A new type of amphiphiles bearingmacrocycle such as cucurbit[7]uril(CB[7])spontaneously forms a nanomaterial in water,specifically vesicles(tACB[7]vesicles)with a positive surface charge,verified through various analy...A new type of amphiphiles bearingmacrocycle such as cucurbit[7]uril(CB[7])spontaneously forms a nanomaterial in water,specifically vesicles(tACB[7]vesicles)with a positive surface charge,verified through various analytical techniques including TIRF,DLS and TEM.Functional validation not only reveals the accessibility of the CB[7]portal on these vesicles allowing CB[7]-based host-vip interactions with various functional vip molecules such as fluorescein isothiocyanate conjugated adamantylammonium and spermine(FITC-AdA and FITC-SPM,respectively)using confocal laser scanning microscopy,but also showcases the effective internalization of tACB[7]vesicles into cancer cells with the anticancer drug oxaliplatin(OxPt),as a vip to CB[7],through in vitro cell experiments.Hence,this study provides a blueprint to impart amphiphilic properties to CB[7]through synthetic design and highlights the potential of CB[7]derivatives as a new class of unconventional amphiphiles self-assembling into functional nanomaterials for advanced drug delivery.展开更多
Three polymer-amphiphile complexes were prepared by combining poly（allylamine hydrochloride）（PAH） with the potassium salt of mono-,di-,and trisubstituted benzoic acid dendrons（4-octyloxybenzoic acid,3,5-dioctylox...Three polymer-amphiphile complexes were prepared by combining poly（allylamine hydrochloride）（PAH） with the potassium salt of mono-,di-,and trisubstituted benzoic acid dendrons（4-octyloxybenzoic acid,3,5-dioctyloxybenzoic acid,and 3,4,5- trioctyloxybenzoic acid）.The solid structure and properties were monitored with FT-IR,XRD,TG,DSC,and polarized optical microscope（POM）.Difference in the tail chain number of the dendritic amphiphile induced two different mesomorphous structures： lamella for the mono-,disubstituted dendron containing complexes and hexagonal column for the trisubstituted dendron containing complexes.These corresponded to the ionic thermotropic liquid crystal SmA andΦ_h phases,respectively.This finding is significant for design of functional nanostructures based on the ionic complexation of polymers and amphiphiles.展开更多
Desiccation tolerance is a crucial characteristic for desert moss surviving in arid regions. Desiccation procedure always induces amphiphiles transferring from the polar cytoplasm into lipid bodies. The behavior of am...Desiccation tolerance is a crucial characteristic for desert moss surviving in arid regions. Desiccation procedure always induces amphiphiles transferring from the polar cytoplasm into lipid bodies. The behavior of amphiphiles transferring can contribute to the enhancement of desiccation tolerance and the reduction of plasma membrane integrity simultaneously. The effects of amphiphiles partitioning into the lipid phase during water loss has been studied for pollen and seeds using electron paramagnetic resonance （EPR） spectroscopy. However, desiccation-tolerant high plants occur among mosses, several angiosperms and higher plants seeds or pollens. They have different strategies for survival in dehydration and rehydration. A desiccation-tolerant moss Tortula desertorurn was used to investigate the behaviors of amphiphilic molecules during drying by spin label technology. There are small amount of amphiphilic probes partitioning into membrane during moss leaves dehydration, comparing with that in higher plants. Cytoplasm viscosity changed from 1.14 into glass state only dehydration less than 60 min. Moss leaves lost plasma membrane integrity slightly,from 0.115 to 0.237, occurred simultaneously with amphiphiles partition. The results showed the more advantages of mosses than higher plants in adapting fast dehydration. We propose that EPR spin label is feasible for studying the amphiphiles partitioning mechanisms in membrane protection and damage for desiccation-tolerant mosses.展开更多
The polymerization of amphiphilic self assemblies is a promising method to synthesize nano structured materials with novel properties. These materials have many attractive features for their application in biomedica...The polymerization of amphiphilic self assemblies is a promising method to synthesize nano structured materials with novel properties. These materials have many attractive features for their application in biomedical area and materials science, such as catalysis, separation, surface modification, and therapeutics areas. A general review on the polymerization of lipids and surfactant self assemblies to amphiphilic self assemblies is given in this paper with 49 references. The polymerization and the subsequently resulted structure of lipids in different morphologies are summarized. The polymerization of polymerizable surfactants(surfmers) in emulsion and liquid crystalline phases are also discussed. The potential application of new nano porous materials is briefly described.展开更多
