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
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
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
Phospholipids have the characteristics of excellent biocompatibility and a especial amphiphilicity.These unique properties make phospholipids most appropriate to be employed as important pharmaceutical excipients and ...Phospholipids have the characteristics of excellent biocompatibility and a especial amphiphilicity.These unique properties make phospholipids most appropriate to be employed as important pharmaceutical excipients and they have a very wide range of applications in drug delivery systems.The aim of this review is to summarize phospholipids and some of their related applications in drug delivery systems,and highlight the relationship between the properties and applications,and the effect of the species of phospholipids on the efficiency of drug delivery.We refer to some relevant literatures,starting from the structures,main sources and properties of phospholipids to introduce their applications in drug delivery systems.The present article focuses on introducing five types of carriers based on phospholipids,including liposomes,intravenous lipid emulsions,micelles,drug-phospholipids complexes and cochleates.展开更多
A series of water soluble aliphatic hyperbranched poly(amido amine)s(PAMAMs) with the same or similar chemical structure of poly(amido amine) dendrimer was successfully synthesized from commercially available AB and C...A series of water soluble aliphatic hyperbranched poly(amido amine)s(PAMAMs) with the same or similar chemical structure of poly(amido amine) dendrimer was successfully synthesized from commercially available AB and C_n types of monomers by one-pot polymerization via the couple-monomer methodology(CMM). The AB type monomer used in this paper was methyl acrylate, and C_n monomers were multi-amino compounds such as ethylenediamine(EDA), diethylenetriamine(DETA), triethylenetetraamine(TETA), tetraethylenepentaamine(TEPA) and pentaethylenehexamine(PEHA). The reaction mechanism was investigated by means of the mass spectra of the reaction intermediates. Adjusting the feed ratio of AB to C_n, hyperbranched polymers with different terminal groups and properties were obtained. FTIR, NMR, DSC, and TGA were used to characterize the polymers. It was found that the polymers′ properties such as solubility, thermal behaviour and encapsulation capability varied with changing the feed ratio of AB to C_n. Benzoyl and palmitoyl groups were introduced into these macromolecules by acidylation to form amphiphilic hyperbranched polymers which have a high capability to encapsulate water soluble dyes such as Congo red. It is expected that the hyperbranched PAMAMs can play an important role in the industrial applications, such as coatings, cross-linking and phase-transferring agents because of their versatility and availability.展开更多
Macromolecule nanocrystal network and strong interfacial interaction are always beneficial to enhance the mechanical property of polymer-based nanocomposites.Poly(vinyl alcohol)(PVA),a typical biocompatible semicrysta...Macromolecule nanocrystal network and strong interfacial interaction are always beneficial to enhance the mechanical property of polymer-based nanocomposites.Poly(vinyl alcohol)(PVA),a typical biocompatible semicrystalline polymer,is an ideal candidate for preparing high performance polymer-based nanocomposites.However,the rich hydrogen bonds between PVA matrix and graphene oxide(GO)can disrupt the formation of PVA nanocrystal network.Thus,it remains a great challenge to achieve both strong and tough PVA-GO nanocomposites.Herein,by introducing a novel Janus-like amphiphilic graphene oxide(JGO),both hydrogen bonding and interfacial crystallization have been constructed between JGO sheets and PVA matrix.Benefiting from amphiphilic interfacial interaction and the enhanced crystal network,both PVA-JGO dried films and their swollen hydrogel films show superior mechanical properties than those of traditional PVA-GO nanocomposites.PVA-JGO dried films exhibit a 264%improvement of toughness at a JGO loading of 1 wt%.Meanwhile,the corresponding PVA-JGO swollen hydrogel films display simultaneous improvement of nearly 8 times increase of tensile strength and 20 times increase of toughness compared to traditional PVA-GO nanocomposite.This work indicates multiple interfacial interactions and macromolecule crystal networks can be concurrent in PVA nanocomposites by innovative modification of nanofillers,providing a new strategy to construct PVA nanocomposites with high strength and high toughness.The integration of outstanding mechanical and swelling resistance properties on PVA-JGO nanocomposite films render their promising applications,such as packaging and toughening hydrogel materials.展开更多
