Four glycoluril-based amphiphilic molecular clips(AMCs)M1~M4 have been prepared for intracellular delivery of short DNA.M1~M4 have two methyl groups on its convex surface and four cations on its aromatic side arm,whic...Four glycoluril-based amphiphilic molecular clips(AMCs)M1~M4 have been prepared for intracellular delivery of short DNA.M1~M4 have two methyl groups on its convex surface and four cations on its aromatic side arm,which can be used to construct self-assembled nanoparticles in aqueous solution driven by hydrophobic interaction.Dynamic light scattering experiments show that M1 and M2 can be driven hydrophobically to aggregate into extremely stable nanoparticles in water at the micromolar concentrations.Fluorescence titration and zeta potential experiments support that the nanoparticles formed by M1 and M2 are able to efficiently encapsulate short DNA(sDNA).Fluorescence imaging and flow cytometry studies reveal that their nano sizes enable intracellular delivery of the encapsulated sDNA into both normal and cancer cells,with delivery percentage reaching up to 94%,while in vitro experiments indicate that the two compounds have excellent biocompatibility and low cytotoxicity.展开更多
Hypocrellins are most suitable for photodynamic therapy (PDT) of the diseases occurring in the superficial layer, such as microvascular diseases, because of their special absorption spectral properties. However, hypoc...Hypocrellins are most suitable for photodynamic therapy (PDT) of the diseases occurring in the superficial layer, such as microvascular diseases, because of their special absorption spectral properties. However, hypocrellins and most of their derivatives are basically lipophilic, while the hydrophilic derivatives lose the PDT activity in vivo. Therefore, the key problem for practical application of PDT of microvascular diseases focuses on finding the derivatives which possess optimized amphiphilicity. Herein, we developed a theoretical method to estimate the amphiphilicity of a molecule by the calculated average polarity. Compared with the experimentally measured results, the method is proved to be applicable. Based on the computation and available experimental results, it can be concluded that the derivative must have the polarities around 0.22 for optimized amphiphilicity.展开更多
Facial amphiphilicity is an extraordinary chemical structure feature of a variety of antimicrobial peptides and polymers.Vast efforts have been dedicated to small molecular,macromolecular and dendrimer-like systems to...Facial amphiphilicity is an extraordinary chemical structure feature of a variety of antimicrobial peptides and polymers.Vast efforts have been dedicated to small molecular,macromolecular and dendrimer-like systems to mimic this highly preferred structure or conformation,including local facial amphiphilicity and global amphiphilicity.This work conceptualizes Facial Amphiphilicity Index(FAI)as a numerical value to quantitatively characterize the measure of chemical compositions and structural features in dictating antimicrobial efficacy.FAI is a ratio of numbers of charges to rings,representing both compositions of hydrophilicity and hydrophobicity.Cationic derivatives of multicyclic compounds were evaluated as model systems for testing antimicrobial selectivity against Gram-negative and Gram-positive bacteria.Both monocyclic and bicyclic compounds are non-antimicrobial regardless of FAIs.Antimicrobial efficacy was observed with systems having larger cross-sectional areas including tricyclic abietic acid and tetracyclic bile acid.While low and high FAIs respectively lead to higher and lower antimicrobial efficacy,in consideration of cytotoxicity,the sweet spot is typically suited with intermediate FAIs for each specific system.This can be well explained by the synergistic hydrophobic-hydrophobic and electrostatic interactions with bacterial cell membranes and the difference between bacterial and mammalian cell membranes.The adoption of FAI would pave a new avenue toward the design of next-generation antimicrobial macromolecules and peptides.展开更多
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
Biocompatible amphiphilic nanoparticles(NPs)with tunable particle morphology and surface property are important for their applications as functional materials.However,previously developed methods to prepare amphiphili...Biocompatible amphiphilic nanoparticles(NPs)with tunable particle morphology and surface property are important for their applications as functional materials.However,previously developed methods to prepare amphiphilic NPs generally involve several steps,especially an additional step for surface modification,greatly hindering their largescale production and widespread applications.Here,a versatile one-step strategy is developed to prepare biocompatible amphiphilic dimer NPs with tunable particle morphology and surface property.The amphiphilic dimer NPs,which consist of a hydrophobic shellac bulb and a hydrophilic poly(lactic acid)(PLA)bulb with PLA-poly(ethylene glycol)(PEG)on the bulb surface,are prepared in a single step by controlled co-precipitation and self-assembly.Amphiphilic PLA-PEG/shellac dimer NPs demonstrate excellent tunability in particle morphology,thus showing good performances in controlling the interfacial curvature and emulsion type.In addition,temperatureresponsive PLA-poly(N-isopropyl acrylamide)(PNIPAM)/shellac dimer NPs are prepared following the same method and emulsions stabilized by them show temperature-triggered response.The applications of PLA-PEG-folic acid(FA)/shellac dimer NPs for drug delivery have also been demonstrated,which show a very good performance.The strategy of preparing the dimer NPs is green,scalable,facile and versatile,which provides a good platform for the design of dimer NPs with tunable particle morphology and surface property for diverse applications.展开更多
This study prepared and characterized amphiphilic carboxymethyl cellulose stearate(CMCS)recycled from sugarcane bagasse agro-waste(SB).The Fourier-transform infrared(FTIR)analysis confirmed cellulose,carboxymethyl cel...This study prepared and characterized amphiphilic carboxymethyl cellulose stearate(CMCS)recycled from sugarcane bagasse agro-waste(SB).The Fourier-transform infrared(FTIR)analysis confirmed cellulose,carboxymethyl cellulose(CMC),and CMCS structures,with CMCS showing increased H-bonding.X-ray diffraction analysis(XRD)revealed reduced crystallinity in CMC and CMCS.CMCS exhibited a hydrophobic nature but dispersed in water,enabling nanoemulsion formation.Optimal nanoemulsion was achieved with CMCS1,showing a particle size of 99 nm.Transmission electron microscopy(TEM)images revealed CMC’s honeycomb structure,transforming into spherical particles in CMCS1.Antimicrobial tests demonstrated strong activity of CMCS formulations against Escherichia coli and Staphylococcus aureus,with CMCS3 exhibiting the highest efficacy.These findings highlight the potential of CMCS-based nanoemulsions for antimicrobial applications and nanoemulsification.展开更多
