterized through elemental analysis and Fourier transform infrared spectroscopy.展开更多
The application of supramolecular host–vip chemistry for controlled photoreactivity and molecular sensing is a highly important field of modern inorganic and physical chemistry.One key aspect is the formation of th...The application of supramolecular host–vip chemistry for controlled photoreactivity and molecular sensing is a highly important field of modern inorganic and physical chemistry.One key aspect is the formation of the triplet state after photoexcitation.Applications of zinc ion Schiff-base derivatives for this purpose are rarely reported in the literature and there is still a lack of investigation into the triplet state formation of these supramolecular complexes.展开更多
A new complex [Pb（phen）2（4-NBA）]2·2（NO3）·H2O（phen = 1,10-phenanthroline,4-NBA = 4-nitrobenzoate） has been hydrothermally synthesized and structurally determined by single-crystal X-ray diffraction,el...A new complex [Pb（phen）2（4-NBA）]2·2（NO3）·H2O（phen = 1,10-phenanthroline,4-NBA = 4-nitrobenzoate） has been hydrothermally synthesized and structurally determined by single-crystal X-ray diffraction,elemental analyses and IR spectroscopy.The complex crystallizes in monoclinic,space group P21/c with a = 13.416（3）,b = 14.065（3）,c = 16.845（3）（A°） ,β = 110.55（3）o,V = 2976.5（10）（A°）^3,Z = 2,Dc = 1.796 g/cm^3,F（000） = 1564,GOOF = 0.962,the final R = 0.0686 and wR = 0.1746.The crystal structure shows that the lead ion is coordinated with two carboxylate O atoms from the 4-NBA anion,and four N atoms from two phen molecules,forming a slightly distorted pentagonalbipyramidal coordination geometry.It is further extended by various supramo-lecular interactions to form a three-dimensional supramolecular network.The TG analysis result shows that this complex begins decomposing at 30 ℃ and decompounding completely at 733 ℃.展开更多
A colorimetric and fluorometric dual probe based on a water-soluble polythiophene derivative(PMTPBA)was designed and synthesized.It can be applied to determination of picric acid(PA) in 100% aqueous solution.The appro...A colorimetric and fluorometric dual probe based on a water-soluble polythiophene derivative(PMTPBA)was designed and synthesized.It can be applied to determination of picric acid(PA) in 100% aqueous solution.The approach relies on the formation of supramolecular polythiophene assemblies in the presence of PA through electrostatic,charge transfer and π-π stacking interactions.This probe could be utilized for the rapid and visual detection of PA both in aqueous solution and solid support with high specificity and sensitivity.The detection limit of this sensor is as low as 5.0 × 10^-8 mol/L.展开更多
The supramolecular terbium complex, {[Tb（SIP）（H2O）5]2（bpy）3（H2O）}n （NaH2SIP = 5-sulfoisophthalic acid monosodium salt and bpy = 4,4＇-bipyridyl）, has been synthesized by the hydrothermal reaction of Tb4O7 wi...The supramolecular terbium complex, {[Tb（SIP）（H2O）5]2（bpy）3（H2O）}n （NaH2SIP = 5-sulfoisophthalic acid monosodium salt and bpy = 4,4＇-bipyridyl）, has been synthesized by the hydrothermal reaction of Tb4O7 with NaH2SIP and bpy at 165 ℃, and characterized by single-crystal X-ray diffraction, elemental analysis, IR spectrum, powder X-ray diffraction and photoluminescence spectrum. It crystallizes in a monoclinic system, space group C2/c, with a = 30.6840（1）, b = 10.9206（2）, c = 17.4967（3） A, β= 111.931（1）°, V = 5438.65（14） A^3, Z = 4, C46H52N6O25S2Tb2, Mr = 1470.90, Dc = 1.796 g/cm^3, p = 2.747 mm^-1, F（000） = 2928, the final R = 0.0654 and wR = 0.1322 for 3806 observed reflections with I 〉 2σ（I）. In the neutral [Tb（SIP）（H2O）5]2 motif, the Tb（III） ions are linked by the SIP ligands to form a one-dimensional zigzag chain propagating along the c axis. The zigzag chains are linked together by hydrogen bonds and π-π stacking interactions to form a two-dimensional supramolecular framework. The uncoordinated bpy molecules act as pillars to extend the two-dimensional sheets into a distinctive pillared three-dimensional supramolecular structure through O-H...N hydrogen bonds. The photoluminescence of the complex was investigated at room temperature in the solid state.展开更多
