Based on special antipolyelectrolyte effect of zwitterion polymer with same quantity of anionic and cationic charges, we developed two types of salt-responsive polyampholytes, one with high molecular weight and low ch...Based on special antipolyelectrolyte effect of zwitterion polymer with same quantity of anionic and cationic charges, we developed two types of salt-responsive polyampholytes, one with high molecular weight and low charge density(HvL) and the other with low molecular weight and high charge density(LvH), by inverse emulsion polymerization. Molecular structure and salt-responsiveness of them were characterized by 1 H-NMR and rheology measurement, respectively. HvL and LvH were evaluated in saturated-salt bentonite suspension and influences of their ratio on apparent viscosity and fluid loss were investigated as well. The results indicate that HvL is better at decreasing fluid loss while LvH is better at maintaining low viscosity. A saturated saltwater drilling fluid centering on HvL and Lv H with simple formula was designed and applied. It is indicated that salt-responsive polyampholytes are fundamentally better than AM-AMPS anionic copolymer and AM-AMPS-DMDAAC amphoteric copolymer. The saturated saltwater drilling fluid has excellent thermal stability, tolerance to bentonite and shale cuttings, and certain resistance to CaCl_2. Salt-responsive polyampholytes can be used in KCl-saturated drilling fluid, with universal adaptability.展开更多
The significant role of the polyelectrolytic nature of non-collagenous proteins (NCPs) in regulating the in vivo mineralization of collagen provides important insights for scientists searching for analogues of NCPs to...The significant role of the polyelectrolytic nature of non-collagenous proteins (NCPs) in regulating the in vivo mineralization of collagen provides important insights for scientists searching for analogues of NCPs to achieve in vitro collagen mineralization. Polyampholyte carboxymethyl chitosan (CMC) has both carboxyl and amino groups, which allows it to act as a cationic or anionic polyelectrolyte below or above its isoelectric point (IP), respectively. In this study, CMC was employed as the analogue of NCPs to stabilize amorphous calcium phosphate (ACP) under acidic conditions (pH < 3.5) via the formation of CMC/ACP nanocomplexes. In the presence of both ACP nanoparticles and acid collagen molecules, ACP nanoparticles could be integrated into collagen fibrils during the process of collagen self-assembly and achieve intrafibrillar mineralization of collagen in vitro (i.e., synchronous self-assembly/mineralization (SSM) of collagen). This mode of mineralization is different from established mechanisms in which mineralization follows the self-assembly (MFS) of collagen. Thus, SSM provides a new strategy for developing materials from mineralized collagen scaffolds.展开更多
In this paper, the continuum self-consistent field theory (SCFT) is applied to study the structure and the interaction of the adsorption of symmetrical ABA polyampholytes (PAs) between two neutral planes. It is fo...In this paper, the continuum self-consistent field theory (SCFT) is applied to study the structure and the interaction of the adsorption of symmetrical ABA polyampholytes (PAs) between two neutral planes. It is found that the amounts of all the conformations decrease with the increase of the charge fraction of polymer chain, and increase with the increase of the bulk salt concentration and become saturated at high bulk salt concentration. The effective interaction between the two planes presented a long-range repulsion. Splitting it into various components and relating with the dependence of the variations of the conformations on environment parameters, we ,try to find the origin of the total long-range interaction between the two planes.展开更多
1H spin-spin relaxation time(T2) measurement of polyampholyte hydrogel poly(methylacrylic acidacryloyloxyethyl trimethylammonium chloride)[P(MA-DAC)] in different pH, ionic strength and temperature was carried o...1H spin-spin relaxation time(T2) measurement of polyampholyte hydrogel poly(methylacrylic acidacryloyloxyethyl trimethylammonium chloride)[P(MA-DAC)] in different pH, ionic strength and temperature was carried out to reveal the molecular mobility. Spontaneous volume transition of the polyampholyte hydrogel was also investigated by spin-spin relaxation time measurement. Meanwhile T2 and the proton component fraction were acquired to study the swelling behaviour of the hydrogel. Moreover the changes of T2 characterized the molecular mo- bility of polyampholyte hydrogel in various swelling states. And the results suggest that the mobility of the main chains and a few free side chains(the long T2) of P(MA-DAC) was dominated by the mesh size in the hydrogel net- work, depending on the swelling ratio(Q) and the mobility of the side chains(the short T2) was influenced by electrostatic interaction between different charges in polymer side chains. Finally the T2 measurements of P(MA-DAC) hydrogel in the spontaneous swelling-deswelling process demonstrated the electrostatic interaction of the charged side chains caused deswelling behavior. At the same time, the mobility state transition temperature of the charged side chains was also studied by the lH spin-spin relaxation time measurements, and the transition activation energy of the side chains is 2.72 kJ.展开更多