The multiple oligopeptides have been regarded as promising alignment media due to their structural diverseness and tendency for self-assembly in solution.Herein,an assembled amphiphilic peptide alignment medium,i.e.,C...The multiple oligopeptides have been regarded as promising alignment media due to their structural diverseness and tendency for self-assembly in solution.Herein,an assembled amphiphilic peptide alignment medium,i.e.,C15eCONH-Phg-Phg-IIIKK-CONH2 with un-natural amino acids for the determination of anisotropic parameters of NMR is introduced.The amphiphilic peptide can be self-assembled at low concentrations in DMSO and is stable and highly homogeneous.The NMR spectrum collected with the addition of the medium had fewer background signals.The utility of the acquired RDC data is demon-strated to determine relative configuration of three natural products,Helminthosporic acid,Estrone,and a-Santonin.展开更多
The development of an efficient dual-function catalytic-sorption system,which seamlessly integrates reaction and separation into a single step for extractant-free systems,represents a transformative advancement in oxi...The development of an efficient dual-function catalytic-sorption system,which seamlessly integrates reaction and separation into a single step for extractant-free systems,represents a transformative advancement in oxidative desulfurization(ODS)process.In this work,we introduce a novel dualfunction amphiphilic biochar(Mo/CBC)catalyst,functionalized with MoO_(3-x)featuring abundant oxygen vacancies,for highly effective extractant-free ODS.The polarity of the biochar was precisely tailored by varying the amount of KOH,leading to the creation of amphiphilic carriers.Subsequent ball milling facilitated the successful loading of MoO_(3-x)onto the biochar surface via an impregnation-calcination route leveraging carbon reduction,resulting in the synthesis of amphiphilic Mo/CBC catalysts.The amphiphilic nature of these catalysts ensures their stable dispersion within the oil phase,while also facilitating their interaction with the oxidant H2O2 and the adsorption of sulfur-containing oxidation products.Characterization techniques,including EPR,XPS,and in situ XRD,verified the existence of abundant oxygen vacancies obtained by carbon reduction on the amphiphilic Mo/CBC catalysts,which significantly boosted their activity in an extractant-free ODs system.Remarkably,the amphiphilic Mo/CBC catalyst displayed exceptional catalytic performance,achieving a desulfurization efficiency of 99.6%in just 10 min without extraction solvent.DFT theoretical calculations further revealed that H_(2)O_(2)readily dissociates into two OH radicals on the O_(vac)-MoO_(3),overcoming a low energy barrier.This process was identified as a key contributor to the catalyst's outstanding ODS performance.Furthermore,other biochar sources,such as rice straw,bamboo,rapeseed oil cake,and walnut oil cake,were investigated to produce Mo-based amphiphilic biochar catalysts,which all showed excellent desulfurization performance.This work establishes a versatile and highly efficient dual-function catalytic-sorption system by designing amphiphilic biochar catalysts enriched with oxygen vacancies,paving the way for the development of universally applicable ODS catalysts for industrial applications.展开更多
The hydration state of amphiphilic block copolymers during the self-assembly transition is closely related to the structure and properties of copolymers. In this study, the temperature-induced self-assembly of copolym...The hydration state of amphiphilic block copolymers during the self-assembly transition is closely related to the structure and properties of copolymers. In this study, the temperature-induced self-assembly of copolymer poly(N,N-dimethylacrylamide)-poly(diacetone acrylamide)(PDMAA_(30)-PDAAM_(60))_(2)in aqueous solution was monitored by near-infrared spectroscopy with water as a probe. The wavelet packet transform was employed to improve the spectral resolution. The spectral information of hydrated water surrounding the hydrophilic PDMAA and hydrophobic PDAAM blocks was then extracted, revealing the significant roles of water in morphological transition of the copolymer from spherical to worm-like micelles. Specifically, water molecules interacting with N atoms and C=O groups of the hydrophilic block gradually decrease during the morphological transition, while hydrogen-bond structures NH–CO of the hydrophobic block gradually break, bringing more water molecules into contact with the hydrophobic block. This work provides a foundation for exploring the role of water molecules during the self-assembly transition of complex block copolymers.展开更多
Conversion and capture of carbon pollutants based on carbon dioxide to valuable green oil-field chemicals are target all over the world for controlling the global warming.The present article used new room temperature ...Conversion and capture of carbon pollutants based on carbon dioxide to valuable green oil-field chemicals are target all over the world for controlling the global warming.The present article used new room temperature amphiphilic imidazolium ionic liquids with superior surface activity in the aqueous solutions to convert carbon dioxide gas to superior amphiphilic calcium carbonate nanoparticles.In this respect,tetra-cationic ionic liquids 2-(4-dodecyldimethylamino)phenyl)-1,3-bis(3-dodecyldimethylammnonio)propyl)bromide-1-H-imidazol-3-ium acetate and 2-(4-hexyldimethylamino)phenyl)-1,3-bis(3-hexcyldimethylammnonio)propyl)bromide-1 H-imidazol-3-ium acetate were prepared.Their chemical structures,thermal as well as their carbon dioxide absorption/desorption characteristicswere evaluated.Theywere used as solvent and capping agent to synthesize calcium carbonate nanoparticles with controlled crystalline lattice,sizes,thermal properties and spherical surface morphologies.The prepared calcium carbonate nanoparticles were used as additives for the commercial water based drilling mud to improve their filter lose and rheology.The data confirm that the lower concentrations of 2-(4-dodecyldimethylamino)phenyl)-1,3-bis(3-dodecyldimethylammnonio)propyl)bromide-1-H-imidazol-3-ium acetate achieved lower seawater filter lose and improved viscosities.展开更多
