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
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 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
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
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
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
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
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
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
The transport of anions across cell membranes is diffi cult because of the negatively charged outer surfaces of cell membranes.To overcome this limitation,herein,we report a system for transporting aromatic anions acr...The transport of anions across cell membranes is diffi cult because of the negatively charged outer surfaces of cell membranes.To overcome this limitation,herein,we report a system for transporting aromatic anions across cellular membranes via self-assembly using a synthetic imidazolium-fused aromatic amphiphile.The amphiphile with cationic and aromatic groups in close proximity to each other could interact with anionic pyranine via electrostatic and aromatic interactions to form supramolecular vesicles.Supramolecular vesicles based on the synthetic imidazoliumfused aromatic amphiphile and pyranine complex transport anionic aromatic pyranine across the membranes of live MCf-7 cells without cytotoxicity.展开更多
Cucurbituril （CB）, a well-known macrocyclic cavitand, has been used extensively to construct supramolecular aggregates. Based on host-vip intertactions, an adamantanyl derivative vip molecule was designed and sy...Cucurbituril （CB）, a well-known macrocyclic cavitand, has been used extensively to construct supramolecular aggregates. Based on host-vip intertactions, an adamantanyl derivative vip molecule was designed and syn- thesized to prepare a supramolecular amphiphile with cucurbit[7]uril. In aqueous solution, the cucurbit[7]uril based supramolecular amphiphiles self-assemble into well-defined vesicles, and their disassembly can be achieved by addition of excess competitive agent 1-adamantanamine hydrochloride. This vesicle functions as a new nanocapsule to encapsulate molecules within its hollow cavity. Through competitive disassembly of supramolecular amphiphiles, the vesicles behave as a novel drug delivery carrier.展开更多
With the development of deoxyribonucleic acid(DNA)nanotechnology,various DNA nanostructures and DNA devices have been constructed,which exhibit potential applications in material science and biomedicine.Taking advanta...With the development of deoxyribonucleic acid(DNA)nanotechnology,various DNA nanostructures and DNA devices have been constructed,which exhibit potential applications in material science and biomedicine.Taking advantage of the programmability and biocompatibility of DNA,novel building block to chemically functionalize DNA with hydrophobic organic molecules has attracted more and more attention.Driving by amphiphilicity,DNA-organic molecular amphiphiles have been demonstrated to self-assemble or further induce hierarchically assemblies,providing novel-specific properties.In this minireview,we summarize the recent progress of DNA organic molecular amphiphiles including their synthesis,self-assembly behavior in aqueous solution,and the amphiphilic self-assembly based on hierarchical DNA nano-structures.We further briefly discuss the perspective of the application of the DNA-organic molecular amphiphiles.展开更多
Cationic amphiphile aggregates exhibit superior antibacterial activity than monomers.However,the antimicrobial mechanism of aggregates has not been well understood because it is difficult to distinguish and monitor ag...Cationic amphiphile aggregates exhibit superior antibacterial activity than monomers.However,the antimicrobial mechanism of aggregates has not been well understood because it is difficult to distinguish and monitor aggregate and monomer in antimicrobial process.Herein,three bola-type cationic amphiphiles with aggregation-induced emission property have been developed to show distinguishable fluorescence in their monomer and aggregate.The hydrophilicity of monomer and the stability of aggregate are finely tuned by tailoring the linkers between two quaternary ammonium end groups and tetraphenylethylene skeleton.The sensitive fluorescence switching of monomer and aggregate achieves the quantitative monitoring of dynamic interaction of three amphiphiles with bacteria.The aggregates with cationic charges first attach to bacterial surface,and the monomers subsequently dissociate from aggregates to penetrate bacterial membrane.Further,our results reveal the vital role of stability of aggregates during antimicrobial process,shedding light on the rational design of high-efficient antimicrobials.展开更多
Amphiphilic molecules have long been regarded as an important class of supramolecular building blocks for the fabrication of nanomaterials. While most previous researches have mainly focused on amphiphlies with flexib...Amphiphilic molecules have long been regarded as an important class of supramolecular building blocks for the fabrication of nanomaterials. While most previous researches have mainly focused on amphiphlies with flexible structures, in this work, four novel amphiphiles possessing wholly-rigid skeletons have been designed and synthe- sized. These molecules were built by using 4,4＇-bipyridin-l-ium or viologen as hydrophilic moieties and phenyl or biphenyl as hydrophobic segments, bridged by a pyridazine unit. Their self-assembly behavior has been investigated by scanning electron microscopy （SEM）, atomic force microscopy （AFM） and transmission electron microscopy （TEM）, which revealed they could self-assemble into well-ordered nanoarchitectures with various morphologies such as vesicles, micro/nanorods and nanotubes in water or methanol, depending on their hydrophilic/hydrophobic fraction ratios.展开更多
