Using molecular dynamics modeling,the change in the shape and density of the macromolecular corona consisting of two oppositely charged polyelectrolytes,including those combined into one block copolymer,on the surface...Using molecular dynamics modeling,the change in the shape and density of the macromolecular corona consisting of two oppositely charged polyelectrolytes,including those combined into one block copolymer,on the surface of a polarized spherical metal nanoparticle was studied.A mathematical model of the structure of the block copolymer chain adsorbed on a polarized spherical nanoparticle is presented for the cases of polyelectrolyte blocks of large and small length.Based on the modeling results,radial and angular distributions of the density of atoms of polyelectrolyte polypeptides adsorbed on the surface of a spherical nanoparticle were calculated depending on its dipole moment.As the dipole moment of the nanoparticle increased,the dense macromolecular shell was destroyed,forming caps of polyelectrolyte macro molecules or fragments of block copolymer of different types on the poles of the polarized nanoparticle.In this case,the macromolecular corona in the region of the poles of the polarized nanoparticle swelled the more strongly,the greater the distance between the charged links in the polymer.展开更多
Conductive hydrogels have garnered widespread attention as a versatile class of flexible electronics.Despite considerable advancements,current methodologies struggle to reconcile the fundamental trade-off between high...Conductive hydrogels have garnered widespread attention as a versatile class of flexible electronics.Despite considerable advancements,current methodologies struggle to reconcile the fundamental trade-off between high conductivity and effective absorption-dominated electromagnetic interference(EMI)shielding,as dictated by classical impedance matching theory.This study addresses these limitations by introducing a novel synthesis of aramid nanofiber/MXene-reinforced polyelectrolyte hydrogels.Leveraging the unique properties of polyelectrolytes,this innovative approach enhances ionic conductivity and exploits the hydration effect of hydrophilic polar groups to induce the formation of intermediate water.This critical innovation facilitates polarization relaxation and rearrangement in response to electromagnetic fields,thereby significantly enhancing the EMI shielding effectiveness of hydrogels.The electromagnetic wave attenuation capacity of these hydrogels was thoroughly evaluated across both X-band and terahertz band frequencies,with further investigation into the impact of varying water content states-hydrated,dried,and frozen-on their electromagnetic properties.Moreover,the hydrogels exhibited promising capabilities beyond mere EMI shielding;they also served effectively as strain sensors for monitoring human motions,indicating their potential applicability in wearable electronics.This work provides a new approach to designing multifunctional hydrogels,advancing the integration of flexible,multifunctional materials in modern electronics,with potential applications in both EMI shielding and wearable technology.展开更多
Moisture-enabled electricity generation(MEG)has emerged as a promising sustainable energy harvesting technology,comparable to photovoltaics,thermoelectrics,and triboelectrics[1].MEGs generate electricity by converting...Moisture-enabled electricity generation(MEG)has emerged as a promising sustainable energy harvesting technology,comparable to photovoltaics,thermoelectrics,and triboelectrics[1].MEGs generate electricity by converting the chemical potential of moisture into electric energy through interactions with hygroscopic materials and nanostructured interfaces.Unlike solar or thermal harvesters,MEGs operate continuously by utilizing ubiquitous atmospheric moisture,granting them unique spatial and temporal adaptability.Despite nearly a decade of progress and the exploration of diverse material systems for MEG,the overall output power remains significantly limited due to inherently low charge carrier concentrations and restricted ion diffusion fluxes[2].As a result,standalone MEG devices often deliver low and unstable output,limiting practical applications.To enhance performance and versatility,recent efforts have explored hybridization of MEG with other ambient energy sources such as triboelectric or thermoelectric effects.展开更多
Strong polyelectrolyte brushes(SPBs)play an important role in enabling material surface functionalization due to their unique stimuli-responsive properties.Although the unexpected pH responsiveness of SPBs has been re...Strong polyelectrolyte brushes(SPBs)play an important role in enabling material surface functionalization due to their unique stimuli-responsive properties.Although the unexpected pH responsiveness of SPBs has been revealed in the past ten years,it is still unclear if the pH-responsive properties of SPBs are affected by the brush thickness.In this study,we employed the positively charged poly[2-(methacryloyloxy)ethyl]trimethylammonium chloride(PMETAC)and negatively charged sodium poly(styrenesulfonate)(NaPSS)brushes as model systems to explore the effect of thickness on the pH-responsive properties of SPBs.The results demonstrate that the pH-responsive properties of SPBs manifest different dependences on the brush thickness.Specifically,for both PMETAC and NaPSS brushes,the pH-responsive hydration and stiffness are influenced by the thickness,and the pH-responsive wettability and adhesion are almost unaffected by the thickness.This work not only provides a clear understanding of the relationship between the brush thickness and the pH responsiveness of SPBs,but also offers a new method to control the pH-responsive properties of SPBs.展开更多