Carbon dioxide(CO_(2))marine sequestration by hydrate method is considered as one of the options to effectively achieve carbon reduction.However,the slow rate of hydrate formation becomes a major limiting factor.In vi...Carbon dioxide(CO_(2))marine sequestration by hydrate method is considered as one of the options to effectively achieve carbon reduction.However,the slow rate of hydrate formation becomes a major limiting factor.In view of the gas-water mass transfer problem which is the main obstacle,this paper explored the amphiphilic amino acids to promote the formation of CO_(2)hydrate and used low-field nuclear magnetic resonance(LNMR)to conduct an innovative study on its kinetics and spatiotemporal distribution.By comparing the promotion performance of L-methionine(L-met),L-cysteine(L-cys),and L-valine(L-val),the comprehensive kinetic promotion ability of L-met was the highest,reducing the induction time by 60.0%,achieving the maximum water conversion of about 57.0%within only 1 h,and reaching a final CO_(2)storage efficiency of 84.6%.LNMR results showed that hydrates were preferentially formed in large and medium pores in the reservoir region.Interestingly,we found that the combined effect of hydrophilic groups and the hydrophobic side chain of L-met not only promoted the rearrangement of water molecules and provided more nucleation sites,but also created a localized CO_(2)supersaturated environment and facilitated gas-water redistribution.Meanwhile,L-met promoted the formation of a hydrate porous structure to ensure the continuous formation of hydrates.This study innovatively explored CO_(2)hydrate formation behavior in amphiphilic amino acids and laid a theoretical foundation for the realization of CO_(2)marine sequestration by hydrate method.展开更多
It is well known that cationic polymers have excellent antimicrobial capacity accompanied with high biotoxicity,to reduce biotoxicity needs to decrease the number of cationic groups on polymers,which will influence an...It is well known that cationic polymers have excellent antimicrobial capacity accompanied with high biotoxicity,to reduce biotoxicity needs to decrease the number of cationic groups on polymers,which will influence antimicrobial activity.It is necessary to design a cationic polymer mimic natural antimicrobial peptide with excellent antibacterial activity and low toxicity to solve the above dilemma.Here,we designed and prepared a series of cationic poly(β-amino ester)s(PBAEs)with different cationic contents,and introducing hydrophobic alkyl chain to adjust the balance between antimicrobial activity and biotoxicity to obtain an ideal antimicrobial polymer.The optimum one of synthesized PBAE(hydrophilic cationic monomer:hydrophobic monomer=5:5)was screened by testing cytotoxicity and minimum inhibitory concentration(MIC),which can effectively kill S.aureus and E.coli with PBAE concentration of15μg/m L by a spread plate bacteriostatic method and dead and alive staining test.The way of PBAE killing bacterial was destroying the membrane like natural antimicrobial peptide observed by scanning electron microscopy(SEM).In addition,PBAE did not exhibit hemolysis and cytotoxicity.In particular,from the result of animal tests,the PBAE was able to promote healing of infected wounds from removing mature S.aureus and E.coli on the surface of infected wound.As a result,our work offers a viable approach for designing antimicrobial materials,highlighting the significant potential of PBAE polymers in the field of biomedical materials.展开更多
Herein,an alkyne-terminated acid/base responsive amphiphilic [2]rotaxane shuttle was synthesized,and then modified onto the glass surface through “click” reaction.The XPS N 1s spectrum and contactangle measurement w...Herein,an alkyne-terminated acid/base responsive amphiphilic [2]rotaxane shuttle was synthesized,and then modified onto the glass surface through “click” reaction.The XPS N 1s spectrum and contactangle measurement were performed to prove the successful immobilization.The amphiphilic [2]rotaxane functionalized surface presented controllable wettability responding to external acid-base stimuli.This bistable rotaxane modified material system promoted the practical application of molecular machines.展开更多
Owing to the spread of COVID-19,it is difficult to ignore the existence and importance of antimicrobial polymers(AMPs)because most protective appliances are made of polymers.Generally,bacteria prefer hydrophilic compo...Owing to the spread of COVID-19,it is difficult to ignore the existence and importance of antimicrobial polymers(AMPs)because most protective appliances are made of polymers.Generally,bacteria prefer hydrophilic compounds,while fungi prefer hydrophobic ones.In recent decades,AMPs have made significant strides due to the versatile design of the functional groups or units for hydrophilic,hydrophobic,or amphiphilic performances.This review summarizes the advances of AMPs itself from the perspective of their wettability.Moreover,this study aims to clarify how the functional groups determine the interaction between the polymer and microorganisms directly affects the antimicrobial efficacy of the designed polymers.Based on the advances,the challenges and outlooks of AMPs from the perspective of wettability are systematically discussed to build a bridge between the structural design of AMPs and the requirements of practical applications.展开更多
Enhancing the stability of supported noble metal catalysts emerges is a major challenge in both science and industry.Herein,a heterogeneous Pd catalyst(Pd/NCF)was prepared by supporting Pd ultrafine metal nanoparticle...Enhancing the stability of supported noble metal catalysts emerges is a major challenge in both science and industry.Herein,a heterogeneous Pd catalyst(Pd/NCF)was prepared by supporting Pd ultrafine metal nanoparticles(NPs)on nitrogen-doped carbon;synthesized by using F127 as a stabilizer,as well as chitosan as a carbon and nitrogen source.The Pd/NCF catalyst was efficient and recyclable for oxidative carbonylation of phenol to diphenyl carbonate,exhibiting higher stability than Pd/NC prepared without F127 addition.The hydrogen bond between chitosan(CTS)and F127 was enhanced by F127,which anchored the N in the free amino group,increasing the N content of the carbon material and ensuring that the support could provide sufficient N sites for the deposition of Pd NPs.This process helped to improve metal dispersion.The increased metal-support interaction,which limits the leaching and coarsening of Pd NPs,improves the stability of the Pd/NCF catalyst.Furthermore,density functional theory calculations indicated that pyridine N stabilized the Pd^(2+)species,significantly inhibiting the loss of Pd^(2+)in Pd/NCF during the reaction process.This work provides a promising avenue towards enhancing the stability of nitrogen-doped carbon-supported metal catalysts.展开更多