Utilizing N-[（4-carboxyphenyl）-sulfonyl]glycine （abbreviated as cbsglyH3）,a new cobalt complex [Co（cbsglyH）（bipy）2]3H2O （bipy = 2,2＇-bipyridine） has been synthesized under mild conditions and characterized ...Utilizing N-[（4-carboxyphenyl）-sulfonyl]glycine （abbreviated as cbsglyH3）,a new cobalt complex [Co（cbsglyH）（bipy）2]3H2O （bipy = 2,2＇-bipyridine） has been synthesized under mild conditions and characterized by IR,elemental analysis,thermogravimetric analysis and X-ray diffraction analysis. It crystallizes in the monoclinic system,space group C2/c with a = 34.978（3）,b = 12.0437（11）,c = 20.0041（19） ,β = 122.2990（10）°,V = 7123.0（11） 3,Z = 8,C29H28CoN5O9S,Mr = 681.55,μ = 0.593 mm-1,Dc = 1.271 Kg/m3,F（000） = 2816,the final R = 0.0434 and wR = 0.1351. The title complex is a monomeric compound which is further assembled by intermolecular hydrogen bonds into a 3-D supramolecular network. Thermogravimetric analysis illustrates that this complex begins decomposing at 100 ℃ and decompounding completely at 560 ℃.展开更多
A new complex, [Cu（HL）（phen）（H2O）]·4H2O（1, H3L·HCl = 5-（（4-carboxypiperidin-1-yl）methyl）isophthalic acid hydrochloride, phen = 1,10-phenanthroline）, has been hydrothermally prepared and character...A new complex, [Cu（HL）（phen）（H2O）]·4H2O（1, H3L·HCl = 5-（（4-carboxypiperidin-1-yl）methyl）isophthalic acid hydrochloride, phen = 1,10-phenanthroline）, has been hydrothermally prepared and characterized by single-crystal X-ray diffraction, IR spectroscopy, elemental analysis and PXRD. Complex 1 crystallizes in monoclinic, space group P21/c with a = 14.5520（14）, b = 12.6659（12）, c = 15.5006（14） A, β = 97.224（2）o, V = 2834.3（5） A3, Z = 4, C27H33N3O11 Cu, Mr = 639.10, Dc = 1.498 g/cm3, μ = 0.837 mm-1, S = 1.047, F（000） = 1332, the final R = 0.0423 and w R = 0.1118 for 18772 observed reflections（I 〉 2σ（I））. The compound is a Cu（Ⅱ） centre mononuclear molecule in the asymmetric unit. The independent binuclear [Cu2（HL）2（phen）2] units are bridged to form a three-dimensional（3D） supramolecular polymer by extensive hydrogen bonds and π-π non-covalent bonding interactions. Moreover, thermogravimetric（TG） analysis and gas adsorption property of 1 were also discussed.展开更多
As a member of the curcuminoid compound family,curcumin(Cur)has many interesting therapeutic properties.However,its low aqueous solubility and stability have resulted in poor bioavailability and restricted clinical ef...As a member of the curcuminoid compound family,curcumin(Cur)has many interesting therapeutic properties.However,its low aqueous solubility and stability have resulted in poor bioavailability and restricted clinical efficacy.Based on size matching,β-cyclodextrin polymer(β-CDP),with its hydrophilic polymer chains and hydrophobic cavities,can form an inclusion complex with Cur.To improve the water solubility and stability of Cur,a simple and eco-friendly grinding method was designed to formβ-CDP inclusion complexes.According to the Boltzmann-Hamel's method and Job's method,the molar ratio of theβ-CD unit inβ-CDP to Cur was determined to be 1:1.The diffusion coefficient and diffusion activation energy of Cur-β-CDP were calculated in an electrochemical study.This supramolecular complex worked well in vitro to inhibit the proliferation of hepatoma carcinoma cells HepG2.Remarkably,this method visibly reduced the undesirable side effects on normal cells,without weakening the anti-cancer activity of the drugs.We expect that the obtained host-vip complex will provide a new approach for delivering natural drug molecules,having low water solubility.展开更多