Polyelectrolytes(PEs)are polymers carrying ionizable groups along the chain backbone and play an important role in life and environmental sciences,industrial applications and other fields.Due to the complicated topolo...Polyelectrolytes(PEs)are polymers carrying ionizable groups along the chain backbone and play an important role in life and environmental sciences,industrial applications and other fields.Due to the complicated topological structure and electrostatic correlations of PEs,PEs exhibit very rich phase behavior and morphologies in both bulk and confined solutions.So far,many theories,simulations and machine learning approaches have been proposed to study the behavior of polyelectrolyte solutions,especially the intrinsic structure-property relationships.In this perspective,from a personal point of view,we present several recent trends in polyelectrolyte solutions.The main themes considered here are accelerated development of sequence-defined polyelectrolyte(SDPE)via artificial intelligence technology,liquid-liquid phase separation in bulk SDPE solutions,adsorption behaviors of SDPE in the vicinity of a single dielectric surface,and surface forces between two charged surfaces mediated by SDPE solutions.展开更多
Knots are discovered in a wide range of systems,from DNA and proteins to catheters and umbilical cords,and have thus attracted much attention from physicists and biophysicists.Langevin dynamics simulations were perfor...Knots are discovered in a wide range of systems,from DNA and proteins to catheters and umbilical cords,and have thus attracted much attention from physicists and biophysicists.Langevin dynamics simulations were performed to study the knotting properties of coarsegrained knotted circular semiflexible polyelectrolyte (PE) in solutions of different concentrations of trivalent salt.We find that the length and position of the knotted region can be controlled by tuning the bending rigidity b of the PE and the salt concentration C_(S).We find that the knot length varies nonmonotonically with b in the presence of salt,and the knot localizes and is the tightest at b=5.As b>5,the knot swells with b increase.In addition,similar modulations of the knot size and position can be achieved by varying the salt concentration C_(S).The knot length varies nonmonotonically with C_(S) for b>0.The knot localizes and becomes tightest at C_(S)=1.5×10^(-4) mol/L in the range of C_(S)≤1.5×10^(-4) mol/L.As C_(S)>1.5×10^(-4) mol/L,the knot of the circular semiflexible PE swells at the expense of the overall size of the PE.Our results lay the foundation for achieving broader and more precise external adjustability of knotted PE size and knot length.展开更多
In this work,we have developed a lignin-derived polymer electrolyte(LSELi),which demonstrates exceptional ionic conductivity of 1.6×10^(-3)S cm^(−1)and a high cation transference number of 0.57 at 25°C.Time ...In this work,we have developed a lignin-derived polymer electrolyte(LSELi),which demonstrates exceptional ionic conductivity of 1.6×10^(-3)S cm^(−1)and a high cation transference number of 0.57 at 25°C.Time of flight secondary ion mass spectrometry(TOF-SIMS)analysis shows that the large-size 1-ethyl-3-methylimidazolium cations(EMIM^(+))can induce the aggregation of the anionic segments in lignosulfonate to reconstruct the three-dimensional(3D)spatial structure of polyelectrolyte,thereby forming a fluent Li^(+)transport 3D network.Dielectric loss spectroscopy further reveals that within this transport network,Li^(+)transport is decoupled from the relaxation of lignosulfonate chain segments,exhibiting characteristics of rapid Li^(+)transport.Furthermore,in-situ distribution of relaxation times analysis indicates that a stable solid electrolyte interface layer is formed at the Li plating interface with LSELi,optimizing the Li plating interface and exhibiting low charge transfer impedance and stable Li plating and stripping.Thus,a substantially prolonged cycling stability and reversibility are obtained in the Li||LSELi||Li battery at 25°C(1800 h at 0.1 mA cm^(−2),0.1 mAh cm^(−2)).At 25°C,the Li||LSELi||LiFePO_(4)cell shows 132 mAh g^(−1)of capacity with 92.7%of retention over 120 cycles at 0.1 mA cm^(−2).展开更多
Molecular dynamics simulations were performed to investigate the sliding dynamics of a small charged ring chain along rigid cyclic diblock polyelectrolyte in catenane immersed in salt solution.We found that both the m...Molecular dynamics simulations were performed to investigate the sliding dynamics of a small charged ring chain along rigid cyclic diblock polyelectrolyte in catenane immersed in salt solution.We found that both the mean-square displacement g_(3)(t)and diffusion coefficient D of ring are influenced by the salt type,electrostatic interaction strength A and salt concentration cs.D first decreases and then increases as A increases when Ais not large.At large A,D decreases with an increase in A owing to the polyelectrolyte charge reversal caused by the aggregation of ions near it.Meanwhile,g_(3)(t)exhibited intermediate oscillating behavior at moderate A in monovalent cation salt solution.The sliding dynamics of ring can be attributed to the free energy landscape for diffusion.According to the potential of mean force(PMF)of ring chain,we found that our simulation results agreed well with the theoretical results of Lifson-Jackson formula.This study can provide a practical model for the diffusion of charged particles in different dielectric and periodic media,and provides a new perspective for regulating the sliding dynamics of mechanically interlocked molecules in electrolyte solutions.展开更多
The scaling-up of electrochemical CO_(2)reduction requires circumventing the CO_(2)loss as carbonates under alkaline conditions.Zero-gap MEA cell configurations with a proton exchange membrane represent an alternative...The scaling-up of electrochemical CO_(2)reduction requires circumventing the CO_(2)loss as carbonates under alkaline conditions.Zero-gap MEA cell configurations with a proton exchange membrane represent an alternative solution in a pure acidic system,but the catalyst layer in direct contact with the hydrated proton environment usually leads to H_(2)evolution dominating.Herein,we show that polydimethyldiallyl-ammonium-chloride-coated Ag(Ag@PDDA)electrode exhibits outstanding performance with a FE of 86%,a single-pass conversion of 72%,and a stability of 28 h for CO production in pure-acid MEA compared with ammonium poly(N-methyl-piperidine-co-pterphenyl)decorated Ag(Ag/QAPPT)and cetyltrimethylammonium bromide decorated Ag(Ag/CTAB).The in situ ATR-SEIRAS reveal that PDDA creates a positive charge-rich protective outer layer and an N-rich hybrid inner layer,which not only suppresses the migration of H+during the electrolysis process and blocks the direct contact between H2O and Ag catalyst,but also promotes the generation from CO_(2)to*COOH in a pure-acid system.This work highlights the importance of polyelectrolyte engineering in regulating the electrocatalytic interface and accelerates the development of proton exchange membrane CO_(2)electrolysis.展开更多