Liquid trimethoxy silane-functionalized cis-polybutadiene(cis-PB-Si(OMe)3),possessing number-average molecular weights of cis-PB segments(Mn,PB)ranging from 1800 g/mol to 5400 g/mol,with cis-1,4 content of ca.80%and h...Liquid trimethoxy silane-functionalized cis-polybutadiene(cis-PB-Si(OMe)3),possessing number-average molecular weights of cis-PB segments(Mn,PB)ranging from 1800 g/mol to 5400 g/mol,with cis-1,4 content of ca.80%and high functionality(>96%)could be synthesized by coordination copolymerization of living cis-PB chain ends with ethenyltrimethoxy-silane with neodymium-based catalytic system.The silicon hydroxyl-functionalized cis-polybutadiene(cis-PB-Si(OH)_(3))-based micelles in water have been achieved by in situ hydrolysis of cis-PB-Si(OMe)_(3)in hexane/water mixture(pH=6.8)at 70℃and by sequential removal of residue hexane.The size of the above micelles with soft elastic cis-PB cores could be remarkably enlarged by loading SiO_(2)nanoparticles on their surfaces via hydrogen bonding interaction.Giant supramolecular long chain aggregates or networks formed by hydrogen bonding interaction and possible O—Si—O chemical bonds between cis-PB-Si(OH)3-based micellar surfaces had relatively large size and thus precipitated from water after several months of storage,leading to production of cis-PB-Si(OH)_(3)solid elastomer with extremely low T_(g)at−107.0℃.The left cis-PB-Si(OH)_(3)-based micelles in water with relatively small size gradually formed the water-insoluble cis-PB-Si(OH)_(3)-based supramolecular aggregates or networks.The cis-PB-Si(OH)_(3)-based supramolecular elastomer exhibited excellent self-healing property within 60 s at 25℃.The elastomer(20 mg)in a joint of 25 mm×30 mm(2.7 mg/cm^(2))provided very strong adhesion for two pieces of glass and the bound glass keep unchanged at room temperature for 98 h even hung with 100 g of steel column below.The cis-PB-Si(OH)3-based supramolecular elastomer would have potential applications in adhesives,self-healing materials,damping materials and elastic materials.展开更多
[Objective] The research was aimed to study the adsorption behavior of p-nitroaniline from aqueous solution by porous hollow carbonaceous spheres （PHCSs）.[Method] The effects of pH,temperature and amount of carbonac...[Objective] The research was aimed to study the adsorption behavior of p-nitroaniline from aqueous solution by porous hollow carbonaceous spheres （PHCSs）.[Method] The effects of pH,temperature and amount of carbonaceous microspheres on adsorption behavior of p-nitroaniline were investigated.[Result] The adsorption amount was affected by temperature slightly,and it decreased with the increase of temperature within a certain range.PHCSs had a higher adsorption capacity as pH was in the range of 2.0-8.0.The adsorption amount of p-nitroaniline was proportional to PHCSs amount within a certain range until it reached a saturation level.The adsorption isotherms of p-nitroaniline appeared to be nonlinear and obeyed to Freundlich equation very well.[Conclusion] The amphiphilic property and the specific chemical functional groups of PHCSs enable them to be a potentially excellent sorbent.展开更多
A new definition of the dual descriptor,namely,thethermodynamic dual descriptor,is developed within the grand canonicalpotential formalism.This new definition is formulated to describe the same △f_r(r)=β/2C[f^+(r)-f...A new definition of the dual descriptor,namely,thethermodynamic dual descriptor,is developed within the grand canonicalpotential formalism.This new definition is formulated to describe the same △f_r(r)=β/2C[f^+(r)-f^-(r)](C>0) physical phenomenon as the original definition proposed by Morell,Grand,and Toro-Labbé(J.Phys.Chem.A2005,109,205),which is characterized by a second-order response of the electron density towards an electron flux.To formulate the new definition,we performed two successive partial derivatives of the average electron density,one with respect to the average number of electrons,and the other with respect to the chemical potential of the electron reservoir.When the derivative is expressed in terms of the three-state ensemble model,in the regime of low temperatures up to temperatures of chemical interest,one finds that the thermodynamic dual descriptor can be expressed as?f_T(r)=(β/2)C[f^+(r)-f^-(r)],whereβ=1/k_BT,Cis a global quantity that depends on the temperature and global electronic properties of the molecule(the first ionization potential and the electron affinity),C=1 for systems with zero fractional charge,and C=C_ω>0(albeit very close to zero)for systems with nonzero fractional charge,,and f^+(r)and f^-(r)are the nucleophilic and electrophilic Fukui functions,respectively.The quantity within the square brackets is the original definition of the dual descriptor.As the local terms(the ones containing regioselectivity information)are equal to those of the dual descriptor,?f_T(r)has the same regioselectivity information,multiplied by the global quantity(β/2)C.This implies that the regioselectivity information contained in the original dual descriptor is preserved at all temperatures different from zero,and for any value of C>0.One of the most important features of this new definition is that it avoidsthe undesired Dirac delta behavior observed when the second order partial derivative of the average density is taken with respect to the average number of electrons,using the exact density dependence of the average number of electrons.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
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.