Pillar[n]arene-based amphiphiles,mainly including amphiphilic pillar[n]arenes and supra-amphiphilic pillar[n]arenes,have obtained considerable interests in recent years due to their fascinating chemical structures,var...Pillar[n]arene-based amphiphiles,mainly including amphiphilic pillar[n]arenes and supra-amphiphilic pillar[n]arenes,have obtained considerable interests in recent years due to their fascinating chemical structures,various self-assembly behaviors,and widely applications.Thanks to the pillar-like frameworks and the rich host-vip recognitions of the cavities,these amphiphiles can be easily controlled to form dimensional and morphologic assemblies for multiple applications.Compared with traditional linear covalent amphiphiles,the introduction of host-vip recognitions facilitated the preparation and controllability of these supramolecular amphiphilic systems.Moreover,the host-vip recognitions endow the assemblies from pillar[n]arene-based amphiphiles with stimuli-responsive functions.In this mini-review,we summarized the chemical structures,self-assembly features,and the applications of pillar[n]arene-based amphiphiles.However,several research topics of pillar[n]arenebased amphiphiles can be further developed in the future,such as larger cavity amphiphilic pillar[n]arenes,co-assembly with 2 D materials and utilization of the host-vip interactions.展开更多
A novel simple two-dimensional square-lattice model of amphiphile at oil-water interface is developed,in which oil and water act as solvent and occupy empty sites and amphiphile occupies chains of sites. In this mode...A novel simple two-dimensional square-lattice model of amphiphile at oil-water interface is developed,in which oil and water act as solvent and occupy empty sites and amphiphile occupies chains of sites. In this model, the oil-water interface is fixed, And amphiphile molecules will be enriched at the oil-water interface. The interfacial concentration of amphiphile calculated by Monte Carlo method shows that it is easier for the hydrophilic-hydrophobic balanced amphiphile to stay at the interface. And the adsorption of amphiphile increases with the increase of amphiphile concentration and the decrease with temperature.展开更多
A series of sphere-rod shape amphiphiles were designed and synthesized by connecting the rod-like oligofluorenes with different lengths （OF,） to the different positions of the spherical [60]fullerene （C60） through...A series of sphere-rod shape amphiphiles were designed and synthesized by connecting the rod-like oligofluorenes with different lengths （OF,） to the different positions of the spherical [60]fullerene （C60） through a rigid linkage. The conjugates were characterized by IH-NMR, 13C-NMR, FTIR, EA and MALDI-TOF mass spectrometry. The optical and electronic properties of the conjugates were studied by UV-Vis absorption spectroscopy, fluorescence spectrometry, and cyclic voltammetry. The results from UV-Vis absorption spectroscopy and cyclic voltammetry indicated that the energy profiles of C60 and OFn remained unchanged when different lengths of OFn were attached to C60. The electron affinities of the OFn-C60 conjugates were close to that of C60, while slight electronic interaction was found between the two individual chromophores （C60 and OFn） in their ground states. The fluorescence spectra exhibited a complete fluorescence quenching in the toluene solution, suggesting an effective energy transfer from OFn to C60. It presents a systematic study on the self- assembly, structure-property relationship, and potential technical applications of the conjugates.展开更多
Control of self-assembly is significant to the preparation of supramolecular materials, but the control of hydration, responsiveness, dimension, catalysis of macrocyclic amphiphiles in an atom-economic manner is still...Control of self-assembly is significant to the preparation of supramolecular materials, but the control of hydration, responsiveness, dimension, catalysis of macrocyclic amphiphiles in an atom-economic manner is still a great challenge. The herein presented 527 Da low-molecular-weight macrocyclic amphiphile was fabricated by utilizing the selenium-containing crown ether as a hydrophobic motif together with guanidinium group as the hydrophilic moiety. The resulting benzo[21]crown-7 based macrocyclic amphiphile readily forms a redox-responsive solid nanoparticles in water, which can further interconnect into wrinkled pattern on-surface, as well as exhibits as a nanozyme for catalyzing disulfid bond formation. The present work highlights the great potential of guanidinium-and selenium-containing crown ethers for the control of functional assemblies.展开更多
The spontaneous condensation of the amphiphilic N-（O,O-dihexadecyl）phosphorylalanine on the cast film was observed by in situ investigation of transmission infrared spectroscopy The particular orientation and ordere...The spontaneous condensation of the amphiphilic N-（O,O-dihexadecyl）phosphorylalanine on the cast film was observed by in situ investigation of transmission infrared spectroscopy The particular orientation and ordered packing of the monomers within the multilayers of the cast film is concluded to attribute to the spontaneous condensation between the monomers.展开更多
Amphiphile-oil-water system is complicated. The real behavior of amphiphile in the interface is still undnown despite that this behavior is very important in determining the stability of emulsion system. In this paper...Amphiphile-oil-water system is complicated. The real behavior of amphiphile in the interface is still undnown despite that this behavior is very important in determining the stability of emulsion system. In this paper, the interface properties of amphiphile at oil-water interface were investigated by a square-lattice model Monte Carlo simulation method. The synergistic effect was found for hydrophobic and hydrophilic amphiphile mixture systems; and the synergistic effect disappears or was weakened as the amphiphile at the interface region became dilute with the increasing of temperature.展开更多