Cationic polyethylenimine （PEI） with dextran fluorescein anionic （DFA） or oligodeoxynucleotide （ODN） could form polyelectrolyte complex by self-assembly as a gene delivery vector. This study was designed to inve...Cationic polyethylenimine （PEI） with dextran fluorescein anionic （DFA） or oligodeoxynucleotide （ODN） could form polyelectrolyte complex by self-assembly as a gene delivery vector. This study was designed to investigate the effects on pharmaceutical characteristics and cell uptake PEI after a long-circulation modification with poly（ethylene glycol） （PEG）. DFA or ODN reacted with PEI or PEI-PEG to form polyelectrolyte complexes. Surface characters of these complexes and the retardation of ODN by PEI and PEI-PEG were evaluated. The uptake rates of DFA/PEI and DFA/PEI-PEG complexes by MCF-7 cells were evaluated by flow cytometry. Confocal laser scanning microscopy was utilized to visualize the internalization of these complexes. ODN/PEI complex showed the dependence of their size and ξ potential on the N/P ratio. ODN/PEI-PEG complex were much less affected by N/P ratio and their size was around 30 100 nm. PEI and PEI-PEG retarded ODN even at N/P ratio as low as 4, and complete retardation was found at N/P ratio of 8. The uptake rate by MCF-7 cells was direct correlated to the DFA concentration and incubation time, and the uptake rate could exceed 99% under the selected condition. The results in this study showed that PEI self-assembly polyelectrolyte complex after stealth or long circulation modification may increase the ability as a gene vector to delivery genes into cells.展开更多
Interaction of anionic polyelectrolyte with cationic gemini surfactant has been investigated by coarse-grained molecular dynamics simulation.Polyelectrolyte facilitates the oppositely charged ionic surfactants to aggr...Interaction of anionic polyelectrolyte with cationic gemini surfactant has been investigated by coarse-grained molecular dynamics simulation.Polyelectrolyte facilitates the oppositely charged ionic surfactants to aggregate by suppressing the electrostatic repulsion between ionic head groups leading to the formation of micellar complex.With addition of surfactant,the conformation of polyion chain changes from stretched to random coiled to spherical,and at the same time more free micelles are formed by surfactants in mixtures.Increasing the length of spacer or tail chain in gemini surfactant will weaken its interaction with polyelectrolyte and simultaneously strengthen its tendency to self-assemble.The simulation results are consistent with experimental observations and reveal that the electrostatic interaction plays an important role in the interaction of polyelectrolyte with gemini sur- factant.展开更多
The achievement of both robust fire-safety and mechanical properties is of vital requirement for carbon fiber(CF)composites.To this end,a facile interracial strategy for fabricating flame-retardant carbon fibers decor...The achievement of both robust fire-safety and mechanical properties is of vital requirement for carbon fiber(CF)composites.To this end,a facile interracial strategy for fabricating flame-retardant carbon fibers decorated by bio-based polyelectrolyte complexes(PEC)consisting of chitosan(CH)and ammonium polyphosphate(APP)was developed,and its corresponding fire-retarded epoxy resin composites(EP/(PEC@CF))without any other additional flame retardants were prepared.The decorated CFs were characterized by SEM-EDX,XPS and XRD,indicating that the flame-retardant PEC coating was successfully constructed on the surface of CF.Thanks to the nitrogen-and phosphorous-containing PEC,the resulting composites exhibited excellent flame retardancy as the limiting oxygen index(LOI)increased from 31.0%of EP/CF to 40.5%and UL-94 V-0 rating was achieved with only 8.1 wt%PEC.EP/(PEC8.1@CF)also performed well in cone calorimetry with the decrease of peak-heat release rate(PHRR)and smoke production rate(SPR)by 50.0%and 30.4%,respectively,and the value of fire growth rate(FIGRA)was also reduced to 3.41 kW·m-2-s-1 from 4.84 kW·m-2·s-1,suggesting a considerably enhanced fire safety.Furthermore,SEM images of the burning residues revealed that the PEC coating exhibited the dominant flame-retardant activity in condensed phase via the formation of compact phosphorus-rich char.In addition,the impact strength of the composite was improved,together with no obvious deterioration of flexural properties and glass transition temperature.Taking advantage of the features,the PEC-decorated carbon fibers and the relevant composites fabricated by the cost-effective and facile strategy would bring more chances for widespread applications.展开更多
Thin film composite(TFC) membranes represent a highly promising platform for efficient nanofiltration(NF)processes. However, the improvement in permeance is impeded by the substrates with low permeances. Herein,highly...Thin film composite(TFC) membranes represent a highly promising platform for efficient nanofiltration(NF)processes. However, the improvement in permeance is impeded by the substrates with low permeances. Herein,highly permeable gradient phenolic membranes with tight selectivity are used as substrates to prepare TFC membranes with high permeances by the layer-by-layer assembly method. The negatively charged phenolic substrates are alternately assembled with polycation polyethylenimine(PEI) and polyanion poly(acrylic acid)(PAA)as a result of electrostatic interactions, forming thin and compact PEI/PAA layers tightly attached to the substrate surface. Benefiting from the high permeances and tight surface pores of the gradient nanoporous structures of the substrates, the produced PEI/PAA membranes exhibit a permeance up to 506 L? m-2?h-1?MPa-1, which is ~2–10 times higher than that of other membranes with similar rejections. The PEI/PAA membranes are capable of retaining N 96.1% of negatively charged dyes following the mechanism of electrostatic repulsion. We demonstrate that the membranes can also separate positively and neutrally charged dyes from water via other mechanisms.This work opens a new avenue for the design and preparation of high-flux NF membranes, which is also applicable to enhance the permeance of other TFC membranes.展开更多