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.
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.
文摘Phospholipids have the characteristics of excellent biocompatibility and a especial amphiphilicity.These unique properties make phospholipids most appropriate to be employed as important pharmaceutical excipients and they have a very wide range of applications in drug delivery systems.The aim of this review is to summarize phospholipids and some of their related applications in drug delivery systems,and highlight the relationship between the properties and applications,and the effect of the species of phospholipids on the efficiency of drug delivery.We refer to some relevant literatures,starting from the structures,main sources and properties of phospholipids to introduce their applications in drug delivery systems.The present article focuses on introducing five types of carriers based on phospholipids,including liposomes,intravenous lipid emulsions,micelles,drug-phospholipids complexes and cochleates.
文摘A series of water soluble aliphatic hyperbranched poly(amido amine)s(PAMAMs) with the same or similar chemical structure of poly(amido amine) dendrimer was successfully synthesized from commercially available AB and C_n types of monomers by one-pot polymerization via the couple-monomer methodology(CMM). The AB type monomer used in this paper was methyl acrylate, and C_n monomers were multi-amino compounds such as ethylenediamine(EDA), diethylenetriamine(DETA), triethylenetetraamine(TETA), tetraethylenepentaamine(TEPA) and pentaethylenehexamine(PEHA). The reaction mechanism was investigated by means of the mass spectra of the reaction intermediates. Adjusting the feed ratio of AB to C_n, hyperbranched polymers with different terminal groups and properties were obtained. FTIR, NMR, DSC, and TGA were used to characterize the polymers. It was found that the polymers′ properties such as solubility, thermal behaviour and encapsulation capability varied with changing the feed ratio of AB to C_n. Benzoyl and palmitoyl groups were introduced into these macromolecules by acidylation to form amphiphilic hyperbranched polymers which have a high capability to encapsulate water soluble dyes such as Congo red. It is expected that the hyperbranched PAMAMs can play an important role in the industrial applications, such as coatings, cross-linking and phase-transferring agents because of their versatility and availability.
基金the National Natural Science Foundation of China(Nos.51773103 and 51603112)Taishan Mountain Scholar Foundation(Nos.TS20081120 and tshw20110510)State Key Laboratory of Bio-Fibers and EcoTextiles(Qingdao University)(No.K2019-09).
文摘Macromolecule nanocrystal network and strong interfacial interaction are always beneficial to enhance the mechanical property of polymer-based nanocomposites.Poly(vinyl alcohol)(PVA),a typical biocompatible semicrystalline polymer,is an ideal candidate for preparing high performance polymer-based nanocomposites.However,the rich hydrogen bonds between PVA matrix and graphene oxide(GO)can disrupt the formation of PVA nanocrystal network.Thus,it remains a great challenge to achieve both strong and tough PVA-GO nanocomposites.Herein,by introducing a novel Janus-like amphiphilic graphene oxide(JGO),both hydrogen bonding and interfacial crystallization have been constructed between JGO sheets and PVA matrix.Benefiting from amphiphilic interfacial interaction and the enhanced crystal network,both PVA-JGO dried films and their swollen hydrogel films show superior mechanical properties than those of traditional PVA-GO nanocomposites.PVA-JGO dried films exhibit a 264%improvement of toughness at a JGO loading of 1 wt%.Meanwhile,the corresponding PVA-JGO swollen hydrogel films display simultaneous improvement of nearly 8 times increase of tensile strength and 20 times increase of toughness compared to traditional PVA-GO nanocomposite.This work indicates multiple interfacial interactions and macromolecule crystal networks can be concurrent in PVA nanocomposites by innovative modification of nanofillers,providing a new strategy to construct PVA nanocomposites with high strength and high toughness.The integration of outstanding mechanical and swelling resistance properties on PVA-JGO nanocomposite films render their promising applications,such as packaging and toughening hydrogel materials.
基金the National Natural Science Foundation of China(NSFC)(Nos.21634002,51790501 and 51521062)the Fundamental Research Funds for the Central Universities(Nos.XK1802-2 and XK1802-1).