A functional amphiphile, N^6 -myristoyl-9-[ 8-（ 1-trimethylamino） octyl ] adenine bromide （MTOAB）, was used to form coliposomes of phosphatidyleholine（PC）, PC/thymine, and PC/TOTB using sonication . The morpholo...A functional amphiphile, N^6 -myristoyl-9-[ 8-（ 1-trimethylamino） octyl ] adenine bromide （MTOAB）, was used to form coliposomes of phosphatidyleholine（PC）, PC/thymine, and PC/TOTB using sonication . The morphologies of the coliposomes were characterized using TEM （transmission electron microscopy）. The UV-Vis spectroscopic behavior of PC/MTOAB/thymine （molar ratio = 5： 1： 1 ） and PC/MTOAB/TOTB （molar ratio = 5： 1： 1 ） of coliposomal solutions showed that as a result of base pairing, absorption intensity showed a decrease at 263 nm with increase of time. The decrease of absorption intensity is ascribed to the hypochromic effect, which is because of the formation of hydrogen bonds between adenine and thymine in the coliposomes. The same effect was also observed for the mixture of aqueous PC/MTOAB liposomes and PC/TOTB liposomes after fusion, whereas the nocomplementary coliposomcs formed from PC/MTOAB and PC/TOTB did not show these spectroscopic changes. The molecular recognition through hydrogen interactions between adenine and thymine is very slow because of the possible occurrence of molecular lateral diffusion and exchange of amphiphile before recognition progresses in coliposomes. These results provide useful information for the design of supramolecular devices such as vesicles and liposomes,which can be used to mimic primitive recognition processes observed in biological systems.展开更多
By introducing a host molecule cucurbit[8]uril(CB[8]) into a charge transfer system containing an amphiphile 1-[11-(naphthalene-2-ylmethoxy)-11-oxoundecyl]pyridinium(NP) and an electron-deficient molecule methyl violo...By introducing a host molecule cucurbit[8]uril(CB[8]) into a charge transfer system containing an amphiphile 1-[11-(naphthalene-2-ylmethoxy)-11-oxoundecyl]pyridinium(NP) and an electron-deficient molecule methyl viologen(MV), a novel and anisotropic ternary building block was constructed by hostvip interactions, thereby leading to the morphology transformation of the final assemblies from thinfilms(NP/MV complexes) into diamond-like structures(NP/MV/CB[8] complexes). These intriguing assemblies were firstly discovered and were similar with the shape of well-known metal organic frameworks(MOFs), but just comprised three small organic molecules without metal ions. This finding can enrich the shape of current supramolecular assemblies and thus contributing to more potential applications in material science.展开更多
A novel amphiphile of 4-[4-(4-decyloxyphenylazo) naphthyloxy] butyl trimethylammonium bromide has been synthesized. It can form the stable bilayer in dilute aqueous solution.
Constitutionally adaptive chemistry of selenium-containing crown ethers(CEs) offers a new platform for controlling/switching the hydration of bolaamphiphile skeletons in water in an effective and simple manner by the ...Constitutionally adaptive chemistry of selenium-containing crown ethers(CEs) offers a new platform for controlling/switching the hydration of bolaamphiphile skeletons in water in an effective and simple manner by the virtue of covalent bonding. The adaptive behaviour of the macrocyclic bolaamphiphiles(transformations between C7SeBola and C7SeOBola) in response to redox environment was found to be a decisive factor.展开更多
Pillar[5]arene-modified amphiphilic peptides with varying numbers of guanidiniocarbonylpyrrol(GCP)moieties have been successfully synthesized,which can self-assemble to multivalent cationic superstructures in aqueous ...Pillar[5]arene-modified amphiphilic peptides with varying numbers of guanidiniocarbonylpyrrol(GCP)moieties have been successfully synthesized,which can self-assemble to multivalent cationic superstructures in aqueous solutions.These assembled peptides can condense DNA into various compact multimolecular aggregates to achieve successful intracellular DNA delivery and demonstrate great potential for gene transfection.Transfection efficiencies of the self-assembled superstructures have been evaluated in vitro with He La and HEK 293T cells.We demonstrate that GCP moiety could enhance the cell transfection ability,owing to its excellent binding towards cytomembrane.It was also found that subtle structure difference in peptides 2 and 3 could result in distinct transfection efficacy,which makes it possible to gain an in-depth understanding of their structure-activity relationship.This work presents a good example of rational structural design in achieving effective gene transfection vectors.展开更多
Fractal structures have attracted considerable scientific interest,and fractal geometry is an effective tool to study the complicated structure and dynamic processes,such as dilation symmetry of disorder structure,per...Fractal structures have attracted considerable scientific interest,and fractal geometry is an effective tool to study the complicated structure and dynamic processes,such as dilation symmetry of disorder structure,percolation,gelation,and metal-insulator transition.Here,we summarized our findings of fractal growth of giant amphiphiles in Langmuir-Blodgett(LB)film.Giant amphiphiles composed of polyhedral oligomeric silsesquioxanes(POSS)derivatives and poly(ethylene oxide)(PEO),with structural diversities of POSS head modification,POSS head number,PEO chain length,are precisely synthesized.The effect of molecular structures and operation parameters on the fractal growth patterns are discussed,in addition,other fractal growth patterns in LB films and in Langmuir films are included,aiming to understand the basic molecular principle of fractal growth in LB system.展开更多