Targeting delivery of tumor-associated carbohydrate antigen(TACA)-based vaccine to antigen-presenting cells(APCs)mediated by endogenous antibodies can improve the immunogenicity of TACA.However,an essential requiremen...Targeting delivery of tumor-associated carbohydrate antigen(TACA)-based vaccine to antigen-presenting cells(APCs)mediated by endogenous antibodies can improve the immunogenicity of TACA.However,an essential requirement of this approach is to generate high titers of endogenous antibodies in vivo through pre-immunization,which complicates the immunization procedure and may cause side effects.Herein,we report a new generation of APC-targeting TACA-based supramolecular complex vaccine,assembled by sialyl Thomsen-nouveau-bovine serum albumin-adamantine(sTn-BSA-Ada)and heptavalent rhamnose(Rha)-modifiedβ-cyclodextrin(β-CD)via host-vip interaction.The complex vaccine retained anti-Rha antibodies recruiting capability and facilitated the APCs uptake of the vaccine via the interaction of the Fc-domain with the Fc receptors on APCs.We demonstrate that direct immunization of complex vaccine elicited anti-Rha and anti-sTn specific immune response synchronously,generating a novel self-enhancement effect that can improve the antigen delivery to APCs in high efficacy.The structure-activity relationship(SAR)study proved that complex vaccine 4 with polyethylene glycol 6(PEG 6)linker in host molecule provoked a robust and specific sTn immune response comparable to the pre-immunization approach.The antisera induced by complex vaccine,either through direct immunization or pre-immunization,exhibited equal potency of cytotoxicity against the sTn expression cancer cells.This study provides a general platform for TACA-based vaccines with self-enhancement effects without the need for pre-immunization.展开更多
A supramolecular complex between β-cyclodextrin and cholesterol was synthesized and characterized via proton 1H NMR spectroscopy. In the supramolecular complex,the stoichiometric proportion of β-cyclodextrin to chol...A supramolecular complex between β-cyclodextrin and cholesterol was synthesized and characterized via proton 1H NMR spectroscopy. In the supramolecular complex,the stoichiometric proportion of β-cyclodextrin to cholesterol is 1：2. The possible conformation of the supramolecular complex was depicted according to the chemical shift variance of proton 1H NMR of the host and vip molecules inside the inclusion complex. Removal efficiency of cholesterol complexed by β-cyclodextrin in our work is increased to a remarkable extent. This result can be applied in the field of drug development to reduce cholesterol in blood and other human organs.展开更多
A silylated-terpyridine（Si TPy） derivative was newly synthesized and reacted with various transition metal ions in the solutions and self-assembled monolayers（SAMs）.Composition and morphology of the SAMs were char...A silylated-terpyridine（Si TPy） derivative was newly synthesized and reacted with various transition metal ions in the solutions and self-assembled monolayers（SAMs）.Composition and morphology of the SAMs were characterized by using absorption spectra,X-ray photoelectron spectra and atomic force microscope.The silylated-TPy compound gave off a luminescent emission at about 456 nm,which slightly shifted to 452 nm in the Zn^2＋-Si TPy and Fe^2＋-Si TPy metalated complexes.The absorbed energy can be further transferred to lanthanide ions（Tb^3＋and Eu^3＋） to give off the typical emissions of the lanthanide complexes together with an emission of the silylated-TPy at about 363 nm.展开更多
基金This work was supported by the National Natural Science Foundation of China (Project 29972033) and the Key Science Research Foundation of Hubei Province of China (Project 98IP1305).
