The synthesis and structure-property correlation of poly（N-（2-hydroxypropyl） methacrylamide） （PHPMA） conjugates with various architectures including random, block, branched or star-like structures and compositio...The synthesis and structure-property correlation of poly（N-（2-hydroxypropyl） methacrylamide） （PHPMA） conjugates with various architectures including random, block, branched or star-like structures and compositions have been thoroughly explored. However, related synthesis and structure-property data are still lacking for comb-like PHPMA. In this work, we report the synthesis of comb-like PHPMA copolymer-doxorubicin （DOX） conjugates with different backbone/side-chain lengths and location of drug moieties. Well-defined comb-like PHPMA-DOX conjugates are obtained via the combination of controlled radical polymerization and fractional precipitation techniques. The influences of structural factors on the biological properties such as cellular uptake, blood circulation and tumor accumulation have been investigated. Long blood circulation and efficient tumor accumulation can be achieved by proper control of the comb number, length and location of drug moieties. These facile comb-like structures possess great potentials in future theranostics for brachytherapy or surgical navigation.展开更多
PEGylated poly（2-（dimethylamino）ethyl methacrylate） with comb-like architecture was synthesized by two-step polymerization. First,poly（oligo（ethylene glycol） malicate）（POEGMA） bearing pendant hydroxyl groups...PEGylated poly（2-（dimethylamino）ethyl methacrylate） with comb-like architecture was synthesized by two-step polymerization. First,poly（oligo（ethylene glycol） malicate）（POEGMA） bearing pendant hydroxyl groups was prepared by direct polycondensation of oligo（ethylene glycol） and malic acid in the presence of scandium triflate as chemoselective catalyst.Then the poly（2- （dimethylamino）ethyl methacrylate） side chains were grafted from the POEGMA backbone by atom transfer radical polymerization （ATRP） after the hydroxyl groups were modified into bromo-ester form,resulting in a PEGylated cationic copolymer with branched architecture.展开更多
A comb-like acrylamide copolymer （HCJ-1） was synthesized by using aqueous free radical polymerization of acrylamide （AM） as main monomer and ether carboxylate as functional monomer. The copolymers were characteriz...A comb-like acrylamide copolymer （HCJ-1） was synthesized by using aqueous free radical polymerization of acrylamide （AM） as main monomer and ether carboxylate as functional monomer. The copolymers were characterized with FT-IR and SEM. The SEM results show that the molecular structure of copolymer is extended in salt water. It is proved that the copolymer shows good salt resistance.The solution properties of HCJ-1 were studied and compared with those of partially hydrolyzed polyacrylamide （HPAM）. The experimental results show that the obtained HCJ-1, compared with HPAM, exhibits a dramatic enhancement in the salt-resistant properties. The apparent viscosity retention rate of 1.5 g/L HCJ-1 aqueous solution and salt solution after 180 days at 60 ℃ are 70.6% and 64.5%, respectively, exhibiting good thermal stability. In addition, HCJ-1 solution also displays the excellent shearing resistance. In a word, the experimental results show the HCJ-1 is a promising profiling agent for high salinity reservoir.展开更多
Three-dimensional Monte Carlo simulations of comb-like polymer chains with various backbone lengths Nb, arm lengths Na and arm densities m are carried out to study the elastic behavior of comb-like polymer chains. The...Three-dimensional Monte Carlo simulations of comb-like polymer chains with various backbone lengths Nb, arm lengths Na and arm densities m are carried out to study the elastic behavior of comb-like polymer chains. The radius of gyration, the shape factors and bond length in different cases during elastic process are calculated, and it is found that the comb-like polymer molecules with longer backbone or shorter arm are more close to linear chains. But the arm density rn affects the chain conformation non-monotonously. Some thermodynamic properties are also studied. Average Helmholtz free energy and elastic force fall increase with elongation ratio 2 for all chains.展开更多