Objectivs Enzyme/prodrug gene therapy provides a potential strategy for the treatment of glioma.Because of the limitations of using viral vectors for clinical application, we investigated the feasibility of cationicam...Objectivs Enzyme/prodrug gene therapy provides a potential strategy for the treatment of glioma.Because of the limitations of using viral vectors for clinical application, we investigated the feasibility of cationicamphiphile-mediated enzyme/prodrug gene transfer into C6 glioma cells. Methods Rat C6 glioma cells weretransfected with pUT599plasmid encoding the herpes simplex virus thymidine kinase (HSV-tk) gene via DOTAPand tested for chemosensitivity of prodrug ganciclovir (GCV). To demonstrate in vitro bystander effect, HSV-tkpositive cells were co-cultured with HSV-tk negative cells at varying proportions. Results DOTAP mediatedHSV-tk gene transfer into C6 cells showed 30%-40% of transfection efficiency. HSV-tk infected C6 glioma cellswere rendered sensitive to concentrations of GCV that were 3-4 logs lower than uninfected cells, with an IC05 of0.087μmol/L. In terms of the bystander effect, the viability of co-cultured cells decreased with increasingpopulations of HSV-tk positive cells after GCV treatment. Conclusion C6 cells were successfully transfected withthe HSV-tk gene via cationic amphiphile and displayed a strong bystander effect after GCV treatment. Cationicamphiphile - mediated HSV- tk/GCV chemosensitivity System may have promise as an intratumoral treatment forglioma.展开更多
Silica-supported branched polyethylenimine（Sil@PEI） is a conventional adsorbent and shows a limited affinity to anionic surfactants and small dyes（K = 106？107 L/mol）. If the PEI is alkylated with cetyl groups（C1...Silica-supported branched polyethylenimine（Sil@PEI） is a conventional adsorbent and shows a limited affinity to anionic surfactants and small dyes（K = 106？107 L/mol）. If the PEI is alkylated with cetyl groups（C16）, the K of the resulting adsorbents（Sil@PEI@C16-x, where x is the fraction of PEI units being alkylated） is significantly improved. Optimization shows that Sil@PEI@C16-0.15 can best reduce aqueous surfactants to a residue around 10？10 mol/L; while Sil@PEI@C16-0.6 can reduce even small aqueous dyes to a residue below 10？10 mol/L, nearly 105-fold lower than that by Sil@PEI. The adsorbents are well recyclable. It is believed that in the case of dyes, the dense cetyl shell can isolate the PEI from the bulky water and thus suppress the competitive binding by water; while in the case of surfactants, the semiclosed cetyl shell can simultaneously meet electrostatic complement and hydrophobic complement to the surfactants.展开更多
A novel class of amphiphiles with sulfate groups at the C-6 position and palmitoyl groups at the C-2, 3 positions of α-, β-, and γ-cyclodextrin (CD) were efficiently synthesized. These compounds formed stable monol...A novel class of amphiphiles with sulfate groups at the C-6 position and palmitoyl groups at the C-2, 3 positions of α-, β-, and γ-cyclodextrin (CD) were efficiently synthesized. These compounds formed stable monolayers with high collapse pressures at the air-water interface. The mixed monolayer behaviors of the 6-O-sulfated CD amphiphiles (SO3-CDC16) in the presence of dipalmitoyl phosphatidylcholine (DPPC) and cholesterol were discussed using the surface pressure-molecular area (π-A) isotherms. The collapse pressures showed maxima at molar ratios of SO3-CDC16 lower than 10 mol%. A morphological analysis of the liposomes containing DPPC and 4 mol% SO3-CDC16 formed in PBS was carried out using transmission electron microscopy with negative staining, and vesicles with maximum diameters of 350-500 nm were observed. Moreover, the releasing ability of these liposomes was examined using a fluorescent compound, calcein. It was clearly shown that liposomes containing SO3-CDC16 could release encapsulated calcein more easily than liposomes consisting only of DPPC, and that the release rate depended on the phase transition temperature of the SO3-CDC16 included in the liposome membrane.展开更多
We present a coarse-grained molecular dynamics simulation study of phase behavior of amphiphilic monolayers at the liquid crystal （LC）/water interface. The results revealed that LCs at interface can influence the la...We present a coarse-grained molecular dynamics simulation study of phase behavior of amphiphilic monolayers at the liquid crystal （LC）/water interface. The results revealed that LCs at interface can influence the lateral ordering of amphiphiles. Particularly, the amphiphile tails along with perpendicularly penetrated LCs between tails undergo a two-dimension phase transition from liquid-expanded into a liquid-condensed phase as their area density at interface reaches 0.93. While, the liquid-condensed phase of the monolayer never appears at oil/water interface with isotropic shape oil particles. These findings reveal the penetration of anisotropic LC can promote ordered lateral organization of amphiphiles. Moreover, we find the phase transition point is shifted to lower surface coverage of amphiphiles when the LCs have larger affinity to the amphiphile tails.展开更多
基金supported by the National Research Foundation of Korea[NRF-2023–00211758].