文摘Interaction between chiral diols BDPDD, DMBDPD and BINOL with prochiral compounds was examined and some new supramolecular complexes were prepared. It was found that these chiral hosts could include prochiral vips, a, b-unsaturated compounds or piper- azinedione derivatives to give inclusion crystals in different molar ratio. Formations of these supramolecular complexes were characterized by the data of IR and 1H NMR spectra.
文摘The most simple method for solventless synthesis of supramolecular complex of CMCR·2BPY·BZP, [CMCR = C-methylcalix[4]resorcinarene, BPY = 4,4'-bipyridine, BZP = benzophenone], is proposed. Although CMCR by itself is high melting point compound (above 300°C), CMCR was found to be dissolved in melt mixture of BPY and BZPeven below 120°C. In the mixture of the three components, the reaction occurs to form CMCR·2BPY·BZP supramolecular complex.
基金This work was supported by the National NatUral Science Foundation of China under grant! No.29733090 and No. 29803003 the Re
文摘MTBPyP (meso-tetrakis(4-N-benzylpyridyl)porphyrin, M=H-2, Zn) bearing positive charge has been shown to associate with SiW12O404- in water solution. The spectral evolution and Job's plots analyses reveal that the relatively stable aggregates contain equal numbers of MTBPyP4(+) and SiW12O404-.
基金support from the National Natural Science Foundation of China(NSFC,21875201)support from the Hong Kong Polytechnic University(University Research Facility in Chemical and Environmental Analysis[UCEA]University Research Facility in Life Sciences[ULS]).
文摘The chemistry of lanthanide supramolecular self-assembly has received much attention with many extraordinary structures discovered due to the unique photophysical properties such as the Laporte forbidden f–f transition,large Stokes shift and long luminescence lifetime of lanthanides.Recent investigations have demonstrated the formation of architectures that are highly sensitive towards different stimuli,such as concentration,light,solvent and counter-anions.Various stimuli have been employed extensively for the preparation of desired supramolecular topologies with specific properties.Moreover,transformation from lower order- to higher order-supramolecular systems has also been observed by various stimuli due to the labile nature of lanthanide ions.This review summarizes recent research on the factors that govern the formation of self-assembled lanthanide supramolecules and aims to provide readers with the information required for designing functional lanthanide supramolecular systems.
基金Project supported by the National Natural Science Foundation of China （No. 20271041） and S haanxi Natural Science Foundation （No. 2002B04）.Acknowledgments We are grateful for Prof. Wen Zhenyi, who supplied the Gaussian 03 software for us. We also thank Prof. Ng Seik Weng at University of Malaya for the solution of the crystal structure of complex 1.
文摘Two supramolecular complexes [Zn（tacd）2]（C6H8O4）·6H2O（1） and [Cu（tacd）2]Cl2·4H2O（2） were synthesized and characterized by elemental analysis, IR spectra, TGA and single-crystal X-ray diffraction analysis. The crystal structure showed that the metal ions in complexes 1 and 2 had similar coordination circumstance. But for the complex 2, it formed a novel two-dimensional supramolecular network with 12-membered rings and four-membered rings via hydrogen bond interaction. The thermal gravimetric analyses indicated that the two complexes had similar steps of weight-loss. On the basis of experiment, the two complexes were calculated by DFT-B3LYP/6-31G（d） in Gaussian 03. The results of calculation are in good agreement with the experiment.
基金Project supported by the National Natural Science Foundation of China （No. 20471 048）.