Cross-linked PEG-based copolymers were obtained via synthesis of polyethylene glycol （PEG） and methoxy polyethylene glycol （MPEG） by the bridging and/or cross-linking agent of 2,4-tolylene diisocyanate （TDI） and...Cross-linked PEG-based copolymers were obtained via synthesis of polyethylene glycol （PEG） and methoxy polyethylene glycol （MPEG） by the bridging and/or cross-linking agent of 2,4-tolylene diisocyanate （TDI） and/or hexamethylene-l,6-diisocyanate homopolymer （HDI trimer）. The effects on the crystallization behaviors of the samples could be found with the changes in molecular weight of MC-PEG and molecular weight of SC-PEG in certain cross-linked density. It is revealed that the samples appear not to crystallize when the molecular weight of MC-PEG and SC-PEG are 1000 g/mol or less than that. The samples begin to crystallize when the molecular weight of either MC-PEG or SC-PEG reaches 2000 g/mol. The crystallinity of crystallized MC-PEG decreases with the increasing molecular weight of uncrystallized SC-PEG and the crystallinity of crystallized SC-PEG declines with the rise of molecular weight of uncrystallizable MC-PEG. The chains of SC-PEG （M_n = 2000 g/mol） can fold and align easilier than those of MC-PEG （M_n = 2000 g/mol）, when the content of PEG is the same.展开更多
The synthesis and characterization of a series of novel comb-like polymethacrylates bearing heterocyclic azo group and mesogenic group are described. The thermal properties of the polymers such as thermal stability an...The synthesis and characterization of a series of novel comb-like polymethacrylates bearing heterocyclic azo group and mesogenic group are described. The thermal properties of the polymers such as thermal stability and phase transition behavior were investigated by thermogravimetric analysis, differential thermal analysis and polarizing optical microscopy techniques. The experimental results show that all the synthesized polymers do not exhibit liquid crystallinity except the homopolymer of the mesogenic monomer MAPB2 and the glass transition temperatures of the polymers increase with increasing content of azo moiety in polymers linearly.展开更多
Fragrances are widely used in cosmetics,apparel and detergents.However,the rapid evaporation of the aro ma shortens the useful life of the aromatic product.Therefore,improving the fragrance retention time of aromatic ...Fragrances are widely used in cosmetics,apparel and detergents.However,the rapid evaporation of the aro ma shortens the useful life of the aromatic product.Therefore,improving the fragrance retention time of aromatic products and prolonging the service life of aromatic products are the key scientific problems that need to be solved in current aromatic products.In this study,zwitterionic comb-like lipid polymers were synthesized to encapsulate the fragrance molecule linalool.The results showed that the zwitterionic comb lipid molecules were capable of encapsulating more linalool than linear lipid molecules.At the same time,the zwitterionic comb-like lipid molecules also limited the slow release rate of the aroma,thereby increasing the fragrance retention time of the nano-fragrance.展开更多
We study the conformation of an amphiphilic comb-like copolymer in a selective solvent by using Brownian dynamics simulations.Our results demonstrate that,there is an optimal total degree of polymerization to form sph...We study the conformation of an amphiphilic comb-like copolymer in a selective solvent by using Brownian dynamics simulations.Our results demonstrate that,there is an optimal total degree of polymerization to form spherical micelles.Only when the total degree of polymerization is less than the optimal total degree of polymerization,a unimolecular spherical micelle can be formed,otherwise,the spherical micelle will be transformed into a cylindrical micelle.When the total degree of polymerization is less than the optimal total degree of polymerization,the radius of gyration and the stretching factor meet an exponential relationship,where the power exponent decreases with the increase of the length of hydrophilic side chains.The fundamental principles uncovered here afford insights for the optimization of molecular design of amphiphilic comb-like copolymers in various applications.展开更多
