Chemistry modifications are usually performed to introduce specific group that can increase properties and functionality of materials. In this study, we present the synthesis of six new functionalized monomers prepare...Chemistry modifications are usually performed to introduce specific group that can increase properties and functionality of materials. In this study, we present the synthesis of six new functionalized monomers prepared by nucleophilic substitution reactions. Reaction of aliphatic and aromatic amines with acryloyl chloride at –20ºC, in presence of triethylamine allowed the synthesis of the corresponding amides. Proton nuclear magnetic resonance (1H NMR) spectroscopy, Fourier-transform infrared (FTIR) spectroscopy and ultraviolet- visible (UV-Vis) measurements confirmed the success of the synthesis with a yield over 90%. These compounds emerged as potentially attractive monomers since they can be used to obtain stimuli-sensitive polymeric materials, due to the presence of amide and pyridine groups.展开更多
In order to investigate the association of fibrin monomer polymerization function (FMPF) with traditional cerebrovascular risk factors and ischemic cerebrovascular disease in old people. 1∶1 paired case-control compa...In order to investigate the association of fibrin monomer polymerization function (FMPF) with traditional cerebrovascular risk factors and ischemic cerebrovascular disease in old people. 1∶1 paired case-control comparative study was performed for FMPF and traditional cerebrovascular risk factors on 110 cases of old ischemic cerebrovascular disease and 110 controls matched on age, sex and living condition. The results showed that cerebrovascular risk factors were more prevalent in case group than in control group. In the case group, FMPF was significantly higher than in control group. There was a significant positive correlation between hypertension and fibrin monomer polymerization velocity (FMPV), hypertension and fibrinogen (Fbg), alcohol consumption and Fbg, but no significant correlation between diabetic mellitus, smoking and FMPF was found. Among the parameters of blood lipids, there were significant positive correlations between total cholesterol (TC) and parameters of FMPF to varying degrees, triglycerides (TG) and FMPV, TG and Fbg. Our results also showed there were significant linear trends between TC and FMPV (P<0. 001), TC and Fbg (P=0. 0087), TG and FMPV/Amax (maximum absorbance)(P=0. 0143) respectively. Multiple logistic regression analysis revealed that FMPF in case group remained significantly higher than control group after adjustment of all risk factors that were significant in univariate analysis. It was concluded that there is a possible pathophysiological link between FMPF and cerebrovascular risk factors. An elevated FMPF is associated with ischemic cerebrovascular disease and an independent risk factor of this disease. In old people, detection of FMPF might be a useful screening to identify individuals at increased cerebrothrombotic risk.展开更多
Functional monomer (MP)_2PT having tertiary aromatic amino group was systhesized from the reaction of N, N-di (2-hydroxypropyl)-p-toluidine with 2-methyl acryloyl chloride. In the presence of organic peroxide, the rad...Functional monomer (MP)_2PT having tertiary aromatic amino group was systhesized from the reaction of N, N-di (2-hydroxypropyl)-p-toluidine with 2-methyl acryloyl chloride. In the presence of organic peroxide, the radical polymerization of (MP)_2PT in toluene took place. The kinetics of (MP)_2PT polymerization and the ESR spectra of LPO-(MP)2PT-MNP systems were determined respectively.展开更多
A molecular modeling approach was used to elucidate template-monomer interaction and the effect of solvent on the recognition of molecularly imprinted polymers （MIPs）. Ciprofloxacin （CIP） was taken as the template...A molecular modeling approach was used to elucidate template-monomer interaction and the effect of solvent on the recognition of molecularly imprinted polymers （MIPs）. Ciprofloxacin （CIP） was taken as the template molecule. The methacrylic acid （MAA）, 4-vinyl pyridine （4-Vpy）, acrylamide （AAM）, and 2-（trifluoromethyl） acrylic acid （TFMAA） were taken as the functional monomers, respectively. Density functional theory （DFT） at the LC-WPBE/6-31g（d,p） level has been adopted to investigate the geometry optimization. The NBO charge and the binding energies of CIP with the monomers were carried out. The molecular imprinting mechanism of CIP and the monomers as well as the influence of solvent was also discussed. Results indicate that CIP and the monomers are matchable in steric structure and chemical groups lead to ordered compounds. The interaction between CIP and TFMAA is the strongest, and when the ratio of CIP-TFMA_A is 1：6, the polymer has the lowest energy in toluene. The computational approach has been applied to provide details of interactions between CIP and the monomers. This research will hopefully shed light on the future study of CIP-MIPs.展开更多