The possibility of delivering DNA effi ciently to cells represents a crucial issue for the treatment of both genetic and acquired diseases.However,even although the effi ciency of non-viral transfection systems has im...The possibility of delivering DNA effi ciently to cells represents a crucial issue for the treatment of both genetic and acquired diseases.However,even although the effi ciency of non-viral transfection systems has improved in the last decade,none have yet proven to be suffi ciently effective in vivo.We report herein our results on the functionalization of single-walled carbon nanotubes(SWNT)and multi-walled carbon nanotubes(MWNT)by two cationic amphiphiles(lipid RPR120535 and pyrenyl polyamine),their use for the complexation of plasmid DNA,and their efficiency in transfecting cells in vitro.The experiments have shown that the efficiency of transfection is higher when using SWNT instead of MWNT,and that transfection effi ciency is similar or slightly higher when using nanoplexes(SWNT/lipid RPR120535/DNA)instead of lipoplexes(lipid RPR120535/DNA)and several orders of magnitude higher than that of naked DNA.This study therefore shows both that the transfection is better when using SWNTs and that it is dependent on the nature of the amphiphilic molecules adsorbed on the nanotubes.展开更多
This paper presents the preparations and characterization of vesicles of four new fluoro- carbon amphiphiles with 1,3-disubstituted glycerol structure in common and different headgroups (OH, 1; CO_2H, 2; quaternary am...This paper presents the preparations and characterization of vesicles of four new fluoro- carbon amphiphiles with 1,3-disubstituted glycerol structure in common and different headgroups (OH, 1; CO_2H, 2; quaternary ammonium salt, 3; and pyridinium salt, 4). These vesicles have higher transition temperature due to the stronger hydrophobic interaction between fluorocarbon chains. Addition of fluorocarbon additives with carboxylic acid or quaternary ammonium salt head group respectively shows different influences on phase behavior of vesicles of 2. These results are discussed based on the interaction within headgroup, hydrophobicity and specific mutahydrophobic interaction between fluoro- and hydrocarbon chains.展开更多
Heteracalixaromatics are an emerging generation of macrocyclic host molecules in supramolecular chemistry. As a typical example of heteracalixaromatics, oxacalix[2]arene[2]triazine adopts a shape-persistent 1,3-altern...Heteracalixaromatics are an emerging generation of macrocyclic host molecules in supramolecular chemistry. As a typical example of heteracalixaromatics, oxacalix[2]arene[2]triazine adopts a shape-persistent 1,3-alternate conformation and can be easily functionalized. Taking it as a platform, a series of oxacalix[2]arene[2]triazine-based amphiphiles bearing long alkyl chains were synthesized through post-macrocyclization functionalization or 3＋1 fragment coupling protocols. The self-assembly behavior of these arnphiphiles in a mixture of tetrahydrofuran （THF） and water was investigated. Dynamic light scattering （DLS） measurements revealed that the size of the self-assembled aggregates is dependent on the structure of the amphiphiles. The long alkyl chain substituents and/or interrnolecular hydrogen bonds were found to promote the self-assembly.展开更多
Naturally,subtle variations in the chemical structures of constituent molecules may significantly affect their multiscale spatial arrangements,properties,and functions.Deceptively simple spherical assemblies supply an...Naturally,subtle variations in the chemical structures of constituent molecules may significantly affect their multiscale spatial arrangements,properties,and functions.Deceptively simple spherical assemblies supply an ideal platform to investigate how subtle chemical differences affect hierarchically assembled structures.Here,the authors report two sets of nanosized shape amphiphiles,which were constructed by a triphenylene core and six polyhedral oligomeric silsesquioxane cages peripherally grafted through linkers.The slight differences in these samples are merely several methylene units in their linkers,including several pairs of constituent isomers.These nanosized shape amphiphiles self-assemble into a variety of unconventional spherical packing structures,which include the Frank-Kasperσphase and dodecagonal quasicrystal.Several types of unconventional phase transitions were systematically investigated.The authors alternated the conventional columnar phases of discotic molecules to unconventional spherical packing phases.These unconventional structures may shed light into discovering discotic mesogens-based materials with new properties and functions.展开更多
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 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.