A theoretical investigation on the pH-induced switching of mixed polyelectrolyte brushes was performed by using a molecular theory. The results indicate that the switching properties of mixed polyelectrolyte brushes a...A theoretical investigation on the pH-induced switching of mixed polyelectrolyte brushes was performed by using a molecular theory. The results indicate that the switching properties of mixed polyelectrolyte brushes are dependent on the pH values. At low pH, negatively charged chains adopt a compact conformation on the bottom of the brush while positively charged chains are highly stretched away from the surface. At high pH values, the inverse transformation takes place. The role of pH determining the polymer chains conformation and charge behavior of mixed polyelectrolyte brushes was analyzed. It is found that there exists a mechanism for reducing strong electrostatic repulsions： stretching of the chains. The H＋ and OH- units play a more important role as counterions of the charged polymers do. The collapse of the polyelectrolyte chains for different pH values could be attributed to the screening of the electrostatic interactions and the counterion-mediated attractive interaction along the chains.展开更多
In general,productions of natural pigment in submerged microorganism culture were much less than that in solid-state fermentation,because the solid-state culture can provide a support carrier for the mycelium. To impr...In general,productions of natural pigment in submerged microorganism culture were much less than that in solid-state fermentation,because the solid-state culture can provide a support carrier for the mycelium. To improve natural pigment production,the cultivation of Monascus purpureus in submerged encapsulated cell was investigated. Monascus purpureus immobilized in polyelectrolyte complex(PEC) microcapsules,which were pre-pared by sodium cellulose sulphate(NaCS) and poly-dimethyl-diallyl-ammonium chloride(PDMDAAC),was a good substitute for submerged cell culture because it mimicked the solid-state environment. The repeated-batch process with encapsulated cells was studied in flasks and a bubble column. The results indicated that the bubble column was more suitable for the encapsulation culture than the shaking flasks because of its good mass transfer performance and minor shear stress on cells. Owing to the protection of the microcapsule's membrane,Monascus purpureus in microcapsules increased approximately three times over that in free cell culture with negligible cell leakage to the medium. The pigment production in the bubble column finally reached 3.82(OD500) ,which was two times higher than in free cell culture. In addition,the duration of each batch was shortened to 15% of that in free cell culture.展开更多
Gold nanoparticles were synthesized through the reduction of tetrachlorauric acid (HAuCl4) by NaBH4, with polyethyleneimine(PEI) as stabilizer. The nanoparticles were characterized by UV-vis spectroscopy and atomic f...Gold nanoparticles were synthesized through the reduction of tetrachlorauric acid (HAuCl4) by NaBH4, with polyethyleneimine(PEI) as stabilizer. The nanoparticles were characterized by UV-vis spectroscopy and atomic force microscopy(AFM).展开更多
SnO_(2)electron transport layer(ETL)is a vital component in perovskite solar cells(PSCs),due to its excellent photoelectric properties and facile fabrication process.In this study,we synthesized a water-soluble and ad...SnO_(2)electron transport layer(ETL)is a vital component in perovskite solar cells(PSCs),due to its excellent photoelectric properties and facile fabrication process.In this study,we synthesized a water-soluble and adhesive polyelectrolyte with ethanolamine(EA)and poly-acrylic acid(PAA).The linear PAA was crosslinked by EA,forming a 3D network that stabilized the SnO_(2)nanoparticle dispersion.An organic–inorganic hybrid ETL is developed by introducing the cross-linked PAA-EA into SnO_(2)ETL,which prevents nano particle agglomeration and facilitates uniform SnO_(2)film formation with fewer defects.Additionally,the PAA-EA-modified SnO_(2)facilitated a uniform and compact perovskite film,enhancing the interface contact and carrier transport.Consequently,the PAA-EA-modified PSCs exhibited excellent PCE of 24.34%and 22.88%with high reproducibility for areas of 0.045 and 1.00 cm~2,respectively.Notably,owing to structure reinforce effect of PAA-EA in SnO_(2)ETL,flexible device demonstrated an impressive PCE of 23.34%while maintaining 90.1%of the initial PCE after 10,000 bending cycles with a bending radius of 5 mm.This successful approach of polyelectrolyte reinforced hybrid organic–inorganic ETL displays great potential for flexible,large-area PSCs application.展开更多
基金the financial support of the Ministry of Science and Higher Education of the Russian Federation within the framework of a grant for conducting large scientific projects in priority areas of scientific and technological development 075-15-2024-550。
文摘Using molecular dynamics modeling,the change in the shape and density of the macromolecular corona consisting of two oppositely charged polyelectrolytes,including those combined into one block copolymer,on the surface of a polarized spherical metal nanoparticle was studied.A mathematical model of the structure of the block copolymer chain adsorbed on a polarized spherical nanoparticle is presented for the cases of polyelectrolyte blocks of large and small length.Based on the modeling results,radial and angular distributions of the density of atoms of polyelectrolyte polypeptides adsorbed on the surface of a spherical nanoparticle were calculated depending on its dipole moment.As the dipole moment of the nanoparticle increased,the dense macromolecular shell was destroyed,forming caps of polyelectrolyte macro molecules or fragments of block copolymer of different types on the poles of the polarized nanoparticle.In this case,the macromolecular corona in the region of the poles of the polarized nanoparticle swelled the more strongly,the greater the distance between the charged links in the polymer.