基金Supported by the China National Science and Technology Major Project(2017ZX05009-003,2016ZX05020-004,2016ZX05040-005)
文摘Based on special antipolyelectrolyte effect of zwitterion polymer with same quantity of anionic and cationic charges, we developed two types of salt-responsive polyampholytes, one with high molecular weight and low charge density(HvL) and the other with low molecular weight and high charge density(LvH), by inverse emulsion polymerization. Molecular structure and salt-responsiveness of them were characterized by 1 H-NMR and rheology measurement, respectively. HvL and LvH were evaluated in saturated-salt bentonite suspension and influences of their ratio on apparent viscosity and fluid loss were investigated as well. The results indicate that HvL is better at decreasing fluid loss while LvH is better at maintaining low viscosity. A saturated saltwater drilling fluid centering on HvL and Lv H with simple formula was designed and applied. It is indicated that salt-responsive polyampholytes are fundamentally better than AM-AMPS anionic copolymer and AM-AMPS-DMDAAC amphoteric copolymer. The saturated saltwater drilling fluid has excellent thermal stability, tolerance to bentonite and shale cuttings, and certain resistance to CaCl_2. Salt-responsive polyampholytes can be used in KCl-saturated drilling fluid, with universal adaptability.
基金financial support of the project from the National Natural Science Foundation of China (Nos. 31870947 and 81571016)
文摘The significant role of the polyelectrolytic nature of non-collagenous proteins (NCPs) in regulating the in vivo mineralization of collagen provides important insights for scientists searching for analogues of NCPs to achieve in vitro collagen mineralization. Polyampholyte carboxymethyl chitosan (CMC) has both carboxyl and amino groups, which allows it to act as a cationic or anionic polyelectrolyte below or above its isoelectric point (IP), respectively. In this study, CMC was employed as the analogue of NCPs to stabilize amorphous calcium phosphate (ACP) under acidic conditions (pH < 3.5) via the formation of CMC/ACP nanocomplexes. In the presence of both ACP nanoparticles and acid collagen molecules, ACP nanoparticles could be integrated into collagen fibrils during the process of collagen self-assembly and achieve intrafibrillar mineralization of collagen in vitro (i.e., synchronous self-assembly/mineralization (SSM) of collagen). This mode of mineralization is different from established mechanisms in which mineralization follows the self-assembly (MFS) of collagen. Thus, SSM provides a new strategy for developing materials from mineralized collagen scaffolds.
基金financially supported by the National Natural Science Foundation of China(Nos.21374011 and 21434001)973 project 2011CB808502
文摘In this paper, the continuum self-consistent field theory (SCFT) is applied to study the structure and the interaction of the adsorption of symmetrical ABA polyampholytes (PAs) between two neutral planes. It is found that the amounts of all the conformations decrease with the increase of the charge fraction of polymer chain, and increase with the increase of the bulk salt concentration and become saturated at high bulk salt concentration. The effective interaction between the two planes presented a long-range repulsion. Splitting it into various components and relating with the dependence of the variations of the conformations on environment parameters, we ,try to find the origin of the total long-range interaction between the two planes.
基金the National Natural Science Foundation of China
文摘1H spin-spin relaxation time(T2) measurement of polyampholyte hydrogel poly(methylacrylic acidacryloyloxyethyl trimethylammonium chloride)[P(MA-DAC)] in different pH, ionic strength and temperature was carried out to reveal the molecular mobility. Spontaneous volume transition of the polyampholyte hydrogel was also investigated by spin-spin relaxation time measurement. Meanwhile T2 and the proton component fraction were acquired to study the swelling behaviour of the hydrogel. Moreover the changes of T2 characterized the molecular mo- bility of polyampholyte hydrogel in various swelling states. And the results suggest that the mobility of the main chains and a few free side chains(the long T2) of P(MA-DAC) was dominated by the mesh size in the hydrogel net- work, depending on the swelling ratio(Q) and the mobility of the side chains(the short T2) was influenced by electrostatic interaction between different charges in polymer side chains. Finally the T2 measurements of P(MA-DAC) hydrogel in the spontaneous swelling-deswelling process demonstrated the electrostatic interaction of the charged side chains caused deswelling behavior. At the same time, the mobility state transition temperature of the charged side chains was also studied by the lH spin-spin relaxation time measurements, and the transition activation energy of the side chains is 2.72 kJ.