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.
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the National Research Foundation of Korea(NRF)grants funded by the Korean government(MSIT)(RS-2024-00352931,NRF-2022R1A4A1031687, RS-2024-00408951)the KIST Institutional Program(2 V10330-24-P042)a Korea University grant.
文摘The transport of anions across cell membranes is diffi cult because of the negatively charged outer surfaces of cell membranes.To overcome this limitation,herein,we report a system for transporting aromatic anions across cellular membranes via self-assembly using a synthetic imidazolium-fused aromatic amphiphile.The amphiphile with cationic and aromatic groups in close proximity to each other could interact with anionic pyranine via electrostatic and aromatic interactions to form supramolecular vesicles.Supramolecular vesicles based on the synthetic imidazoliumfused aromatic amphiphile and pyranine complex transport anionic aromatic pyranine across the membranes of live MCf-7 cells without cytotoxicity.
文摘Cucurbituril （CB）, a well-known macrocyclic cavitand, has been used extensively to construct supramolecular aggregates. Based on host-vip intertactions, an adamantanyl derivative vip molecule was designed and syn- thesized to prepare a supramolecular amphiphile with cucurbit[7]uril. In aqueous solution, the cucurbit[7]uril based supramolecular amphiphiles self-assemble into well-defined vesicles, and their disassembly can be achieved by addition of excess competitive agent 1-adamantanamine hydrochloride. This vesicle functions as a new nanocapsule to encapsulate molecules within its hollow cavity. Through competitive disassembly of supramolecular amphiphiles, the vesicles behave as a novel drug delivery carrier.
基金National Natural Science Foundation of China,Grant/Award Numbers:21890731,21821001,21604066。
文摘With the development of deoxyribonucleic acid(DNA)nanotechnology,various DNA nanostructures and DNA devices have been constructed,which exhibit potential applications in material science and biomedicine.Taking advantage of the programmability and biocompatibility of DNA,novel building block to chemically functionalize DNA with hydrophobic organic molecules has attracted more and more attention.Driving by amphiphilicity,DNA-organic molecular amphiphiles have been demonstrated to self-assemble or further induce hierarchically assemblies,providing novel-specific properties.In this minireview,we summarize the recent progress of DNA organic molecular amphiphiles including their synthesis,self-assembly behavior in aqueous solution,and the amphiphilic self-assembly based on hierarchical DNA nano-structures.We further briefly discuss the perspective of the application of the DNA-organic molecular amphiphiles.
基金National Natural Science Foundation of China,Grant/Award Number:22002137Natural Science Foundation of Jiangsu Province,Grant/Award Number:BK20200920+1 种基金Beijing Natural Science Foundation,Grant/Award Number:2212013Shenzhen Key Laboratory of Functional Aggregate Materials,Grant/Award Number:ZDSYS20211021111400001。
文摘Cationic amphiphile aggregates exhibit superior antibacterial activity than monomers.However,the antimicrobial mechanism of aggregates has not been well understood because it is difficult to distinguish and monitor aggregate and monomer in antimicrobial process.Herein,three bola-type cationic amphiphiles with aggregation-induced emission property have been developed to show distinguishable fluorescence in their monomer and aggregate.The hydrophilicity of monomer and the stability of aggregate are finely tuned by tailoring the linkers between two quaternary ammonium end groups and tetraphenylethylene skeleton.The sensitive fluorescence switching of monomer and aggregate achieves the quantitative monitoring of dynamic interaction of three amphiphiles with bacteria.The aggregates with cationic charges first attach to bacterial surface,and the monomers subsequently dissociate from aggregates to penetrate bacterial membrane.Further,our results reveal the vital role of stability of aggregates during antimicrobial process,shedding light on the rational design of high-efficient antimicrobials.
基金We thank the National Natural Science Foundation of China （No. 21502216） and the Technology Commis- sion of Shanghai Municipality （No. 15ZR1449500） for the financial support.