Inadequate strength and stability of active crude oil emulsions stabilized by conventional surfactants always lead to a limited plugging rate of plugging agents.Thus,to address this issue,the synthesis of amphiphilic ...Inadequate strength and stability of active crude oil emulsions stabilized by conventional surfactants always lead to a limited plugging rate of plugging agents.Thus,to address this issue,the synthesis of amphiphilic Janus nanosheets was effectively carried out for enhancing the system performances and subsequently characterized.Based on the outcomes of orthogonal tests,an assessment was conducted on the nanosheet and surfactant formulations to optimize the enhancement of emulsion properties.The experimental demonstration of the complex system has revealed its remarkable emulsifying capability,ability to decrease interfacial tension and improve rheological behavior at high temperature(80℃)and high salinity(35,000 ppm)conditions.Involving probable mechanism of the system performance enhancement is elucidated by considering the synergistic effect between surfactants and nanosheets.Furthermore,variables including water-to-oil ratio,salinity,temperature and stirring intensity during operation,which affect the properties of prepared emulsions,were investigated in detail.The efficacy and stability of the complex system in obstructing medium and high permeability cores were demonstrated.Notably,the core with a high permeability of 913.58 mD exhibited a plugging rate of 98.55%.This study establishes the foundations of medium and high permeability reservoirs plugging with novel active crude oil plugging agents in severe environments.展开更多
Marine corrosion and biofouling are challenges that affect marine industrial equipment,and protecting equipment with functional coatings is a simple and effective approach.However,it is extremely difficult to combine ...Marine corrosion and biofouling are challenges that affect marine industrial equipment,and protecting equipment with functional coatings is a simple and effective approach.However,it is extremely difficult to combine anti-corrosion and anti-fouling properties in a single coating.In this work,we combine reduced graphene oxide(rGO)/silver nanoparticles(AgNPs)with a hydrophilic polymer in a bio-based silicone-epoxy resin to create a coating with both anti-fouling and anti-corrosion properties.The excel-lent anti-fouling performance of the coating results from a ternary synergistic mechanism involving foul-ing release,contact inhibition,and a hydration effect,while the outstanding anti-corrosion performance is provided by a ternary synergistic anti-corrosion mechanism that includes a dense interpenetrating net-work(IPN)structure,a barrier effect,and passivation.The results show that the obtained coating pos-sesses superior anti-fouling activity against protein,bacteria,algae,and other marine organisms,as well as excellent anti-corrosion and certain self-healing properties due to its dynamic cross-linked net-work of rGO/AgNPs and the hydrophilic polymer.This work provides an anti-corrosion and anti-fouling integrated coating for marine industrial equipment.展开更多
An amphiphilic derivative with a large Stokes shift by introducing flexible hydrophilic long chains into a rigid ethylene-pyrene compound have been successfully synthesized.The alkylated compound exhibited a notable c...An amphiphilic derivative with a large Stokes shift by introducing flexible hydrophilic long chains into a rigid ethylene-pyrene compound have been successfully synthesized.The alkylated compound exhibited a notable change in charge distribution,facilitating cation-π interactions.Through the process of amphiphilic self-assembly,the formation of highly ordered aggregates enabled effective photo-dimerization under 449 nm LED irradiation.Notably,this photo-responsive technology not only exhibited advanced multi-color emission effects,including white light emission but also exhibited environmentally friendly behavior in the aqueous phase.展开更多
Stimuli-triggered release and alleviating resistance of iridium(Ⅲ)-based drugs at tumor sites remains challengeable for clinical hepatoma therapy.Herein,a doxorubicin@iridium-transferrin(DOX@Ir-TF)nanovesicle was syn...Stimuli-triggered release and alleviating resistance of iridium(Ⅲ)-based drugs at tumor sites remains challengeable for clinical hepatoma therapy.Herein,a doxorubicin@iridium-transferrin(DOX@Ir-TF)nanovesicle was synthesized by carboxylated-transferrin(TF)and doxorubicin-loaded amphiphilic iridium-amino with quaternary ammonium(QA)groups and disulfide bonds.The QA groups enhanced photophysical properties and broadened production capacity of photoinduced-reactive oxygen species(ROS),while the disulfide-bridged bonds regulated oxidative stress levels through reacting with glutathione(GSH);simultaneously,modification of TF improved recognition and endocytosis of the nanovesicle for tumor cells.Based on in-vitro results,a controlled-release behavior of DOX upon a dualresponsiveness of GSH and near-infrared ray(NIR)irradiation was presented,along with high-efficiency generation of ROS.After an intravenous injection,the nanovesicle was targeted at tumor sites,realizing TF-navigated photoacoustic imaging guidance and synergistic chemotherapy-photodynamic therapy under NIR/GSH stimulations.Overall,newly-synthesized DOX@Ir-TF nanovesicle provided a potential in subcutaneous hepatocellular carcinoma therapy due to integrations of targeting delivery,dual-stimuli responsive release,synergistic therapy strategy,and real-time monitoring.展开更多
Exploring novel materials with excellent photothermal conversion capabilities for solar photothermal water evaporation is considered as an ideal strategy to simultaneously realize the direct and full use of the widely...Exploring novel materials with excellent photothermal conversion capabilities for solar photothermal water evaporation is considered as an ideal strategy to simultaneously realize the direct and full use of the widely distributed solar energy and alleviate the world's freshwater scarcity.Herein,an amphiphilic photothermal membrane is prepared through the self-assembly of hydrophilic heteropoly blue(HPB,H_(3)PMo_(12)O_(40))and hydrophobic surfactant(dioctadecyl dimethyl ammonium bromide,DODA).Benefiting from the synergistic effects of alternating functional hydrophilic HPB and hydrophobic DODA layers,the flexible membrane based on two-dimensional DODA-HPB self-assemblies(DODA-HPB/Nylon66)exhibits superior photothermal conversion properties,showing promising prospects in applications of solar desalination and wastewater treatment.展开更多
文摘Four glycoluril-based amphiphilic molecular clips(AMCs)M1~M4 have been prepared for intracellular delivery of short DNA.M1~M4 have two methyl groups on its convex surface and four cations on its aromatic side arm,which can be used to construct self-assembled nanoparticles in aqueous solution driven by hydrophobic interaction.Dynamic light scattering experiments show that M1 and M2 can be driven hydrophobically to aggregate into extremely stable nanoparticles in water at the micromolar concentrations.Fluorescence titration and zeta potential experiments support that the nanoparticles formed by M1 and M2 are able to efficiently encapsulate short DNA(sDNA).Fluorescence imaging and flow cytometry studies reveal that their nano sizes enable intracellular delivery of the encapsulated sDNA into both normal and cancer cells,with delivery percentage reaching up to 94%,while in vitro experiments indicate that the two compounds have excellent biocompatibility and low cytotoxicity.