Ultrahigh molecular weight functionalized isotactic polypropylene(f-UHMW-iPP)through the direct copolymerization of propylene with polar monomers is highly desirable but has not been accessed thus far because it invol...Ultrahigh molecular weight functionalized isotactic polypropylene(f-UHMW-iPP)through the direct copolymerization of propylene with polar monomers is highly desirable but has not been accessed thus far because it involves challenging regio-and stereochemistry along with usually reduced molecular weight.Herein,in contrast to the unsuccessful catalyst strategy,a polar monomer-assisted strategy is used to access the above material.The introduction of O-or S-functionalized long-chain polar olefins into the hafnium-catalyzed copolymerization of propylene(and bulkierα-olefins)significantly increases the copolymer molecular weight with a maximum observed increase of+488%.f-UHMW-iPP and functionalized isotactic poly(α-olefin)s(M_(w)>2000 kDa,[mmmm]:99%)are thus prepared at ambient conditions.The incorporation of 1 mol%of polar monomer improves the surface property and significantly increases the long-sought toughness(860%)of brittle iPP,without reducing the tensile strength(42 MPa)due to the key achievement of ultrahigh molecular weight.A discussion of the mechanism involved in the beneficial effects of incorporating the polar monomer is herein presented by an in-depth density functional theory calculation.展开更多
The random copolymers of isobutylene (IB) with polar comonomers of 4-acetoxystyrene (ACS) or 4-tert-butoxystyrene (TBO), P(IB-co-ACS) and P(IB-co-TBO), could be successfully synthesized via cationic copolymerization w...The random copolymers of isobutylene (IB) with polar comonomers of 4-acetoxystyrene (ACS) or 4-tert-butoxystyrene (TBO), P(IB-co-ACS) and P(IB-co-TBO), could be successfully synthesized via cationic copolymerization with FeCh-based initiating system. The kinetics of the cationic copolymerization process was in situ investigated by inserting a diamond probe into the reaction system by ATR-FTIR spectroscopy. The chemical structure and incorporation content of polar comonomers in the copolymers were characterized by GPC with RI/UV dual detectors and 1H-NMR spectroscopy. The corresponding functionalized random copolymers of IB with vinyl phenol P(IB-co-POH) carrying phenolic hydroxyl side groups could be further prepared via the complete hydrolysis of acetoxyl side groups in P(IB-co-ACS) or tert-butoxyl side groups in P(IB-co-TBO) copolymers. The functionalized P(IB-co-POH) copolymers became hydrophilic with water contact angle (WCA) of ca. 80° for the self-assembly in hot water, compared to the hydrophobic polyisobutylene with WCA of ca. 110°. The functionalized P(IB-co-POH) copolymers also displayed an excellent self-healing property due to the interaction of intermolecular hydrogen bonding and formation of three dimentional supramolecular networks from phenolic hydroxyl side groups. Furthermore, P(IB-co-POH) copolymers also provided a good matrix for the homogeneous dispersion for silica nanoparticles due to the formation of hydrogen bonding between copolymer chains and silica nanoparticles.展开更多
文摘Chemistry modifications are usually performed to introduce specific group that can increase properties and functionality of materials. In this study, we present the synthesis of six new functionalized monomers prepared by nucleophilic substitution reactions. Reaction of aliphatic and aromatic amines with acryloyl chloride at –20ºC, in presence of triethylamine allowed the synthesis of the corresponding amides. Proton nuclear magnetic resonance (1H NMR) spectroscopy, Fourier-transform infrared (FTIR) spectroscopy and ultraviolet- visible (UV-Vis) measurements confirmed the success of the synthesis with a yield over 90%. These compounds emerged as potentially attractive monomers since they can be used to obtain stimuli-sensitive polymeric materials, due to the presence of amide and pyridine groups.
文摘In order to investigate the association of fibrin monomer polymerization function (FMPF) with traditional cerebrovascular risk factors and ischemic cerebrovascular disease in old people. 1∶1 paired case-control comparative study was performed for FMPF and traditional cerebrovascular risk factors on 110 cases of old ischemic cerebrovascular disease and 110 controls matched on age, sex and living condition. The results showed that cerebrovascular risk factors were more prevalent in case group than in control group. In the case group, FMPF was significantly higher than in control group. There was a significant positive correlation between hypertension and fibrin monomer polymerization velocity (FMPV), hypertension and fibrinogen (Fbg), alcohol consumption and Fbg, but no significant correlation between diabetic mellitus, smoking and FMPF was found. Among the parameters of blood lipids, there were significant positive correlations between total cholesterol (TC) and parameters of FMPF to varying degrees, triglycerides (TG) and FMPV, TG and Fbg. Our results also showed there were significant linear trends between TC and FMPV (P<0. 001), TC and Fbg (P=0. 0087), TG and FMPV/Amax (maximum absorbance)(P=0. 0143) respectively. Multiple logistic regression analysis revealed that FMPF in case group remained significantly higher than control group after adjustment of all risk factors that were significant in univariate analysis. It was concluded that there is a possible pathophysiological link between FMPF and cerebrovascular risk factors. An elevated FMPF is associated with ischemic cerebrovascular disease and an independent risk factor of this disease. In old people, detection of FMPF might be a useful screening to identify individuals at increased cerebrothrombotic risk.