文摘A new type of amphiphiles bearingmacrocycle such as cucurbit[7]uril(CB[7])spontaneously forms a nanomaterial in water,specifically vesicles(tACB[7]vesicles)with a positive surface charge,verified through various analytical techniques including TIRF,DLS and TEM.Functional validation not only reveals the accessibility of the CB[7]portal on these vesicles allowing CB[7]-based host-vip interactions with various functional vip molecules such as fluorescein isothiocyanate conjugated adamantylammonium and spermine(FITC-AdA and FITC-SPM,respectively)using confocal laser scanning microscopy,but also showcases the effective internalization of tACB[7]vesicles into cancer cells with the anticancer drug oxaliplatin(OxPt),as a vip to CB[7],through in vitro cell experiments.Hence,this study provides a blueprint to impart amphiphilic properties to CB[7]through synthetic design and highlights the potential of CB[7]derivatives as a new class of unconventional amphiphiles self-assembling into functional nanomaterials for advanced drug delivery.
基金the financial support from the NSFC(No50873037)the PCSIRT(NoIRT0827)+2 种基金the Fundamental Research Funds for the Central Universities(No2009ZM0017)China Postdoctoral Science Foundation(No20100470908)the NSF of Guangdong Province(No10451064101005118) is gratefully acknowledged
文摘Three polymer-amphiphile complexes were prepared by combining poly（allylamine hydrochloride）（PAH） with the potassium salt of mono-,di-,and trisubstituted benzoic acid dendrons（4-octyloxybenzoic acid,3,5-dioctyloxybenzoic acid,and 3,4,5- trioctyloxybenzoic acid）.The solid structure and properties were monitored with FT-IR,XRD,TG,DSC,and polarized optical microscope（POM）.Difference in the tail chain number of the dendritic amphiphile induced two different mesomorphous structures： lamella for the mono-,disubstituted dendron containing complexes and hexagonal column for the trisubstituted dendron containing complexes.These corresponded to the ionic thermotropic liquid crystal SmA andΦ_h phases,respectively.This finding is significant for design of functional nanostructures based on the ionic complexation of polymers and amphiphiles.
基金the National Natural Science Foundation of China （No.30371002）.
文摘Desiccation tolerance is a crucial characteristic for desert moss surviving in arid regions. Desiccation procedure always induces amphiphiles transferring from the polar cytoplasm into lipid bodies. The behavior of amphiphiles transferring can contribute to the enhancement of desiccation tolerance and the reduction of plasma membrane integrity simultaneously. The effects of amphiphiles partitioning into the lipid phase during water loss has been studied for pollen and seeds using electron paramagnetic resonance （EPR） spectroscopy. However, desiccation-tolerant high plants occur among mosses, several angiosperms and higher plants seeds or pollens. They have different strategies for survival in dehydration and rehydration. A desiccation-tolerant moss Tortula desertorurn was used to investigate the behaviors of amphiphilic molecules during drying by spin label technology. There are small amount of amphiphilic probes partitioning into membrane during moss leaves dehydration, comparing with that in higher plants. Cytoplasm viscosity changed from 1.14 into glass state only dehydration less than 60 min. Moss leaves lost plasma membrane integrity slightly,from 0.115 to 0.237, occurred simultaneously with amphiphiles partition. The results showed the more advantages of mosses than higher plants in adapting fast dehydration. We propose that EPR spin label is feasible for studying the amphiphiles partitioning mechanisms in membrane protection and damage for desiccation-tolerant mosses.
基金Supported by National Natural Science Foundation(No.0 5 1730 0 3) Beijing Science and Technology New Star Program(No.H0 10 4 10 0 10 112 ) and Im portant Natural Science Foundation of Beijing(No.2 0 310 0 1) .
文摘The polymerization of amphiphilic self assemblies is a promising method to synthesize nano structured materials with novel properties. These materials have many attractive features for their application in biomedical area and materials science, such as catalysis, separation, surface modification, and therapeutics areas. A general review on the polymerization of lipids and surfactant self assemblies to amphiphilic self assemblies is given in this paper with 49 references. The polymerization and the subsequently resulted structure of lipids in different morphologies are summarized. The polymerization of polymerizable surfactants(surfmers) in emulsion and liquid crystalline phases are also discussed. The potential application of new nano porous materials is briefly described.