文摘Liquid trimethoxy silane-functionalized cis-polybutadiene(cis-PB-Si(OMe)3),possessing number-average molecular weights of cis-PB segments(Mn,PB)ranging from 1800 g/mol to 5400 g/mol,with cis-1,4 content of ca.80%and high functionality(>96%)could be synthesized by coordination copolymerization of living cis-PB chain ends with ethenyltrimethoxy-silane with neodymium-based catalytic system.The silicon hydroxyl-functionalized cis-polybutadiene(cis-PB-Si(OH)_(3))-based micelles in water have been achieved by in situ hydrolysis of cis-PB-Si(OMe)_(3)in hexane/water mixture(pH=6.8)at 70℃and by sequential removal of residue hexane.The size of the above micelles with soft elastic cis-PB cores could be remarkably enlarged by loading SiO_(2)nanoparticles on their surfaces via hydrogen bonding interaction.Giant supramolecular long chain aggregates or networks formed by hydrogen bonding interaction and possible O—Si—O chemical bonds between cis-PB-Si(OH)3-based micellar surfaces had relatively large size and thus precipitated from water after several months of storage,leading to production of cis-PB-Si(OH)_(3)solid elastomer with extremely low T_(g)at−107.0℃.The left cis-PB-Si(OH)_(3)-based micelles in water with relatively small size gradually formed the water-insoluble cis-PB-Si(OH)_(3)-based supramolecular aggregates or networks.The cis-PB-Si(OH)_(3)-based supramolecular elastomer exhibited excellent self-healing property within 60 s at 25℃.The elastomer(20 mg)in a joint of 25 mm×30 mm(2.7 mg/cm^(2))provided very strong adhesion for two pieces of glass and the bound glass keep unchanged at room temperature for 98 h even hung with 100 g of steel column below.The cis-PB-Si(OH)3-based supramolecular elastomer would have potential applications in adhesives,self-healing materials,damping materials and elastic materials.
文摘[Objective] The research was aimed to study the adsorption behavior of p-nitroaniline from aqueous solution by porous hollow carbonaceous spheres （PHCSs）.[Method] The effects of pH,temperature and amount of carbonaceous microspheres on adsorption behavior of p-nitroaniline were investigated.[Result] The adsorption amount was affected by temperature slightly,and it decreased with the increase of temperature within a certain range.PHCSs had a higher adsorption capacity as pH was in the range of 2.0-8.0.The adsorption amount of p-nitroaniline was proportional to PHCSs amount within a certain range until it reached a saturation level.The adsorption isotherms of p-nitroaniline appeared to be nonlinear and obeyed to Freundlich equation very well.[Conclusion] The amphiphilic property and the specific chemical functional groups of PHCSs enable them to be a potentially excellent sorbent.
基金PWA thanks NSERC for support from the Canada Research Chairs, Compute Canada, and an NSERC Discovery Grant. MFP thanks Universidad Autonoma Metropolitana-Iztapalapa for a Visiting Professor Invitation. JLG and AV thank Conacyt for Grants 237045 and 128369
文摘A new definition of the dual descriptor,namely,thethermodynamic dual descriptor,is developed within the grand canonicalpotential formalism.This new definition is formulated to describe the same △f_r(r)=β/2C[f^+(r)-f^-(r)](C>0) physical phenomenon as the original definition proposed by Morell,Grand,and Toro-Labbé(J.Phys.Chem.A2005,109,205),which is characterized by a second-order response of the electron density towards an electron flux.To formulate the new definition,we performed two successive partial derivatives of the average electron density,one with respect to the average number of electrons,and the other with respect to the chemical potential of the electron reservoir.When the derivative is expressed in terms of the three-state ensemble model,in the regime of low temperatures up to temperatures of chemical interest,one finds that the thermodynamic dual descriptor can be expressed as?f_T(r)=(β/2)C[f^+(r)-f^-(r)],whereβ=1/k_BT,Cis a global quantity that depends on the temperature and global electronic properties of the molecule(the first ionization potential and the electron affinity),C=1 for systems with zero fractional charge,and C=C_ω>0(albeit very close to zero)for systems with nonzero fractional charge,,and f^+(r)and f^-(r)are the nucleophilic and electrophilic Fukui functions,respectively.The quantity within the square brackets is the original definition of the dual descriptor.As the local terms(the ones containing regioselectivity information)are equal to those of the dual descriptor,?f_T(r)has the same regioselectivity information,multiplied by the global quantity(β/2)C.This implies that the regioselectivity information contained in the original dual descriptor is preserved at all temperatures different from zero,and for any value of C>0.One of the most important features of this new definition is that it avoidsthe undesired Dirac delta behavior observed when the second order partial derivative of the average density is taken with respect to the average number of electrons,using the exact density dependence of the average number of electrons.
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.