文摘Functional monomer (MP)_2PT having tertiary aromatic amino group was systhesized from the reaction of N, N-di (2-hydroxypropyl)-p-toluidine with 2-methyl acryloyl chloride. In the presence of organic peroxide, the radical polymerization of (MP)_2PT in toluene took place. The kinetics of (MP)_2PT polymerization and the ESR spectra of LPO-(MP)2PT-MNP systems were determined respectively.
基金Supported by the Natural Science Foundation of Jilin Province (No. 201215180)the Science and Technology Research Projects for Education Department of Jilin Province (No. 201359)Science and Technology Development Plan of Jilin Province (No. 20130206099sf)
文摘A molecular modeling approach was used to elucidate template-monomer interaction and the effect of solvent on the recognition of molecularly imprinted polymers （MIPs）. Ciprofloxacin （CIP） was taken as the template molecule. The methacrylic acid （MAA）, 4-vinyl pyridine （4-Vpy）, acrylamide （AAM）, and 2-（trifluoromethyl） acrylic acid （TFMAA） were taken as the functional monomers, respectively. Density functional theory （DFT） at the LC-WPBE/6-31g（d,p） level has been adopted to investigate the geometry optimization. The NBO charge and the binding energies of CIP with the monomers were carried out. The molecular imprinting mechanism of CIP and the monomers as well as the influence of solvent was also discussed. Results indicate that CIP and the monomers are matchable in steric structure and chemical groups lead to ordered compounds. The interaction between CIP and TFMAA is the strongest, and when the ratio of CIP-TFMA_A is 1：6, the polymer has the lowest energy in toluene. The computational approach has been applied to provide details of interactions between CIP and the monomers. This research will hopefully shed light on the future study of CIP-MIPs.
基金support from the National Natural Science Foundation of China(grant nos.22122110,22171038)the Jilin Provincial Science and Technology Department Program for Distinguished Young Scholars.
文摘Ultrahigh molecular weight functionalized isotactic polypropylene(f-UHMW-iPP)through the direct copolymerization of propylene with polar monomers is highly desirable but has not been accessed thus far because it involves challenging regio-and stereochemistry along with usually reduced molecular weight.Herein,in contrast to the unsuccessful catalyst strategy,a polar monomer-assisted strategy is used to access the above material.The introduction of O-or S-functionalized long-chain polar olefins into the hafnium-catalyzed copolymerization of propylene(and bulkierα-olefins)significantly increases the copolymer molecular weight with a maximum observed increase of+488%.f-UHMW-iPP and functionalized isotactic poly(α-olefin)s(M_(w)>2000 kDa,[mmmm]:99%)are thus prepared at ambient conditions.The incorporation of 1 mol%of polar monomer improves the surface property and significantly increases the long-sought toughness(860%)of brittle iPP,without reducing the tensile strength(42 MPa)due to the key achievement of ultrahigh molecular weight.A discussion of the mechanism involved in the beneficial effects of incorporating the polar monomer is herein presented by an in-depth density functional theory calculation.
基金financially supported by the National Natural Science Foundation of China (Nos. 21574007 and 51521062)the Fundamental Research Funds for the Central Universities (No. XK1802-2)
文摘The random copolymers of isobutylene (IB) with polar comonomers of 4-acetoxystyrene (ACS) or 4-tert-butoxystyrene (TBO), P(IB-co-ACS) and P(IB-co-TBO), could be successfully synthesized via cationic copolymerization with FeCh-based initiating system. The kinetics of the cationic copolymerization process was in situ investigated by inserting a diamond probe into the reaction system by ATR-FTIR spectroscopy. The chemical structure and incorporation content of polar comonomers in the copolymers were characterized by GPC with RI/UV dual detectors and 1H-NMR spectroscopy. The corresponding functionalized random copolymers of IB with vinyl phenol P(IB-co-POH) carrying phenolic hydroxyl side groups could be further prepared via the complete hydrolysis of acetoxyl side groups in P(IB-co-ACS) or tert-butoxyl side groups in P(IB-co-TBO) copolymers. The functionalized P(IB-co-POH) copolymers became hydrophilic with water contact angle (WCA) of ca. 80° for the self-assembly in hot water, compared to the hydrophobic polyisobutylene with WCA of ca. 110°. The functionalized P(IB-co-POH) copolymers also displayed an excellent self-healing property due to the interaction of intermolecular hydrogen bonding and formation of three dimentional supramolecular networks from phenolic hydroxyl side groups. Furthermore, P(IB-co-POH) copolymers also provided a good matrix for the homogeneous dispersion for silica nanoparticles due to the formation of hydrogen bonding between copolymer chains and silica nanoparticles.