文摘Hypocrellins are most suitable for photodynamic therapy (PDT) of the diseases occurring in the superficial layer, such as microvascular diseases, because of their special absorption spectral properties. However, hypocrellins and most of their derivatives are basically lipophilic, while the hydrophilic derivatives lose the PDT activity in vivo. Therefore, the key problem for practical application of PDT of microvascular diseases focuses on finding the derivatives which possess optimized amphiphilicity. Herein, we developed a theoretical method to estimate the amphiphilicity of a molecule by the calculated average polarity. Compared with the experimentally measured results, the method is proved to be applicable. Based on the computation and available experimental results, it can be concluded that the derivative must have the polarities around 0.22 for optimized amphiphilicity.
文摘Facial amphiphilicity is an extraordinary chemical structure feature of a variety of antimicrobial peptides and polymers.Vast efforts have been dedicated to small molecular,macromolecular and dendrimer-like systems to mimic this highly preferred structure or conformation,including local facial amphiphilicity and global amphiphilicity.This work conceptualizes Facial Amphiphilicity Index(FAI)as a numerical value to quantitatively characterize the measure of chemical compositions and structural features in dictating antimicrobial efficacy.FAI is a ratio of numbers of charges to rings,representing both compositions of hydrophilicity and hydrophobicity.Cationic derivatives of multicyclic compounds were evaluated as model systems for testing antimicrobial selectivity against Gram-negative and Gram-positive bacteria.Both monocyclic and bicyclic compounds are non-antimicrobial regardless of FAIs.Antimicrobial efficacy was observed with systems having larger cross-sectional areas including tricyclic abietic acid and tetracyclic bile acid.While low and high FAIs respectively lead to higher and lower antimicrobial efficacy,in consideration of cytotoxicity,the sweet spot is typically suited with intermediate FAIs for each specific system.This can be well explained by the synergistic hydrophobic-hydrophobic and electrostatic interactions with bacterial cell membranes and the difference between bacterial and mammalian cell membranes.The adoption of FAI would pave a new avenue toward the design of next-generation antimicrobial macromolecules and peptides.
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supported by National Natural Science Foundation of China(No.22278352)National Key Research and Development Program of China(No.2021YFC3001100)+3 种基金Longyan City Science and Technology Plan Project(No.2020LYF17043)Longyan City Science and Technology Plan Project(No.2020LYF17042)ARC Discovery Project(No.DP200101238)and NHMRC Investigator Grant(No.APP2008698)supported by the Harvard Materials Research Science and Engineering Center(No.DMR2011754)。
文摘Biocompatible amphiphilic nanoparticles(NPs)with tunable particle morphology and surface property are important for their applications as functional materials.However,previously developed methods to prepare amphiphilic NPs generally involve several steps,especially an additional step for surface modification,greatly hindering their largescale production and widespread applications.Here,a versatile one-step strategy is developed to prepare biocompatible amphiphilic dimer NPs with tunable particle morphology and surface property.The amphiphilic dimer NPs,which consist of a hydrophobic shellac bulb and a hydrophilic poly(lactic acid)(PLA)bulb with PLA-poly(ethylene glycol)(PEG)on the bulb surface,are prepared in a single step by controlled co-precipitation and self-assembly.Amphiphilic PLA-PEG/shellac dimer NPs demonstrate excellent tunability in particle morphology,thus showing good performances in controlling the interfacial curvature and emulsion type.In addition,temperatureresponsive PLA-poly(N-isopropyl acrylamide)(PNIPAM)/shellac dimer NPs are prepared following the same method and emulsions stabilized by them show temperature-triggered response.The applications of PLA-PEG-folic acid(FA)/shellac dimer NPs for drug delivery have also been demonstrated,which show a very good performance.The strategy of preparing the dimer NPs is green,scalable,facile and versatile,which provides a good platform for the design of dimer NPs with tunable particle morphology and surface property for diverse applications.
文摘This study prepared and characterized amphiphilic carboxymethyl cellulose stearate(CMCS)recycled from sugarcane bagasse agro-waste(SB).The Fourier-transform infrared(FTIR)analysis confirmed cellulose,carboxymethyl cellulose(CMC),and CMCS structures,with CMCS showing increased H-bonding.X-ray diffraction analysis(XRD)revealed reduced crystallinity in CMC and CMCS.CMCS exhibited a hydrophobic nature but dispersed in water,enabling nanoemulsion formation.Optimal nanoemulsion was achieved with CMCS1,showing a particle size of 99 nm.Transmission electron microscopy(TEM)images revealed CMC’s honeycomb structure,transforming into spherical particles in CMCS1.Antimicrobial tests demonstrated strong activity of CMCS formulations against Escherichia coli and Staphylococcus aureus,with CMCS3 exhibiting the highest efficacy.These findings highlight the potential of CMCS-based nanoemulsions for antimicrobial applications and nanoemulsification.
基金supported by the National Natural Science Foundation of China(21874158)the Science and Technology Major Program of Gansu Province of China(22ZD6FA006 and 23ZDFA015)+1 种基金We are also grateful for the financial support from the Science and Technology Program of Henan Province(232102311180)the foundation for the University Young Key Teacher of Henan Province(2024GGJS116).