基金supported by the National Natural Science Foundation of China(52375204)Shaanxi Provincial Science and Technology Innovation Team(2024RS-CXTD-63)+4 种基金Xianyang 2023 Key Research and Development Plan(L2023-ZDYF-QYCX-009)the Fundamental Research Funds for the Central Universities(D5000230356)2024“Double First-Class University”Construction Special Fund Project(0604024GH0201332,0604024SH0201332)Zhiyuan Laboratory(NO.ZYL2024007)Horizon Europe Framework Programme(101086071-CUPOLA).
文摘Conductive hydrogels have garnered widespread attention as a versatile class of flexible electronics.Despite considerable advancements,current methodologies struggle to reconcile the fundamental trade-off between high conductivity and effective absorption-dominated electromagnetic interference(EMI)shielding,as dictated by classical impedance matching theory.This study addresses these limitations by introducing a novel synthesis of aramid nanofiber/MXene-reinforced polyelectrolyte hydrogels.Leveraging the unique properties of polyelectrolytes,this innovative approach enhances ionic conductivity and exploits the hydration effect of hydrophilic polar groups to induce the formation of intermediate water.This critical innovation facilitates polarization relaxation and rearrangement in response to electromagnetic fields,thereby significantly enhancing the EMI shielding effectiveness of hydrogels.The electromagnetic wave attenuation capacity of these hydrogels was thoroughly evaluated across both X-band and terahertz band frequencies,with further investigation into the impact of varying water content states-hydrated,dried,and frozen-on their electromagnetic properties.Moreover,the hydrogels exhibited promising capabilities beyond mere EMI shielding;they also served effectively as strain sensors for monitoring human motions,indicating their potential applicability in wearable electronics.This work provides a new approach to designing multifunctional hydrogels,advancing the integration of flexible,multifunctional materials in modern electronics,with potential applications in both EMI shielding and wearable technology.
基金the financial support of the National Natural Science Foundation of China(No.22205165).
文摘Moisture-enabled electricity generation(MEG)has emerged as a promising sustainable energy harvesting technology,comparable to photovoltaics,thermoelectrics,and triboelectrics[1].MEGs generate electricity by converting the chemical potential of moisture into electric energy through interactions with hygroscopic materials and nanostructured interfaces.Unlike solar or thermal harvesters,MEGs operate continuously by utilizing ubiquitous atmospheric moisture,granting them unique spatial and temporal adaptability.Despite nearly a decade of progress and the exploration of diverse material systems for MEG,the overall output power remains significantly limited due to inherently low charge carrier concentrations and restricted ion diffusion fluxes[2].As a result,standalone MEG devices often deliver low and unstable output,limiting practical applications.To enhance performance and versatility,recent efforts have explored hybridization of MEG with other ambient energy sources such as triboelectric or thermoelectric effects.
基金financially supported by the National Natural Science Foundation of China(Nos.22273098,52033001 and 22303032)the Key Project of Anhui Province Science and Technology Innovation Platform(No.S202305a12020030)+1 种基金the Science and Technology Program Project of Zhejiang Province,China(No.2025ZY01057)partially carried out at the USTC Center for Micro and Nanoscale Research and Fabrication。
文摘Strong polyelectrolyte brushes(SPBs)play an important role in enabling material surface functionalization due to their unique stimuli-responsive properties.Although the unexpected pH responsiveness of SPBs has been revealed in the past ten years,it is still unclear if the pH-responsive properties of SPBs are affected by the brush thickness.In this study,we employed the positively charged poly[2-(methacryloyloxy)ethyl]trimethylammonium chloride(PMETAC)and negatively charged sodium poly(styrenesulfonate)(NaPSS)brushes as model systems to explore the effect of thickness on the pH-responsive properties of SPBs.The results demonstrate that the pH-responsive properties of SPBs manifest different dependences on the brush thickness.Specifically,for both PMETAC and NaPSS brushes,the pH-responsive hydration and stiffness are influenced by the thickness,and the pH-responsive wettability and adhesion are almost unaffected by the thickness.This work not only provides a clear understanding of the relationship between the brush thickness and the pH responsiveness of SPBs,but also offers a new method to control the pH-responsive properties of SPBs.
基金supported by the National Natural Science Foundation of China(Nos.22273112 and 22203100).