Combining Brownian dynamics simulations and self-consistent field theory,we demonstrate that the architectural parameters of coreshell comb-like chains have a decisive influence on their final self-assembled conformat...Combining Brownian dynamics simulations and self-consistent field theory,we demonstrate that the architectural parameters of coreshell comb-like chains have a decisive influence on their final self-assembled conformations.When the ratio of hydrophilic and hydrophobic segments is N_(g,g)∶N_(g,r)=3∶1,no core-shell structure is observed,and unsegregated chains or clusters are substituted.When N_(g,g)∶N_(g,r)=3∶2or 3∶3,the core-shell comb-like chains can be assembled into single micelles or structures where several small micelles are strung together by the backbone,which is similar to the pearl-necklace structure formed by the polyelectrolytes in poor solvent.With the increase of backbone length or grafting density,the probability of forming single micelles becomes lower,but the structures of two,three or more small micelles strung together are more observed.Our results indicate how to obtain the desired self-assembled structures of core-shell comb-like chains by regulating the architectural parameters,which could provide insights for the optimization of molecular design in various applications.展开更多
Comb-like acrylic acid poly（ethylene glycol） methyl ether ester （MPEGA）-co-acrylamide （AM） copolymer [P（MPEGA-co-AM）] as novel phase change materials （PCMs） was successfully synthesized via free-radical wate...Comb-like acrylic acid poly（ethylene glycol） methyl ether ester （MPEGA）-co-acrylamide （AM） copolymer [P（MPEGA-co-AM）] as novel phase change materials （PCMs） was successfully synthesized via free-radical water solution polymerization. The structures of P（MPEGA-co-AM） was characterized by Fourier Transform Infrared （FT-lR）. The experimental results showed that P（MPEGA-co-AM） copolymer possessed high molecular weight （Mo =66 kg/mol）, narrow molecular weight distribution （PDI≈1.14）. The phase transition temperature of copolymer decreases to 31℃, which is very much appreciated and urgently needed for smart PCM related to human body. Moreover, P（MPEGA-co-AM） had good thermal stability even at 380℃.展开更多
Well-defined comb-like branched polymers having one branch in each repeating unit have been suc-cessfully synthesized by the coupling reaction of living polystyrene(PS)and polyisoprene(PI)anions with 1,1-diphenylethen...Well-defined comb-like branched polymers having one branch in each repeating unit have been suc-cessfully synthesized by the coupling reaction of living polystyrene(PS)and polyisoprene(PI)anions with 1,1-diphenylethenyl(DPE)groups along PS backbone pre-pared via atom transfer radical polymerization(ATRP)of 4-vinylbenzyloxy benzophenone(Sc)followed by Wittig reaction.The resulting comb-like branched poly-mers were characterized by IR,1H-NMR,gel permeation chromatography(GPC)and static light scattering(SLS)in detail.The effect of living chains and DPE group molar ratio on grafting efficiency was discussed.The results show the coupling reaction of living chains and DPE groups was highly effective,and the coupling efficiency can be controlled via the feed molar ratios of living chains and DPE groups.Moreover,the effect of molecular weights of backbone(PSe)and PSLi or PILi on grafting efficiency was also discussed.The results show that when excess living polymers were used,the almost quantitative grafting efficiency could be achieved.展开更多
The 3-section SG-DBR tunable laser is fabricate d using an ion implantation quantum-well intermixing process.The over 30nm discontinuous tuning range is achieved with the SMRS greater than 30dB.
基金supported by the National Natural Science Foundation of China(Nos.51503013,51390481,21774008and 81472412)supported by the Fundamental Research Funds for the Central Universities(Nos.ZY1519 and XK1701)+1 种基金the long-term subsidy mechanism from the Ministry of Financethe Ministry of Education of PRC for BUCT
文摘The synthesis and structure-property correlation of poly（N-（2-hydroxypropyl） methacrylamide） （PHPMA） conjugates with various architectures including random, block, branched or star-like structures and compositions have been thoroughly explored. However, related synthesis and structure-property data are still lacking for comb-like PHPMA. In this work, we report the synthesis of comb-like PHPMA copolymer-doxorubicin （DOX） conjugates with different backbone/side-chain lengths and location of drug moieties. Well-defined comb-like PHPMA-DOX conjugates are obtained via the combination of controlled radical polymerization and fractional precipitation techniques. The influences of structural factors on the biological properties such as cellular uptake, blood circulation and tumor accumulation have been investigated. Long blood circulation and efficient tumor accumulation can be achieved by proper control of the comb number, length and location of drug moieties. These facile comb-like structures possess great potentials in future theranostics for brachytherapy or surgical navigation.