文摘The multiple oligopeptides have been regarded as promising alignment media due to their structural diverseness and tendency for self-assembly in solution.Herein,an assembled amphiphilic peptide alignment medium,i.e.,C15eCONH-Phg-Phg-IIIKK-CONH2 with un-natural amino acids for the determination of anisotropic parameters of NMR is introduced.The amphiphilic peptide can be self-assembled at low concentrations in DMSO and is stable and highly homogeneous.The NMR spectrum collected with the addition of the medium had fewer background signals.The utility of the acquired RDC data is demon-strated to determine relative configuration of three natural products,Helminthosporic acid,Estrone,and a-Santonin.
基金supported by the National Natural Science Foundation of China(22162008)the Science and Technology Supporting Project of Guizhou Province([2022]208)+1 种基金the Guizhou Province Local Government Overseas Study Programthe open project of Guizhou Provincial Double Carbon and Renewable Energy Technology Innovation Research Institute.
文摘The development of an efficient dual-function catalytic-sorption system,which seamlessly integrates reaction and separation into a single step for extractant-free systems,represents a transformative advancement in oxidative desulfurization(ODS)process.In this work,we introduce a novel dualfunction amphiphilic biochar(Mo/CBC)catalyst,functionalized with MoO_(3-x)featuring abundant oxygen vacancies,for highly effective extractant-free ODS.The polarity of the biochar was precisely tailored by varying the amount of KOH,leading to the creation of amphiphilic carriers.Subsequent ball milling facilitated the successful loading of MoO_(3-x)onto the biochar surface via an impregnation-calcination route leveraging carbon reduction,resulting in the synthesis of amphiphilic Mo/CBC catalysts.The amphiphilic nature of these catalysts ensures their stable dispersion within the oil phase,while also facilitating their interaction with the oxidant H2O2 and the adsorption of sulfur-containing oxidation products.Characterization techniques,including EPR,XPS,and in situ XRD,verified the existence of abundant oxygen vacancies obtained by carbon reduction on the amphiphilic Mo/CBC catalysts,which significantly boosted their activity in an extractant-free ODs system.Remarkably,the amphiphilic Mo/CBC catalyst displayed exceptional catalytic performance,achieving a desulfurization efficiency of 99.6%in just 10 min without extraction solvent.DFT theoretical calculations further revealed that H_(2)O_(2)readily dissociates into two OH radicals on the O_(vac)-MoO_(3),overcoming a low energy barrier.This process was identified as a key contributor to the catalyst's outstanding ODS performance.Furthermore,other biochar sources,such as rice straw,bamboo,rapeseed oil cake,and walnut oil cake,were investigated to produce Mo-based amphiphilic biochar catalysts,which all showed excellent desulfurization performance.This work establishes a versatile and highly efficient dual-function catalytic-sorption system by designing amphiphilic biochar catalysts enriched with oxygen vacancies,paving the way for the development of universally applicable ODS catalysts for industrial applications.
基金supported by the National Natural Science Foundation of China (Nos. 22174075 and 22374082)the Haihe Laboratory of Sustainable Chemical Transformations。
文摘The hydration state of amphiphilic block copolymers during the self-assembly transition is closely related to the structure and properties of copolymers. In this study, the temperature-induced self-assembly of copolymer poly(N,N-dimethylacrylamide)-poly(diacetone acrylamide)(PDMAA_(30)-PDAAM_(60))_(2)in aqueous solution was monitored by near-infrared spectroscopy with water as a probe. The wavelet packet transform was employed to improve the spectral resolution. The spectral information of hydrated water surrounding the hydrophilic PDMAA and hydrophobic PDAAM blocks was then extracted, revealing the significant roles of water in morphological transition of the copolymer from spherical to worm-like micelles. Specifically, water molecules interacting with N atoms and C=O groups of the hydrophilic block gradually decrease during the morphological transition, while hydrogen-bond structures NH–CO of the hydrophobic block gradually break, bringing more water molecules into contact with the hydrophobic block. This work provides a foundation for exploring the role of water molecules during the self-assembly transition of complex block copolymers.
基金supported by Science,Technology&Innovation Funding Authority(STDF)under grant(No.47062).
文摘Conversion and capture of carbon pollutants based on carbon dioxide to valuable green oil-field chemicals are target all over the world for controlling the global warming.The present article used new room temperature amphiphilic imidazolium ionic liquids with superior surface activity in the aqueous solutions to convert carbon dioxide gas to superior amphiphilic calcium carbonate nanoparticles.In this respect,tetra-cationic ionic liquids 2-(4-dodecyldimethylamino)phenyl)-1,3-bis(3-dodecyldimethylammnonio)propyl)bromide-1-H-imidazol-3-ium acetate and 2-(4-hexyldimethylamino)phenyl)-1,3-bis(3-hexcyldimethylammnonio)propyl)bromide-1 H-imidazol-3-ium acetate were prepared.Their chemical structures,thermal as well as their carbon dioxide absorption/desorption characteristicswere evaluated.Theywere used as solvent and capping agent to synthesize calcium carbonate nanoparticles with controlled crystalline lattice,sizes,thermal properties and spherical surface morphologies.The prepared calcium carbonate nanoparticles were used as additives for the commercial water based drilling mud to improve their filter lose and rheology.The data confirm that the lower concentrations of 2-(4-dodecyldimethylamino)phenyl)-1,3-bis(3-dodecyldimethylammnonio)propyl)bromide-1-H-imidazol-3-ium acetate achieved lower seawater filter lose and improved viscosities.