基金supported by the National Natural Science Foundation of China(Nos.21801139,21871227)Natural Science Foundation of Jiangsu Province(No.BK20180942)the Natural Science Foundation of Nantong University for High-Level Talent(No.03083004)。
文摘Pillar[n]arene-based amphiphiles,mainly including amphiphilic pillar[n]arenes and supra-amphiphilic pillar[n]arenes,have obtained considerable interests in recent years due to their fascinating chemical structures,various self-assembly behaviors,and widely applications.Thanks to the pillar-like frameworks and the rich host-vip recognitions of the cavities,these amphiphiles can be easily controlled to form dimensional and morphologic assemblies for multiple applications.Compared with traditional linear covalent amphiphiles,the introduction of host-vip recognitions facilitated the preparation and controllability of these supramolecular amphiphilic systems.Moreover,the host-vip recognitions endow the assemblies from pillar[n]arene-based amphiphiles with stimuli-responsive functions.In this mini-review,we summarized the chemical structures,self-assembly features,and the applications of pillar[n]arene-based amphiphiles.However,several research topics of pillar[n]arenebased amphiphiles can be further developed in the future,such as larger cavity amphiphilic pillar[n]arenes,co-assembly with 2 D materials and utilization of the host-vip interactions.
基金Supported by the National Natural Science Foundation of China (No. 29736170)and the Natural Science Foundation of Zhejiang Province(No. RC01051).
文摘A novel simple two-dimensional square-lattice model of amphiphile at oil-water interface is developed,in which oil and water act as solvent and occupy empty sites and amphiphile occupies chains of sites. In this model, the oil-water interface is fixed, And amphiphile molecules will be enriched at the oil-water interface. The interfacial concentration of amphiphile calculated by Monte Carlo method shows that it is easier for the hydrophilic-hydrophobic balanced amphiphile to stay at the interface. And the adsorption of amphiphile increases with the increase of amphiphile concentration and the decrease with temperature.
基金financially supported by the International Science&Technology Cooperation Program of China(No.2010DFB70470)the Natural Science Foundation of Shanghai(No.10ZR1407600)
文摘A series of sphere-rod shape amphiphiles were designed and synthesized by connecting the rod-like oligofluorenes with different lengths （OF,） to the different positions of the spherical [60]fullerene （C60） through a rigid linkage. The conjugates were characterized by IH-NMR, 13C-NMR, FTIR, EA and MALDI-TOF mass spectrometry. The optical and electronic properties of the conjugates were studied by UV-Vis absorption spectroscopy, fluorescence spectrometry, and cyclic voltammetry. The results from UV-Vis absorption spectroscopy and cyclic voltammetry indicated that the energy profiles of C60 and OFn remained unchanged when different lengths of OFn were attached to C60. The electron affinities of the OFn-C60 conjugates were close to that of C60, while slight electronic interaction was found between the two individual chromophores （C60 and OFn） in their ground states. The fluorescence spectra exhibited a complete fluorescence quenching in the toluene solution, suggesting an effective energy transfer from OFn to C60. It presents a systematic study on the self- assembly, structure-property relationship, and potential technical applications of the conjugates.
基金financial support from the National Natural Science Foundation of China (Nos. 21901210,22071196, 22007078)Key R&D Program of Shaanxi Province (No.2021KWZ-18)+4 种基金Aeronautical Science Foundation of China (No. ASFC-2020Z061053001)Opening Project of State Key Laboratory of Polymer Materials Engineering (Sichuan University)(No. klpme2021-05-03)Student Innovation and Entrepreneurship Education Center of the Student Work Department of the Party Committee of NPU(No. 2021-cxcy-012)Fundamental Research Funds for the Central Universitiesand Fellowship from CSC Innovative Team Program(No. CXXM20190099)。
文摘Control of self-assembly is significant to the preparation of supramolecular materials, but the control of hydration, responsiveness, dimension, catalysis of macrocyclic amphiphiles in an atom-economic manner is still a great challenge. The herein presented 527 Da low-molecular-weight macrocyclic amphiphile was fabricated by utilizing the selenium-containing crown ether as a hydrophobic motif together with guanidinium group as the hydrophilic moiety. The resulting benzo[21]crown-7 based macrocyclic amphiphile readily forms a redox-responsive solid nanoparticles in water, which can further interconnect into wrinkled pattern on-surface, as well as exhibits as a nanozyme for catalyzing disulfid bond formation. The present work highlights the great potential of guanidinium-and selenium-containing crown ethers for the control of functional assemblies.
基金supports from the National Natural Science Foundation of China(No.20272032,NSFCBIC20320130046)the Teaching and Research Award Program for Outstanding Young Teachers in Higher Education Institutions of MOE,P.R.C.(TRAPOYT)the Specialized research Fund for the Doctoral Program of Higher Education(SRFDP)(No.20030003049)
文摘The spontaneous condensation of the amphiphilic N-（O,O-dihexadecyl）phosphorylalanine on the cast film was observed by in situ investigation of transmission infrared spectroscopy The particular orientation and ordered packing of the monomers within the multilayers of the cast film is concluded to attribute to the spontaneous condensation between the monomers.
基金Supported by the National Natural Science Foundation of China (No. 29736170) the Natural Science Foundation of Zhejiang Province (No. RC01051).
文摘Amphiphile-oil-water system is complicated. The real behavior of amphiphile in the interface is still undnown despite that this behavior is very important in determining the stability of emulsion system. In this paper, the interface properties of amphiphile at oil-water interface were investigated by a square-lattice model Monte Carlo simulation method. The synergistic effect was found for hydrophobic and hydrophilic amphiphile mixture systems; and the synergistic effect disappears or was weakened as the amphiphile at the interface region became dilute with the increasing of temperature.