文摘Two novel supramolecular complexes [Cu（bpapa）（dhbd）]·CHaOH （1） and [Cu（bpapa）（ma）]·ma （2） （bpapa= bis[6-（2-pyridylamino）pyrid-2-yl]amine, dhbd=2,3-dihydroxybutanedioate dianion, ma=a-methacrylate） were rationally designed, synthesized and characterized by single crystal X-ray diffraction, IR, electronic spectroscopy and thermogravimetric analyses. Complex 1 was the first oligo-a-pyfidylamino complex based on hydroxypolycarboxylate and self-assembled into a 3D honeycomb configuration network with open channels and tubes containing 1D ladder-shaped double chains formed by hydrogen bonds and aromatic π-π stacking interactions. Complex 2 constructed a 2D supramolecular network extended by 1D chains from dimeric supramolecular synthon through noncovalent supramolecular interactions. In the two complexes, the chelating monohelical ligand adopted all-anti configuration. Density functional theory calculations were applied to 1 and 2.
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.:82104399)the Science and Technology Project of Haihe Laboratory of Modern Chinese Medicine,China(Grant No.:22HHZYSS00001).
文摘Parkinson's disease(PD)is a debilitating and progressive neurodegenerative disorder with complex pathology and multiple membrane barriers that hinder drug delivery,resulting in the absence of ideal therapeutic drugs with minimal side effects[1].Recently,natural medicine has garnered significant attention due to its remarkable efficacy and limited side effects.Icariin,a naturally occurring flavonoid,exhibits excellent potential as a therapeutic agent for neurodegenerative disease[2].However,its clinical application is limited by poor water solubility,low bioavailability,and high clearance rates.Here,an aqueous formulation of icariin/hydroxypropyl-β-cyclodextrin(HP-β-CD)supramolecular inclusion complex was obtained to optimize icariin properties.Furthermore,icariin cyclodextrin supramolecular inclusion complex based thermosensitive(icariin gels)was innovated.At lower temperatures,it remained in a liquid phase with high fluidity.Upon reaching the gelation temperature,it underwent a transition to a gel phase with significantly reduced fluidity,which may be suitable for the design of an intranasal delivery system for PD treatment.The innovative approach capitalizes on the exceptional characteristics of HP-β-CD,which was utilized to synergize with nasal delivery for targeted brain delivery and with icariin for PD treatment[3,4].
基金supported by the National Natural Science Foundation of China(21173100 and 21320102001)~~
文摘The catalytic epoxidation of olefin was investigated on two copper complex-modified molybdenum oxides with a 3D supramolecular structure, [Cu（bipy）]4[Mo15O47].2H2O （1） and [Cu1（bix）][（Cu1bix） （δ-MoVl8O26）0.5] （2） （bipy = 4,4＇-bipyridine, bix = 1,4-bis（imidazole-1-ylmethyl）benzene）. Both compounds were catalytically active and stable for the epoxidation of cyclooctene, 1-octene, and styrene with tert-butyl hydroperoxide （t-BuOOH） as oxidant. The excellent catalytic performance was attributed to the presence of stable coordination bonds between the molybdenum oxide and copper complex, which resulted in the formation of easily accessible Mo species with high electropositivity. In addition, the copper complex also acted as an active site for the activation of t-BuOOH, thus im- proving these copper complex-modified polyoxometalates.
基金project supported by the National Natural Science Foundation of China(21875192)Outstanding Youth Science and Technology Talents Program of Sichuan(19JCQN0085)the Basic Research Project of Sichuan Province for Science and Technology Development(2019YJ0355)。
文摘Three novel rare-earth,nitrogen-rich and oxygen heterocyclic supramolecular complexes,namely[Nd(BTF)_(2)(H_(2)O)_(5)]_(n),[Sm(BTF)_(2)(H_(2)O)_(5)]_(n),and[Eu(BTF)_(2)(H_(2)O)_(5)]_(n),were synthesized.A single crystal was obtained by the solvent evaporation method,and the structure and coordination mode of metal complexes were determined by single crystal X-ray diffraction.Results show that the supramolecular complexes contain many hydrogen bonds and thus have good thermal stability(T_(dec)>540 K).The thermal decomposition of ammonium perchlorate(AP)catalyzed by the complexes was investigated by differential thermal analysis,which reveals a pre-eminent catalytic effect on AP.The high temperature decomposition peak of AP can be advanced by nearly 90 K at the amount of added complexes of 10 wt%,and the activation energy of AP descent range is from 70 to 150 kJ/mol.The other properties were fully characterized through elemental analysis and Fourier transform infrared spectroscopy.