文摘Polyelectrolytes(PEs)are polymers carrying ionizable groups along the chain backbone and play an important role in life and environmental sciences,industrial applications and other fields.Due to the complicated topological structure and electrostatic correlations of PEs,PEs exhibit very rich phase behavior and morphologies in both bulk and confined solutions.So far,many theories,simulations and machine learning approaches have been proposed to study the behavior of polyelectrolyte solutions,especially the intrinsic structure-property relationships.In this perspective,from a personal point of view,we present several recent trends in polyelectrolyte solutions.The main themes considered here are accelerated development of sequence-defined polyelectrolyte(SDPE)via artificial intelligence technology,liquid-liquid phase separation in bulk SDPE solutions,adsorption behaviors of SDPE in the vicinity of a single dielectric surface,and surface forces between two charged surfaces mediated by SDPE solutions.
基金financially supported by the National Natural Science Foundation of China (No. 22363005)Jiangxi Provincial Natural Science Foundation (Nos. GJJ2200416 and 20202BABL203015)。
文摘Knots are discovered in a wide range of systems,from DNA and proteins to catheters and umbilical cords,and have thus attracted much attention from physicists and biophysicists.Langevin dynamics simulations were performed to study the knotting properties of coarsegrained knotted circular semiflexible polyelectrolyte (PE) in solutions of different concentrations of trivalent salt.We find that the length and position of the knotted region can be controlled by tuning the bending rigidity b of the PE and the salt concentration C_(S).We find that the knot length varies nonmonotonically with b in the presence of salt,and the knot localizes and is the tightest at b=5.As b>5,the knot swells with b increase.In addition,similar modulations of the knot size and position can be achieved by varying the salt concentration C_(S).The knot length varies nonmonotonically with C_(S) for b>0.The knot localizes and becomes tightest at C_(S)=1.5×10^(-4) mol/L in the range of C_(S)≤1.5×10^(-4) mol/L.As C_(S)>1.5×10^(-4) mol/L,the knot of the circular semiflexible PE swells at the expense of the overall size of the PE.Our results lay the foundation for achieving broader and more precise external adjustability of knotted PE size and knot length.
基金support from the National Natural Science Foundation of China(NSFC,22393901,22021001,22272143,22441030)the National Key Research and Development Program(2021YFA1502300)+1 种基金the Fundamental Research Funds for the Central Universities(20720220009)the Natural Science Foundation of Fujian Province,China(Grant No.2024J01213135)。
文摘In this work,we have developed a lignin-derived polymer electrolyte(LSELi),which demonstrates exceptional ionic conductivity of 1.6×10^(-3)S cm^(−1)and a high cation transference number of 0.57 at 25°C.Time of flight secondary ion mass spectrometry(TOF-SIMS)analysis shows that the large-size 1-ethyl-3-methylimidazolium cations(EMIM^(+))can induce the aggregation of the anionic segments in lignosulfonate to reconstruct the three-dimensional(3D)spatial structure of polyelectrolyte,thereby forming a fluent Li^(+)transport 3D network.Dielectric loss spectroscopy further reveals that within this transport network,Li^(+)transport is decoupled from the relaxation of lignosulfonate chain segments,exhibiting characteristics of rapid Li^(+)transport.Furthermore,in-situ distribution of relaxation times analysis indicates that a stable solid electrolyte interface layer is formed at the Li plating interface with LSELi,optimizing the Li plating interface and exhibiting low charge transfer impedance and stable Li plating and stripping.Thus,a substantially prolonged cycling stability and reversibility are obtained in the Li||LSELi||Li battery at 25°C(1800 h at 0.1 mA cm^(−2),0.1 mAh cm^(−2)).At 25°C,the Li||LSELi||LiFePO_(4)cell shows 132 mAh g^(−1)of capacity with 92.7%of retention over 120 cycles at 0.1 mA cm^(−2).
基金supported by the National Natural Science Foundation of China(Nos.22173080,22403062,and22363005)the Jiangxi Provincial Natural Science Foundation(No.20202BABL203015)。
文摘Molecular dynamics simulations were performed to investigate the sliding dynamics of a small charged ring chain along rigid cyclic diblock polyelectrolyte in catenane immersed in salt solution.We found that both the mean-square displacement g_(3)(t)and diffusion coefficient D of ring are influenced by the salt type,electrostatic interaction strength A and salt concentration cs.D first decreases and then increases as A increases when Ais not large.At large A,D decreases with an increase in A owing to the polyelectrolyte charge reversal caused by the aggregation of ions near it.Meanwhile,g_(3)(t)exhibited intermediate oscillating behavior at moderate A in monovalent cation salt solution.The sliding dynamics of ring can be attributed to the free energy landscape for diffusion.According to the potential of mean force(PMF)of ring chain,we found that our simulation results agreed well with the theoretical results of Lifson-Jackson formula.This study can provide a practical model for the diffusion of charged particles in different dielectric and periodic media,and provides a new perspective for regulating the sliding dynamics of mechanically interlocked molecules in electrolyte solutions.
基金financial support of the National Natural Science Foundation of China(NSFC)(52394202,52021004,52301232,and 52476056)the Natural Science Foundation of Chongqing Province(2024NSCQ-MSX1109).