基金supported by the National Key Research and Development Program of China for Young Scientists(Grant No.2023YFB4104100)the National Natural Science Foundation of China(Grant 52176057)+3 种基金the National Key Research and Development Program of China(Grant No.2023YFB4104201)supported by the Unveiling and Commanding Foundation of Liaoning Province(Grant 2023JH1/10400003)the Shenzhen Science and Technology Program(No.JCYJ20220818095605012)supported by the Young Changjiang Scholars programme of China。
文摘Carbon dioxide(CO_(2))marine sequestration by hydrate method is considered as one of the options to effectively achieve carbon reduction.However,the slow rate of hydrate formation becomes a major limiting factor.In view of the gas-water mass transfer problem which is the main obstacle,this paper explored the amphiphilic amino acids to promote the formation of CO_(2)hydrate and used low-field nuclear magnetic resonance(LNMR)to conduct an innovative study on its kinetics and spatiotemporal distribution.By comparing the promotion performance of L-methionine(L-met),L-cysteine(L-cys),and L-valine(L-val),the comprehensive kinetic promotion ability of L-met was the highest,reducing the induction time by 60.0%,achieving the maximum water conversion of about 57.0%within only 1 h,and reaching a final CO_(2)storage efficiency of 84.6%.LNMR results showed that hydrates were preferentially formed in large and medium pores in the reservoir region.Interestingly,we found that the combined effect of hydrophilic groups and the hydrophobic side chain of L-met not only promoted the rearrangement of water molecules and provided more nucleation sites,but also created a localized CO_(2)supersaturated environment and facilitated gas-water redistribution.Meanwhile,L-met promoted the formation of a hydrate porous structure to ensure the continuous formation of hydrates.This study innovatively explored CO_(2)hydrate formation behavior in amphiphilic amino acids and laid a theoretical foundation for the realization of CO_(2)marine sequestration by hydrate method.
基金financially supported by the Natural Science Foundation of Jilin Province Science and Technology Department(No.20230101221JC)the National Natural Science Foundation of China(Nos.52173115,52073278,52203189)the Research Foundation for Advanced Talents of Xiamen University of Technology(Nos.5010423019,YKJ22052R)。
文摘It is well known that cationic polymers have excellent antimicrobial capacity accompanied with high biotoxicity,to reduce biotoxicity needs to decrease the number of cationic groups on polymers,which will influence antimicrobial activity.It is necessary to design a cationic polymer mimic natural antimicrobial peptide with excellent antibacterial activity and low toxicity to solve the above dilemma.Here,we designed and prepared a series of cationic poly(β-amino ester)s(PBAEs)with different cationic contents,and introducing hydrophobic alkyl chain to adjust the balance between antimicrobial activity and biotoxicity to obtain an ideal antimicrobial polymer.The optimum one of synthesized PBAE(hydrophilic cationic monomer:hydrophobic monomer=5:5)was screened by testing cytotoxicity and minimum inhibitory concentration(MIC),which can effectively kill S.aureus and E.coli with PBAE concentration of15μg/m L by a spread plate bacteriostatic method and dead and alive staining test.The way of PBAE killing bacterial was destroying the membrane like natural antimicrobial peptide observed by scanning electron microscopy(SEM).In addition,PBAE did not exhibit hemolysis and cytotoxicity.In particular,from the result of animal tests,the PBAE was able to promote healing of infected wounds from removing mature S.aureus and E.coli on the surface of infected wound.As a result,our work offers a viable approach for designing antimicrobial materials,highlighting the significant potential of PBAE polymers in the field of biomedical materials.
基金supported by the National Natural Science Foundation of China(Nos.21901063,U20041101)Young Talents Personnel Fund of Henan Agricultural University(No.30500604)Key Science and Technology Foundation of Henan Province(Nos.242102230178,232102310379)。
文摘Herein,an alkyne-terminated acid/base responsive amphiphilic [2]rotaxane shuttle was synthesized,and then modified onto the glass surface through “click” reaction.The XPS N 1s spectrum and contactangle measurement were performed to prove the successful immobilization.The amphiphilic [2]rotaxane functionalized surface presented controllable wettability responding to external acid-base stimuli.This bistable rotaxane modified material system promoted the practical application of molecular machines.
基金supported by the National Natural Science Foundation of China(Nos.52273118,22275013)。
文摘Owing to the spread of COVID-19,it is difficult to ignore the existence and importance of antimicrobial polymers(AMPs)because most protective appliances are made of polymers.Generally,bacteria prefer hydrophilic compounds,while fungi prefer hydrophobic ones.In recent decades,AMPs have made significant strides due to the versatile design of the functional groups or units for hydrophilic,hydrophobic,or amphiphilic performances.This review summarizes the advances of AMPs itself from the perspective of their wettability.Moreover,this study aims to clarify how the functional groups determine the interaction between the polymer and microorganisms directly affects the antimicrobial efficacy of the designed polymers.Based on the advances,the challenges and outlooks of AMPs from the perspective of wettability are systematically discussed to build a bridge between the structural design of AMPs and the requirements of practical applications.
基金support by the National Natural Science Foundation of China(U21A20306,U20A20152)Natural Science Foundation of Hebei Province(B2022202077).
文摘Enhancing the stability of supported noble metal catalysts emerges is a major challenge in both science and industry.Herein,a heterogeneous Pd catalyst(Pd/NCF)was prepared by supporting Pd ultrafine metal nanoparticles(NPs)on nitrogen-doped carbon;synthesized by using F127 as a stabilizer,as well as chitosan as a carbon and nitrogen source.The Pd/NCF catalyst was efficient and recyclable for oxidative carbonylation of phenol to diphenyl carbonate,exhibiting higher stability than Pd/NC prepared without F127 addition.The hydrogen bond between chitosan(CTS)and F127 was enhanced by F127,which anchored the N in the free amino group,increasing the N content of the carbon material and ensuring that the support could provide sufficient N sites for the deposition of Pd NPs.This process helped to improve metal dispersion.The increased metal-support interaction,which limits the leaching and coarsening of Pd NPs,improves the stability of the Pd/NCF catalyst.Furthermore,density functional theory calculations indicated that pyridine N stabilized the Pd^(2+)species,significantly inhibiting the loss of Pd^(2+)in Pd/NCF during the reaction process.This work provides a promising avenue towards enhancing the stability of nitrogen-doped carbon-supported metal catalysts.