基金the German Science Foundation(DFG)for funding though SPP2102.Computational time from the ZIH Dresden is gratefully acknowledged.We like to thank Prof.D.M.Guldi(Friedrich-Alexander-Universiteat Erlangen-Nuernberg)and his group for their support during the singlet oxygen phosphorescence measurements.
文摘The application of supramolecular host–vip chemistry for controlled photoreactivity and molecular sensing is a highly important field of modern inorganic and physical chemistry.One key aspect is the formation of the triplet state after photoexcitation.Applications of zinc ion Schiff-base derivatives for this purpose are rarely reported in the literature and there is still a lack of investigation into the triplet state formation of these supramolecular complexes.
基金supported by the National Natural Science Foundation of China (No. 20947003)China Postdoctoral Science Foundation (No. 20090461066)
文摘A new complex [Pb（phen）2（4-NBA）]2·2（NO3）·H2O（phen = 1,10-phenanthroline,4-NBA = 4-nitrobenzoate） has been hydrothermally synthesized and structurally determined by single-crystal X-ray diffraction,elemental analyses and IR spectroscopy.The complex crystallizes in monoclinic,space group P21/c with a = 13.416（3）,b = 14.065（3）,c = 16.845（3）（A°） ,β = 110.55（3）o,V = 2976.5（10）（A°）^3,Z = 2,Dc = 1.796 g/cm^3,F（000） = 1564,GOOF = 0.962,the final R = 0.0686 and wR = 0.1746.The crystal structure shows that the lead ion is coordinated with two carboxylate O atoms from the 4-NBA anion,and four N atoms from two phen molecules,forming a slightly distorted pentagonalbipyramidal coordination geometry.It is further extended by various supramo-lecular interactions to form a three-dimensional supramolecular network.The TG analysis result shows that this complex begins decomposing at 30 ℃ and decompounding completely at 733 ℃.
基金financially supported by the National Natural Science Foundation of China(No.31871877)Chinese Universities Scientific Fund(Nos.2018QC151,2019TC036)+1 种基金the"Talents Scheme"Program of Beijing(No.31050003)the Research Fund Program of Guangdong Provincial Key Laboratory of Radionuclides Pollution Control and Resources(No.2017B030314182)。
文摘A colorimetric and fluorometric dual probe based on a water-soluble polythiophene derivative(PMTPBA)was designed and synthesized.It can be applied to determination of picric acid(PA) in 100% aqueous solution.The approach relies on the formation of supramolecular polythiophene assemblies in the presence of PA through electrostatic,charge transfer and π-π stacking interactions.This probe could be utilized for the rapid and visual detection of PA both in aqueous solution and solid support with high specificity and sensitivity.The detection limit of this sensor is as low as 5.0 × 10^-8 mol/L.