文摘The scaling-up of electrochemical CO_(2)reduction requires circumventing the CO_(2)loss as carbonates under alkaline conditions.Zero-gap MEA cell configurations with a proton exchange membrane represent an alternative solution in a pure acidic system,but the catalyst layer in direct contact with the hydrated proton environment usually leads to H_(2)evolution dominating.Herein,we show that polydimethyldiallyl-ammonium-chloride-coated Ag(Ag@PDDA)electrode exhibits outstanding performance with a FE of 86%,a single-pass conversion of 72%,and a stability of 28 h for CO production in pure-acid MEA compared with ammonium poly(N-methyl-piperidine-co-pterphenyl)decorated Ag(Ag/QAPPT)and cetyltrimethylammonium bromide decorated Ag(Ag/CTAB).The in situ ATR-SEIRAS reveal that PDDA creates a positive charge-rich protective outer layer and an N-rich hybrid inner layer,which not only suppresses the migration of H+during the electrolysis process and blocks the direct contact between H2O and Ag catalyst,but also promotes the generation from CO_(2)to*COOH in a pure-acid system.This work highlights the importance of polyelectrolyte engineering in regulating the electrocatalytic interface and accelerates the development of proton exchange membrane CO_(2)electrolysis.
基金National Nature Science Foundation of China (Grant No.30772665)Beijing Nature Science Foundation (Grant No.7083111).
文摘Cationic polyethylenimine （PEI） with dextran fluorescein anionic （DFA） or oligodeoxynucleotide （ODN） could form polyelectrolyte complex by self-assembly as a gene delivery vector. This study was designed to investigate the effects on pharmaceutical characteristics and cell uptake PEI after a long-circulation modification with poly（ethylene glycol） （PEG）. DFA or ODN reacted with PEI or PEI-PEG to form polyelectrolyte complexes. Surface characters of these complexes and the retardation of ODN by PEI and PEI-PEG were evaluated. The uptake rates of DFA/PEI and DFA/PEI-PEG complexes by MCF-7 cells were evaluated by flow cytometry. Confocal laser scanning microscopy was utilized to visualize the internalization of these complexes. ODN/PEI complex showed the dependence of their size and ξ potential on the N/P ratio. ODN/PEI-PEG complex were much less affected by N/P ratio and their size was around 30 100 nm. PEI and PEI-PEG retarded ODN even at N/P ratio as low as 4, and complete retardation was found at N/P ratio of 8. The uptake rate by MCF-7 cells was direct correlated to the DFA concentration and incubation time, and the uptake rate could exceed 99% under the selected condition. The results in this study showed that PEI self-assembly polyelectrolyte complex after stealth or long circulation modification may increase the ability as a gene vector to delivery genes into cells.
基金Supported by the National Natural Science Foundation of China （No.20476025）, the Doctoral Research Foundation of the Ministry of Education of China （No.20050251004）, E-institute of Shanghai High Institution Grid （No.200303） and Shanghai Municipal Science and Technology Commission of China （No.05DJ14002）.
文摘Interaction of anionic polyelectrolyte with cationic gemini surfactant has been investigated by coarse-grained molecular dynamics simulation.Polyelectrolyte facilitates the oppositely charged ionic surfactants to aggregate by suppressing the electrostatic repulsion between ionic head groups leading to the formation of micellar complex.With addition of surfactant,the conformation of polyion chain changes from stretched to random coiled to spherical,and at the same time more free micelles are formed by surfactants in mixtures.Increasing the length of spacer or tail chain in gemini surfactant will weaken its interaction with polyelectrolyte and simultaneously strengthen its tendency to self-assemble.The simulation results are consistent with experimental observations and reveal that the electrostatic interaction plays an important role in the interaction of polyelectrolyte with gemini sur- factant.
基金Financial supports by the National Natural Science Foundation of China(Nos.51773137 and 51721091)the Sichuan Province Youth Science and Technology Innovation Team(No.2017TD0006)
文摘The achievement of both robust fire-safety and mechanical properties is of vital requirement for carbon fiber(CF)composites.To this end,a facile interracial strategy for fabricating flame-retardant carbon fibers decorated by bio-based polyelectrolyte complexes(PEC)consisting of chitosan(CH)and ammonium polyphosphate(APP)was developed,and its corresponding fire-retarded epoxy resin composites(EP/(PEC@CF))without any other additional flame retardants were prepared.The decorated CFs were characterized by SEM-EDX,XPS and XRD,indicating that the flame-retardant PEC coating was successfully constructed on the surface of CF.Thanks to the nitrogen-and phosphorous-containing PEC,the resulting composites exhibited excellent flame retardancy as the limiting oxygen index(LOI)increased from 31.0%of EP/CF to 40.5%and UL-94 V-0 rating was achieved with only 8.1 wt%PEC.EP/(PEC8.1@CF)also performed well in cone calorimetry with the decrease of peak-heat release rate(PHRR)and smoke production rate(SPR)by 50.0%and 30.4%,respectively,and the value of fire growth rate(FIGRA)was also reduced to 3.41 kW·m-2-s-1 from 4.84 kW·m-2·s-1,suggesting a considerably enhanced fire safety.Furthermore,SEM images of the burning residues revealed that the PEC coating exhibited the dominant flame-retardant activity in condensed phase via the formation of compact phosphorus-rich char.In addition,the impact strength of the composite was improved,together with no obvious deterioration of flexural properties and glass transition temperature.Taking advantage of the features,the PEC-decorated carbon fibers and the relevant composites fabricated by the cost-effective and facile strategy would bring more chances for widespread applications.
基金Supported by the National Basic Research Program of China(2015CB655301)the Natural Science Foundation of China(21825803)+2 种基金and the Natural Science Foundation of Jiangsu Province(BK20150063)the Program of Excellent Innovation Teams of Jiangsu Higher Education Institutionsthe Project of Priority Academic Program Development of Jiangsu Higher Education Institutions(PAPD).