基金the financial supports from the Major State Basic Research Project(No. 2011CB606001)the Committee of Science and Technology of Zhejiang Provincea project supported by Scientific Research Fund of Ztiejiang Provincial Education Department(No.Y201121828)
文摘PEGylated poly（2-（dimethylamino）ethyl methacrylate） with comb-like architecture was synthesized by two-step polymerization. First,poly（oligo（ethylene glycol） malicate）（POEGMA） bearing pendant hydroxyl groups was prepared by direct polycondensation of oligo（ethylene glycol） and malic acid in the presence of scandium triflate as chemoselective catalyst.Then the poly（2- （dimethylamino）ethyl methacrylate） side chains were grafted from the POEGMA backbone by atom transfer radical polymerization （ATRP） after the hydroxyl groups were modified into bromo-ester form,resulting in a PEGylated cationic copolymer with branched architecture.
文摘A comb-like acrylamide copolymer （HCJ-1） was synthesized by using aqueous free radical polymerization of acrylamide （AM） as main monomer and ether carboxylate as functional monomer. The copolymers were characterized with FT-IR and SEM. The SEM results show that the molecular structure of copolymer is extended in salt water. It is proved that the copolymer shows good salt resistance.The solution properties of HCJ-1 were studied and compared with those of partially hydrolyzed polyacrylamide （HPAM）. The experimental results show that the obtained HCJ-1, compared with HPAM, exhibits a dramatic enhancement in the salt-resistant properties. The apparent viscosity retention rate of 1.5 g/L HCJ-1 aqueous solution and salt solution after 180 days at 60 ℃ are 70.6% and 64.5%, respectively, exhibiting good thermal stability. In addition, HCJ-1 solution also displays the excellent shearing resistance. In a word, the experimental results show the HCJ-1 is a promising profiling agent for high salinity reservoir.
基金supported by the National Natural Science Foundation of China(No.20704033)
文摘Three-dimensional Monte Carlo simulations of comb-like polymer chains with various backbone lengths Nb, arm lengths Na and arm densities m are carried out to study the elastic behavior of comb-like polymer chains. The radius of gyration, the shape factors and bond length in different cases during elastic process are calculated, and it is found that the comb-like polymer molecules with longer backbone or shorter arm are more close to linear chains. But the arm density rn affects the chain conformation non-monotonously. Some thermodynamic properties are also studied. Average Helmholtz free energy and elastic force fall increase with elongation ratio 2 for all chains.
基金financially supported by the National Natural Science Foundation of China(Nos.51173130,21374077 and 51573131)
文摘Cross-linked PEG-based copolymers were obtained via synthesis of polyethylene glycol （PEG） and methoxy polyethylene glycol （MPEG） by the bridging and/or cross-linking agent of 2,4-tolylene diisocyanate （TDI） and/or hexamethylene-l,6-diisocyanate homopolymer （HDI trimer）. The effects on the crystallization behaviors of the samples could be found with the changes in molecular weight of MC-PEG and molecular weight of SC-PEG in certain cross-linked density. It is revealed that the samples appear not to crystallize when the molecular weight of MC-PEG and SC-PEG are 1000 g/mol or less than that. The samples begin to crystallize when the molecular weight of either MC-PEG or SC-PEG reaches 2000 g/mol. The crystallinity of crystallized MC-PEG decreases with the increasing molecular weight of uncrystallized SC-PEG and the crystallinity of crystallized SC-PEG declines with the rise of molecular weight of uncrystallizable MC-PEG. The chains of SC-PEG （M_n = 2000 g/mol） can fold and align easilier than those of MC-PEG （M_n = 2000 g/mol）, when the content of PEG is the same.
文摘The synthesis and characterization of a series of novel comb-like polymethacrylates bearing heterocyclic azo group and mesogenic group are described. The thermal properties of the polymers such as thermal stability and phase transition behavior were investigated by thermogravimetric analysis, differential thermal analysis and polarizing optical microscopy techniques. The experimental results show that all the synthesized polymers do not exhibit liquid crystallinity except the homopolymer of the mesogenic monomer MAPB2 and the glass transition temperatures of the polymers increase with increasing content of azo moiety in polymers linearly.