基金the Education Department of Jiangxi Province (No. 2007-125)the Initial Fund for Doctors from Jiangxi Normal University
文摘The supramolecular terbium complex, {[Tb（SIP）（H2O）5]2（bpy）3（H2O）}n （NaH2SIP = 5-sulfoisophthalic acid monosodium salt and bpy = 4,4＇-bipyridyl）, has been synthesized by the hydrothermal reaction of Tb4O7 with NaH2SIP and bpy at 165 ℃, and characterized by single-crystal X-ray diffraction, elemental analysis, IR spectrum, powder X-ray diffraction and photoluminescence spectrum. It crystallizes in a monoclinic system, space group C2/c, with a = 30.6840（1）, b = 10.9206（2）, c = 17.4967（3） A, β= 111.931（1）°, V = 5438.65（14） A^3, Z = 4, C46H52N6O25S2Tb2, Mr = 1470.90, Dc = 1.796 g/cm^3, p = 2.747 mm^-1, F（000） = 2928, the final R = 0.0654 and wR = 0.1322 for 3806 observed reflections with I 〉 2σ（I）. In the neutral [Tb（SIP）（H2O）5]2 motif, the Tb（III） ions are linked by the SIP ligands to form a one-dimensional zigzag chain propagating along the c axis. The zigzag chains are linked together by hydrogen bonds and π-π stacking interactions to form a two-dimensional supramolecular framework. The uncoordinated bpy molecules act as pillars to extend the two-dimensional sheets into a distinctive pillared three-dimensional supramolecular structure through O-H...N hydrogen bonds. The photoluminescence of the complex was investigated at room temperature in the solid state.
基金supported by the National Natural Science Foundation of China (Nos. 20771054 and 20471026)Henan Tackle Key Problem of Science and Technology (Nos. 072102270030 and 072102270034)
文摘Utilizing N-[（4-carboxyphenyl）-sulfonyl]glycine （abbreviated as cbsglyH3）,a new cobalt complex [Co（cbsglyH）（bipy）2]3H2O （bipy = 2,2＇-bipyridine） has been synthesized under mild conditions and characterized by IR,elemental analysis,thermogravimetric analysis and X-ray diffraction analysis. It crystallizes in the monoclinic system,space group C2/c with a = 34.978（3）,b = 12.0437（11）,c = 20.0041（19） ,β = 122.2990（10）°,V = 7123.0（11） 3,Z = 8,C29H28CoN5O9S,Mr = 681.55,μ = 0.593 mm-1,Dc = 1.271 Kg/m3,F（000） = 2816,the final R = 0.0434 and wR = 0.1351. The title complex is a monomeric compound which is further assembled by intermolecular hydrogen bonds into a 3-D supramolecular network. Thermogravimetric analysis illustrates that this complex begins decomposing at 100 ℃ and decompounding completely at 560 ℃.
基金Supported by the National Natural Science Foundation of China(No.21171040)National Undergraduates Innovation Project(201510371010)
文摘A new complex, [Cu（HL）（phen）（H2O）]·4H2O（1, H3L·HCl = 5-（（4-carboxypiperidin-1-yl）methyl）isophthalic acid hydrochloride, phen = 1,10-phenanthroline）, has been hydrothermally prepared and characterized by single-crystal X-ray diffraction, IR spectroscopy, elemental analysis and PXRD. Complex 1 crystallizes in monoclinic, space group P21/c with a = 14.5520（14）, b = 12.6659（12）, c = 15.5006（14） A, β = 97.224（2）o, V = 2834.3（5） A3, Z = 4, C27H33N3O11 Cu, Mr = 639.10, Dc = 1.498 g/cm3, μ = 0.837 mm-1, S = 1.047, F（000） = 1332, the final R = 0.0423 and w R = 0.1118 for 18772 observed reflections（I 〉 2σ（I））. The compound is a Cu（Ⅱ） centre mononuclear molecule in the asymmetric unit. The independent binuclear [Cu2（HL）2（phen）2] units are bridged to form a three-dimensional（3D） supramolecular polymer by extensive hydrogen bonds and π-π non-covalent bonding interactions. Moreover, thermogravimetric（TG） analysis and gas adsorption property of 1 were also discussed.