文摘Amphiphilic molecules have long been regarded as an important class of supramolecular building blocks for the fabrication of nanomaterials. While most previous researches have mainly focused on amphiphlies with flexible structures, in this work, four novel amphiphiles possessing wholly-rigid skeletons have been designed and synthe- sized. These molecules were built by using 4,4＇-bipyridin-l-ium or viologen as hydrophilic moieties and phenyl or biphenyl as hydrophobic segments, bridged by a pyridazine unit. Their self-assembly behavior has been investigated by scanning electron microscopy （SEM）, atomic force microscopy （AFM） and transmission electron microscopy （TEM）, which revealed they could self-assemble into well-ordered nanoarchitectures with various morphologies such as vesicles, micro/nanorods and nanotubes in water or methanol, depending on their hydrophilic/hydrophobic fraction ratios.
文摘The possibility of delivering DNA effi ciently to cells represents a crucial issue for the treatment of both genetic and acquired diseases.However,even although the effi ciency of non-viral transfection systems has improved in the last decade,none have yet proven to be suffi ciently effective in vivo.We report herein our results on the functionalization of single-walled carbon nanotubes(SWNT)and multi-walled carbon nanotubes(MWNT)by two cationic amphiphiles(lipid RPR120535 and pyrenyl polyamine),their use for the complexation of plasmid DNA,and their efficiency in transfecting cells in vitro.The experiments have shown that the efficiency of transfection is higher when using SWNT instead of MWNT,and that transfection effi ciency is similar or slightly higher when using nanoplexes(SWNT/lipid RPR120535/DNA)instead of lipoplexes(lipid RPR120535/DNA)and several orders of magnitude higher than that of naked DNA.This study therefore shows both that the transfection is better when using SWNTs and that it is dependent on the nature of the amphiphilic molecules adsorbed on the nanotubes.
基金the National Natural Science Foundation of China.
文摘This paper presents the preparations and characterization of vesicles of four new fluoro- carbon amphiphiles with 1,3-disubstituted glycerol structure in common and different headgroups (OH, 1; CO_2H, 2; quaternary ammonium salt, 3; and pyridinium salt, 4). These vesicles have higher transition temperature due to the stronger hydrophobic interaction between fluorocarbon chains. Addition of fluorocarbon additives with carboxylic acid or quaternary ammonium salt head group respectively shows different influences on phase behavior of vesicles of 2. These results are discussed based on the interaction within headgroup, hydrophobicity and specific mutahydrophobic interaction between fluoro- and hydrocarbon chains.
基金supported by the National Natural Science Foundation of China(21272239,91427301,21521002)Ministry of Science and Technology(2013CB834504)
文摘Heteracalixaromatics are an emerging generation of macrocyclic host molecules in supramolecular chemistry. As a typical example of heteracalixaromatics, oxacalix[2]arene[2]triazine adopts a shape-persistent 1,3-alternate conformation and can be easily functionalized. Taking it as a platform, a series of oxacalix[2]arene[2]triazine-based amphiphiles bearing long alkyl chains were synthesized through post-macrocyclization functionalization or 3＋1 fragment coupling protocols. The self-assembly behavior of these arnphiphiles in a mixture of tetrahydrofuran （THF） and water was investigated. Dynamic light scattering （DLS） measurements revealed that the size of the self-assembled aggregates is dependent on the structure of the amphiphiles. The long alkyl chain substituents and/or interrnolecular hydrogen bonds were found to promote the self-assembly.
基金This study was supported by the Key-Area Research and Development Program of Guangdong Province(nos.2019B010941002 and 2020B010182002)the National Natural Science Foundation of China(nos.71890871 and U1832220)+2 种基金the Guangdong Provincial Key Laboratory of Functional and Intelligent Hybrid Materials and Devices(no.2019B121203003)Guangdong Project(no.2016ZT06C322)the Fundamental Research Funds for the Central Universities(no.2019JQ05).
文摘Naturally,subtle variations in the chemical structures of constituent molecules may significantly affect their multiscale spatial arrangements,properties,and functions.Deceptively simple spherical assemblies supply an ideal platform to investigate how subtle chemical differences affect hierarchically assembled structures.Here,the authors report two sets of nanosized shape amphiphiles,which were constructed by a triphenylene core and six polyhedral oligomeric silsesquioxane cages peripherally grafted through linkers.The slight differences in these samples are merely several methylene units in their linkers,including several pairs of constituent isomers.These nanosized shape amphiphiles self-assemble into a variety of unconventional spherical packing structures,which include the Frank-Kasperσphase and dodecagonal quasicrystal.Several types of unconventional phase transitions were systematically investigated.The authors alternated the conventional columnar phases of discotic molecules to unconventional spherical packing phases.These unconventional structures may shed light into discovering discotic mesogens-based materials with new properties and functions.