基金financially supported by the National High Technology Research and Development Program(No.2016YFA0200303)the Beijing Natural Science Foundation(Nos.L172046,2192057)the National Natural Science Foundation of China(Nos.31771095,21875254 and 51573188)。
文摘Fragrances are widely used in cosmetics,apparel and detergents.However,the rapid evaporation of the aro ma shortens the useful life of the aromatic product.Therefore,improving the fragrance retention time of aromatic products and prolonging the service life of aromatic products are the key scientific problems that need to be solved in current aromatic products.In this study,zwitterionic comb-like lipid polymers were synthesized to encapsulate the fragrance molecule linalool.The results showed that the zwitterionic comb lipid molecules were capable of encapsulating more linalool than linear lipid molecules.At the same time,the zwitterionic comb-like lipid molecules also limited the slow release rate of the aroma,thereby increasing the fragrance retention time of the nano-fragrance.
基金financially supported by the Scientific Research Project of Yili Normal University(No.2022YSYB009)。
文摘We study the conformation of an amphiphilic comb-like copolymer in a selective solvent by using Brownian dynamics simulations.Our results demonstrate that,there is an optimal total degree of polymerization to form spherical micelles.Only when the total degree of polymerization is less than the optimal total degree of polymerization,a unimolecular spherical micelle can be formed,otherwise,the spherical micelle will be transformed into a cylindrical micelle.When the total degree of polymerization is less than the optimal total degree of polymerization,the radius of gyration and the stretching factor meet an exponential relationship,where the power exponent decreases with the increase of the length of hydrophilic side chains.The fundamental principles uncovered here afford insights for the optimization of molecular design of amphiphilic comb-like copolymers in various applications.
基金financially supported by the Scientific Research Project of Yili Normal University(No.2022YSYB009)the National Natural Science Foundation of China(No.2019M651340)。
文摘Combining Brownian dynamics simulations and self-consistent field theory,we demonstrate that the architectural parameters of coreshell comb-like chains have a decisive influence on their final self-assembled conformations.When the ratio of hydrophilic and hydrophobic segments is N_(g,g)∶N_(g,r)=3∶1,no core-shell structure is observed,and unsegregated chains or clusters are substituted.When N_(g,g)∶N_(g,r)=3∶2or 3∶3,the core-shell comb-like chains can be assembled into single micelles or structures where several small micelles are strung together by the backbone,which is similar to the pearl-necklace structure formed by the polyelectrolytes in poor solvent.With the increase of backbone length or grafting density,the probability of forming single micelles becomes lower,but the structures of two,three or more small micelles strung together are more observed.Our results indicate how to obtain the desired self-assembled structures of core-shell comb-like chains by regulating the architectural parameters,which could provide insights for the optimization of molecular design in various applications.
文摘Comb-like acrylic acid poly（ethylene glycol） methyl ether ester （MPEGA）-co-acrylamide （AM） copolymer [P（MPEGA-co-AM）] as novel phase change materials （PCMs） was successfully synthesized via free-radical water solution polymerization. The structures of P（MPEGA-co-AM） was characterized by Fourier Transform Infrared （FT-lR）. The experimental results showed that P（MPEGA-co-AM） copolymer possessed high molecular weight （Mo =66 kg/mol）, narrow molecular weight distribution （PDI≈1.14）. The phase transition temperature of copolymer decreases to 31℃, which is very much appreciated and urgently needed for smart PCM related to human body. Moreover, P（MPEGA-co-AM） had good thermal stability even at 380℃.
文摘Well-defined comb-like branched polymers having one branch in each repeating unit have been suc-cessfully synthesized by the coupling reaction of living polystyrene(PS)and polyisoprene(PI)anions with 1,1-diphenylethenyl(DPE)groups along PS backbone pre-pared via atom transfer radical polymerization(ATRP)of 4-vinylbenzyloxy benzophenone(Sc)followed by Wittig reaction.The resulting comb-like branched poly-mers were characterized by IR,1H-NMR,gel permeation chromatography(GPC)and static light scattering(SLS)in detail.The effect of living chains and DPE group molar ratio on grafting efficiency was discussed.The results show the coupling reaction of living chains and DPE groups was highly effective,and the coupling efficiency can be controlled via the feed molar ratios of living chains and DPE groups.Moreover,the effect of molecular weights of backbone(PSe)and PSLi or PILi on grafting efficiency was also discussed.The results show that when excess living polymers were used,the almost quantitative grafting efficiency could be achieved.
文摘The 3-section SG-DBR tunable laser is fabricate d using an ion implantation quantum-well intermixing process.The over 30nm discontinuous tuning range is achieved with the SMRS greater than 30dB.