基金supported by the National Natural Science Foundation of China(Nos.21703200 and 21773203)the Chey Institute for Advanced Studies International Scholar Exchange Fellowship for the Academic Year of 2021-2022China Scholarship Council Program(No.201908320084)。
文摘As a member of the curcuminoid compound family,curcumin(Cur)has many interesting therapeutic properties.However,its low aqueous solubility and stability have resulted in poor bioavailability and restricted clinical efficacy.Based on size matching,β-cyclodextrin polymer(β-CDP),with its hydrophilic polymer chains and hydrophobic cavities,can form an inclusion complex with Cur.To improve the water solubility and stability of Cur,a simple and eco-friendly grinding method was designed to formβ-CDP inclusion complexes.According to the Boltzmann-Hamel's method and Job's method,the molar ratio of theβ-CD unit inβ-CDP to Cur was determined to be 1:1.The diffusion coefficient and diffusion activation energy of Cur-β-CDP were calculated in an electrochemical study.This supramolecular complex worked well in vitro to inhibit the proliferation of hepatoma carcinoma cells HepG2.Remarkably,this method visibly reduced the undesirable side effects on normal cells,without weakening the anti-cancer activity of the drugs.We expect that the obtained host-vip complex will provide a new approach for delivering natural drug molecules,having low water solubility.
基金supported by the National Natural Science Foundation of China(No.22177040)the Natural Science Foundation of Jiangsu Province(No.BK20200601)partly funded by the 111 Project(No.111-2-06).
文摘Targeting delivery of tumor-associated carbohydrate antigen(TACA)-based vaccine to antigen-presenting cells(APCs)mediated by endogenous antibodies can improve the immunogenicity of TACA.However,an essential requirement of this approach is to generate high titers of endogenous antibodies in vivo through pre-immunization,which complicates the immunization procedure and may cause side effects.Herein,we report a new generation of APC-targeting TACA-based supramolecular complex vaccine,assembled by sialyl Thomsen-nouveau-bovine serum albumin-adamantine(sTn-BSA-Ada)and heptavalent rhamnose(Rha)-modifiedβ-cyclodextrin(β-CD)via host-vip interaction.The complex vaccine retained anti-Rha antibodies recruiting capability and facilitated the APCs uptake of the vaccine via the interaction of the Fc-domain with the Fc receptors on APCs.We demonstrate that direct immunization of complex vaccine elicited anti-Rha and anti-sTn specific immune response synchronously,generating a novel self-enhancement effect that can improve the antigen delivery to APCs in high efficacy.The structure-activity relationship(SAR)study proved that complex vaccine 4 with polyethylene glycol 6(PEG 6)linker in host molecule provoked a robust and specific sTn immune response comparable to the pre-immunization approach.The antisera induced by complex vaccine,either through direct immunization or pre-immunization,exhibited equal potency of cytotoxicity against the sTn expression cancer cells.This study provides a general platform for TACA-based vaccines with self-enhancement effects without the need for pre-immunization.
基金Supported by Autonomous Research Foundation (DC10040106)Central University Special Research Foundation
文摘A supramolecular complex between β-cyclodextrin and cholesterol was synthesized and characterized via proton 1H NMR spectroscopy. In the supramolecular complex,the stoichiometric proportion of β-cyclodextrin to cholesterol is 1：2. The possible conformation of the supramolecular complex was depicted according to the chemical shift variance of proton 1H NMR of the host and vip molecules inside the inclusion complex. Removal efficiency of cholesterol complexed by β-cyclodextrin in our work is increased to a remarkable extent. This result can be applied in the field of drug development to reduce cholesterol in blood and other human organs.
基金supported by National Natural Science Foundation of China (No.21373058)Program for Changjiang Scholars and Innovative Research Team in University (No.IRT1117)
文摘A silylated-terpyridine（Si TPy） derivative was newly synthesized and reacted with various transition metal ions in the solutions and self-assembled monolayers（SAMs）.Composition and morphology of the SAMs were characterized by using absorption spectra,X-ray photoelectron spectra and atomic force microscope.The silylated-TPy compound gave off a luminescent emission at about 456 nm,which slightly shifted to 452 nm in the Zn^2＋-Si TPy and Fe^2＋-Si TPy metalated complexes.The absorbed energy can be further transferred to lanthanide ions（Tb^3＋and Eu^3＋） to give off the typical emissions of the lanthanide complexes together with an emission of the silylated-TPy at about 363 nm.