基金Supported by the National Natural Science Foundation of China(Nos. 50473005 and 20274015).
文摘A functional amphiphile, N^6 -myristoyl-9-[ 8-（ 1-trimethylamino） octyl ] adenine bromide （MTOAB）, was used to form coliposomes of phosphatidyleholine（PC）, PC/thymine, and PC/TOTB using sonication . The morphologies of the coliposomes were characterized using TEM （transmission electron microscopy）. The UV-Vis spectroscopic behavior of PC/MTOAB/thymine （molar ratio = 5： 1： 1 ） and PC/MTOAB/TOTB （molar ratio = 5： 1： 1 ） of coliposomal solutions showed that as a result of base pairing, absorption intensity showed a decrease at 263 nm with increase of time. The decrease of absorption intensity is ascribed to the hypochromic effect, which is because of the formation of hydrogen bonds between adenine and thymine in the coliposomes. The same effect was also observed for the mixture of aqueous PC/MTOAB liposomes and PC/TOTB liposomes after fusion, whereas the nocomplementary coliposomcs formed from PC/MTOAB and PC/TOTB did not show these spectroscopic changes. The molecular recognition through hydrogen interactions between adenine and thymine is very slow because of the possible occurrence of molecular lateral diffusion and exchange of amphiphile before recognition progresses in coliposomes. These results provide useful information for the design of supramolecular devices such as vesicles and liposomes,which can be used to mimic primitive recognition processes observed in biological systems.
基金the financial supports from the National Natural Science Foundation of China (Nos. 31860516, 21662009, 21702037)Frontiers Science Center for Asymmetric Synthesis and Medicinal Molecules, Department of Education, Guizhou Province [Qianjiaohe KY No. (2020)004]Program of Introducing Talents of Discipline to Universities of China (111 Program, No. D20023)。
文摘By introducing a host molecule cucurbit[8]uril(CB[8]) into a charge transfer system containing an amphiphile 1-[11-(naphthalene-2-ylmethoxy)-11-oxoundecyl]pyridinium(NP) and an electron-deficient molecule methyl viologen(MV), a novel and anisotropic ternary building block was constructed by hostvip interactions, thereby leading to the morphology transformation of the final assemblies from thinfilms(NP/MV complexes) into diamond-like structures(NP/MV/CB[8] complexes). These intriguing assemblies were firstly discovered and were similar with the shape of well-known metal organic frameworks(MOFs), but just comprised three small organic molecules without metal ions. This finding can enrich the shape of current supramolecular assemblies and thus contributing to more potential applications in material science.
文摘A novel amphiphile of 4-[4-(4-decyloxyphenylazo) naphthyloxy] butyl trimethylammonium bromide has been synthesized. It can form the stable bilayer in dilute aqueous solution.
基金the financial support from the National Natural Science Foundation of China (Nos. 52001255, 21901209, 21901210, 22071196, 22007078)Key R&D Program of Shaanxi Province (No. 2021KWZ-18)+2 种基金Aeronautical Science Foundation of China (No. ASFC-2020Z061053001)Fundamental Research Funds for the Central Universities (Nos. 3102019smxy001, 3102019ghxm005)Fellowship from CSC Innovative Team Program (No. CXXM20190099)。
文摘Constitutionally adaptive chemistry of selenium-containing crown ethers(CEs) offers a new platform for controlling/switching the hydration of bolaamphiphile skeletons in water in an effective and simple manner by the virtue of covalent bonding. The adaptive behaviour of the macrocyclic bolaamphiphiles(transformations between C7SeBola and C7SeOBola) in response to redox environment was found to be a decisive factor.
基金supported by the Natural Science Foundation of Jiangsu Province(Nos.BK20200432,BK20211179)National Natural Science Foundation of China(Nos.22271154,M-0411)the Fundamental Research Funds for the Central Universities(Nos.NG2022003,NS2021040)。
文摘Pillar[5]arene-modified amphiphilic peptides with varying numbers of guanidiniocarbonylpyrrol(GCP)moieties have been successfully synthesized,which can self-assemble to multivalent cationic superstructures in aqueous solutions.These assembled peptides can condense DNA into various compact multimolecular aggregates to achieve successful intracellular DNA delivery and demonstrate great potential for gene transfection.Transfection efficiencies of the self-assembled superstructures have been evaluated in vitro with He La and HEK 293T cells.We demonstrate that GCP moiety could enhance the cell transfection ability,owing to its excellent binding towards cytomembrane.It was also found that subtle structure difference in peptides 2 and 3 could result in distinct transfection efficacy,which makes it possible to gain an in-depth understanding of their structure-activity relationship.This work presents a good example of rational structural design in achieving effective gene transfection vectors.
基金financially supported by the Research Fund Program of Guangdong Provincial Key Laboratory of Function and Intelligent Hybrid Materials and Devices(No.2019B121203003).