文摘Thin film composite(TFC) membranes represent a highly promising platform for efficient nanofiltration(NF)processes. However, the improvement in permeance is impeded by the substrates with low permeances. Herein,highly permeable gradient phenolic membranes with tight selectivity are used as substrates to prepare TFC membranes with high permeances by the layer-by-layer assembly method. The negatively charged phenolic substrates are alternately assembled with polycation polyethylenimine(PEI) and polyanion poly(acrylic acid)(PAA)as a result of electrostatic interactions, forming thin and compact PEI/PAA layers tightly attached to the substrate surface. Benefiting from the high permeances and tight surface pores of the gradient nanoporous structures of the substrates, the produced PEI/PAA membranes exhibit a permeance up to 506 L? m-2?h-1?MPa-1, which is ~2–10 times higher than that of other membranes with similar rejections. The PEI/PAA membranes are capable of retaining N 96.1% of negatively charged dyes following the mechanism of electrostatic repulsion. We demonstrate that the membranes can also separate positively and neutrally charged dyes from water via other mechanisms.This work opens a new avenue for the design and preparation of high-flux NF membranes, which is also applicable to enhance the permeance of other TFC membranes.
基金financially supported by the National Natural Science Foundation of China(Nos.21264016 and 11265015)the General Foundation of Yi Li Normal University(No.2013YSYB17)
文摘A theoretical investigation on the pH-induced switching of mixed polyelectrolyte brushes was performed by using a molecular theory. The results indicate that the switching properties of mixed polyelectrolyte brushes are dependent on the pH values. At low pH, negatively charged chains adopt a compact conformation on the bottom of the brush while positively charged chains are highly stretched away from the surface. At high pH values, the inverse transformation takes place. The role of pH determining the polymer chains conformation and charge behavior of mixed polyelectrolyte brushes was analyzed. It is found that there exists a mechanism for reducing strong electrostatic repulsions： stretching of the chains. The H＋ and OH- units play a more important role as counterions of the charged polymers do. The collapse of the polyelectrolyte chains for different pH values could be attributed to the screening of the electrostatic interactions and the counterion-mediated attractive interaction along the chains.
基金Supported by the National Basic Research Program of China（2007CB707805） the National Natural Science Foundation of China（20876139）
文摘In general,productions of natural pigment in submerged microorganism culture were much less than that in solid-state fermentation,because the solid-state culture can provide a support carrier for the mycelium. To improve natural pigment production,the cultivation of Monascus purpureus in submerged encapsulated cell was investigated. Monascus purpureus immobilized in polyelectrolyte complex(PEC) microcapsules,which were pre-pared by sodium cellulose sulphate(NaCS) and poly-dimethyl-diallyl-ammonium chloride(PDMDAAC),was a good substitute for submerged cell culture because it mimicked the solid-state environment. The repeated-batch process with encapsulated cells was studied in flasks and a bubble column. The results indicated that the bubble column was more suitable for the encapsulation culture than the shaking flasks because of its good mass transfer performance and minor shear stress on cells. Owing to the protection of the microcapsule's membrane,Monascus purpureus in microcapsules increased approximately three times over that in free cell culture with negligible cell leakage to the medium. The pigment production in the bubble column finally reached 3.82(OD500) ,which was two times higher than in free cell culture. In addition,the duration of each batch was shortened to 15% of that in free cell culture.
基金This work was supported by the National Natural Science Foundation of China(No.29975028).
文摘Gold nanoparticles were synthesized through the reduction of tetrachlorauric acid (HAuCl4) by NaBH4, with polyethyleneimine(PEI) as stabilizer. The nanoparticles were characterized by UV-vis spectroscopy and atomic force microscopy(AFM).
基金supported by the National Key R&D Program of China(2019YFB1503201)the National Natural Science Foundation of China(52172238,52102304,51902264)+3 种基金the Natural Science Foundation of Shanxi Province(2020JM-093)the Open project of Shaanxi Laboratory of Aerospace Power(2021SXSYS-01-03)the Science Technology and Innovation Commission of Shenzhen Municipality(JCYJ20190807111605472)the Fundamental Research Funds for the Central Universities(3102019JC0005,5000220118)。
文摘SnO_(2)electron transport layer(ETL)is a vital component in perovskite solar cells(PSCs),due to its excellent photoelectric properties and facile fabrication process.In this study,we synthesized a water-soluble and adhesive polyelectrolyte with ethanolamine(EA)and poly-acrylic acid(PAA).The linear PAA was crosslinked by EA,forming a 3D network that stabilized the SnO_(2)nanoparticle dispersion.An organic–inorganic hybrid ETL is developed by introducing the cross-linked PAA-EA into SnO_(2)ETL,which prevents nano particle agglomeration and facilitates uniform SnO_(2)film formation with fewer defects.Additionally,the PAA-EA-modified SnO_(2)facilitated a uniform and compact perovskite film,enhancing the interface contact and carrier transport.Consequently,the PAA-EA-modified PSCs exhibited excellent PCE of 24.34%and 22.88%with high reproducibility for areas of 0.045 and 1.00 cm~2,respectively.Notably,owing to structure reinforce effect of PAA-EA in SnO_(2)ETL,flexible device demonstrated an impressive PCE of 23.34%while maintaining 90.1%of the initial PCE after 10,000 bending cycles with a bending radius of 5 mm.This successful approach of polyelectrolyte reinforced hybrid organic–inorganic ETL displays great potential for flexible,large-area PSCs application.