基金financially supported by National Natural Science Foundation of China(52374053)Beijing Natural Science Foundation(2204092)Beijing Municipal Excellent Talent Training Funds Youth Advanced Individual Project(2018000020124G163)。
文摘Inadequate strength and stability of active crude oil emulsions stabilized by conventional surfactants always lead to a limited plugging rate of plugging agents.Thus,to address this issue,the synthesis of amphiphilic Janus nanosheets was effectively carried out for enhancing the system performances and subsequently characterized.Based on the outcomes of orthogonal tests,an assessment was conducted on the nanosheet and surfactant formulations to optimize the enhancement of emulsion properties.The experimental demonstration of the complex system has revealed its remarkable emulsifying capability,ability to decrease interfacial tension and improve rheological behavior at high temperature(80℃)and high salinity(35,000 ppm)conditions.Involving probable mechanism of the system performance enhancement is elucidated by considering the synergistic effect between surfactants and nanosheets.Furthermore,variables including water-to-oil ratio,salinity,temperature and stirring intensity during operation,which affect the properties of prepared emulsions,were investigated in detail.The efficacy and stability of the complex system in obstructing medium and high permeability cores were demonstrated.Notably,the core with a high permeability of 913.58 mD exhibited a plugging rate of 98.55%.This study establishes the foundations of medium and high permeability reservoirs plugging with novel active crude oil plugging agents in severe environments.
基金supported by the Major Project of Ningbo Science and Technology Innovation 2025(2021Z092)the Defense Industrial Technology Development Program(JCKY2021513B001).
文摘Marine corrosion and biofouling are challenges that affect marine industrial equipment,and protecting equipment with functional coatings is a simple and effective approach.However,it is extremely difficult to combine anti-corrosion and anti-fouling properties in a single coating.In this work,we combine reduced graphene oxide(rGO)/silver nanoparticles(AgNPs)with a hydrophilic polymer in a bio-based silicone-epoxy resin to create a coating with both anti-fouling and anti-corrosion properties.The excel-lent anti-fouling performance of the coating results from a ternary synergistic mechanism involving foul-ing release,contact inhibition,and a hydration effect,while the outstanding anti-corrosion performance is provided by a ternary synergistic anti-corrosion mechanism that includes a dense interpenetrating net-work(IPN)structure,a barrier effect,and passivation.The results show that the obtained coating pos-sesses superior anti-fouling activity against protein,bacteria,algae,and other marine organisms,as well as excellent anti-corrosion and certain self-healing properties due to its dynamic cross-linked net-work of rGO/AgNPs and the hydrophilic polymer.This work provides an anti-corrosion and anti-fouling integrated coating for marine industrial equipment.
基金supported by the National Natural Science Foundation of China(No.21602124)Fluorine Silicone Materials Collaborative Fund of Shandong Provincial Natural Science Foundation(No.ZR2021LFG007)+1 种基金Key R&D Program of Shandong Province(No.2019JZZY020229)the Young Scholars Program of Shandong University(No.2018WLJH40)。
文摘An amphiphilic derivative with a large Stokes shift by introducing flexible hydrophilic long chains into a rigid ethylene-pyrene compound have been successfully synthesized.The alkylated compound exhibited a notable change in charge distribution,facilitating cation-π interactions.Through the process of amphiphilic self-assembly,the formation of highly ordered aggregates enabled effective photo-dimerization under 449 nm LED irradiation.Notably,this photo-responsive technology not only exhibited advanced multi-color emission effects,including white light emission but also exhibited environmentally friendly behavior in the aqueous phase.
基金supported by the National Key R&D Program of China(Nos.2022YFB3808000,2022YFB3808001)the Project for High-Level Talent Innovation and Entrepreneurship of Quanzhou(No.2022C016R)+1 种基金the Medical Innovation Project of Science and Technology Program of Fujian Provincial Health Commission(No.2021CXA006)the Key Program of Qingyuan Innovation Laboratory(No.00221002).
文摘Stimuli-triggered release and alleviating resistance of iridium(Ⅲ)-based drugs at tumor sites remains challengeable for clinical hepatoma therapy.Herein,a doxorubicin@iridium-transferrin(DOX@Ir-TF)nanovesicle was synthesized by carboxylated-transferrin(TF)and doxorubicin-loaded amphiphilic iridium-amino with quaternary ammonium(QA)groups and disulfide bonds.The QA groups enhanced photophysical properties and broadened production capacity of photoinduced-reactive oxygen species(ROS),while the disulfide-bridged bonds regulated oxidative stress levels through reacting with glutathione(GSH);simultaneously,modification of TF improved recognition and endocytosis of the nanovesicle for tumor cells.Based on in-vitro results,a controlled-release behavior of DOX upon a dualresponsiveness of GSH and near-infrared ray(NIR)irradiation was presented,along with high-efficiency generation of ROS.After an intravenous injection,the nanovesicle was targeted at tumor sites,realizing TF-navigated photoacoustic imaging guidance and synergistic chemotherapy-photodynamic therapy under NIR/GSH stimulations.Overall,newly-synthesized DOX@Ir-TF nanovesicle provided a potential in subcutaneous hepatocellular carcinoma therapy due to integrations of targeting delivery,dual-stimuli responsive release,synergistic therapy strategy,and real-time monitoring.
基金supported by the National Natural Science Foundation of China(22071020,22171041,22271043,22205034)Natural Science Foundation of Jilin Province Science and Technology Department(20220101045JC)the Fundamental Research Funds for the Central Universities(2412021QD008,2412022QD012)
文摘Exploring novel materials with excellent photothermal conversion capabilities for solar photothermal water evaporation is considered as an ideal strategy to simultaneously realize the direct and full use of the widely distributed solar energy and alleviate the world's freshwater scarcity.Herein,an amphiphilic photothermal membrane is prepared through the self-assembly of hydrophilic heteropoly blue(HPB,H_(3)PMo_(12)O_(40))and hydrophobic surfactant(dioctadecyl dimethyl ammonium bromide,DODA).Benefiting from the synergistic effects of alternating functional hydrophilic HPB and hydrophobic DODA layers,the flexible membrane based on two-dimensional DODA-HPB self-assemblies(DODA-HPB/Nylon66)exhibits superior photothermal conversion properties,showing promising prospects in applications of solar desalination and wastewater treatment.