文摘Fractal structures have attracted considerable scientific interest,and fractal geometry is an effective tool to study the complicated structure and dynamic processes,such as dilation symmetry of disorder structure,percolation,gelation,and metal-insulator transition.Here,we summarized our findings of fractal growth of giant amphiphiles in Langmuir-Blodgett(LB)film.Giant amphiphiles composed of polyhedral oligomeric silsesquioxanes(POSS)derivatives and poly(ethylene oxide)(PEO),with structural diversities of POSS head modification,POSS head number,PEO chain length,are precisely synthesized.The effect of molecular structures and operation parameters on the fractal growth patterns are discussed,in addition,other fractal growth patterns in LB films and in Langmuir films are included,aiming to understand the basic molecular principle of fractal growth in LB system.
文摘Objectivs Enzyme/prodrug gene therapy provides a potential strategy for the treatment of glioma.Because of the limitations of using viral vectors for clinical application, we investigated the feasibility of cationicamphiphile-mediated enzyme/prodrug gene transfer into C6 glioma cells. Methods Rat C6 glioma cells weretransfected with pUT599plasmid encoding the herpes simplex virus thymidine kinase (HSV-tk) gene via DOTAPand tested for chemosensitivity of prodrug ganciclovir (GCV). To demonstrate in vitro bystander effect, HSV-tkpositive cells were co-cultured with HSV-tk negative cells at varying proportions. Results DOTAP mediatedHSV-tk gene transfer into C6 cells showed 30%-40% of transfection efficiency. HSV-tk infected C6 glioma cellswere rendered sensitive to concentrations of GCV that were 3-4 logs lower than uninfected cells, with an IC05 of0.087μmol/L. In terms of the bystander effect, the viability of co-cultured cells decreased with increasingpopulations of HSV-tk positive cells after GCV treatment. Conclusion C6 cells were successfully transfected withthe HSV-tk gene via cationic amphiphile and displayed a strong bystander effect after GCV treatment. Cationicamphiphile - mediated HSV- tk/GCV chemosensitivity System may have promise as an intratumoral treatment forglioma.
文摘Silica-supported branched polyethylenimine（Sil@PEI） is a conventional adsorbent and shows a limited affinity to anionic surfactants and small dyes（K = 106？107 L/mol）. If the PEI is alkylated with cetyl groups（C16）, the K of the resulting adsorbents（Sil@PEI@C16-x, where x is the fraction of PEI units being alkylated） is significantly improved. Optimization shows that Sil@PEI@C16-0.15 can best reduce aqueous surfactants to a residue around 10？10 mol/L; while Sil@PEI@C16-0.6 can reduce even small aqueous dyes to a residue below 10？10 mol/L, nearly 105-fold lower than that by Sil@PEI. The adsorbents are well recyclable. It is believed that in the case of dyes, the dense cetyl shell can isolate the PEI from the bulky water and thus suppress the competitive binding by water; while in the case of surfactants, the semiclosed cetyl shell can simultaneously meet electrostatic complement and hydrophobic complement to the surfactants.
文摘A novel class of amphiphiles with sulfate groups at the C-6 position and palmitoyl groups at the C-2, 3 positions of α-, β-, and γ-cyclodextrin (CD) were efficiently synthesized. These compounds formed stable monolayers with high collapse pressures at the air-water interface. The mixed monolayer behaviors of the 6-O-sulfated CD amphiphiles (SO3-CDC16) in the presence of dipalmitoyl phosphatidylcholine (DPPC) and cholesterol were discussed using the surface pressure-molecular area (π-A) isotherms. The collapse pressures showed maxima at molar ratios of SO3-CDC16 lower than 10 mol%. A morphological analysis of the liposomes containing DPPC and 4 mol% SO3-CDC16 formed in PBS was carried out using transmission electron microscopy with negative staining, and vesicles with maximum diameters of 350-500 nm were observed. Moreover, the releasing ability of these liposomes was examined using a fluorescent compound, calcein. It was clearly shown that liposomes containing SO3-CDC16 could release encapsulated calcein more easily than liposomes consisting only of DPPC, and that the release rate depended on the phase transition temperature of the SO3-CDC16 included in the liposome membrane.
基金financially supported by the Naional Natural Science Foundation of China(Nos.21174154,50930002 and 20874110)the Supercomputer Center of Chinese Academy of Sciences
文摘We present a coarse-grained molecular dynamics simulation study of phase behavior of amphiphilic monolayers at the liquid crystal （LC）/water interface. The results revealed that LCs at interface can influence the lateral ordering of amphiphiles. Particularly, the amphiphile tails along with perpendicularly penetrated LCs between tails undergo a two-dimension phase transition from liquid-expanded into a liquid-condensed phase as their area density at interface reaches 0.93. While, the liquid-condensed phase of the monolayer never appears at oil/water interface with isotropic shape oil particles. These findings reveal the penetration of anisotropic LC can promote ordered lateral organization of amphiphiles. Moreover, we find the phase transition point is shifted to lower surface coverage of amphiphiles when the LCs have larger affinity to the amphiphile tails.
