共查询到20条相似文献,搜索用时 507 毫秒
1.
Man Fai Leung Junmin Zhu Frank W. Harris Pei Li 《Macromolecular rapid communications》2004,25(21):1819-1823
Summary: A new method has been developed to prepare smart polymeric microgels that consist of well‐defined temperature‐sensitive cores with pH‐sensitive shells. The microgels were obtained directly from aqueous graft copolymerizations of N‐isopropylacrylamide and N,N‐methylenebisacrylamide from water‐soluble polymers containing amino groups such as poly(ethyleneimine) and chitosan. The gel diameters ranged from 300 to 400 nm. The unique core‐shell nanostructures, which had narrow size distributions, exhibited tuneable responses to pH and temperature.
2.
Chia‐Fen Lee Chia‐Cheng Lin Wen‐Yen Chiu 《Journal of polymer science. Part A, Polymer chemistry》2008,46(17):5734-5741
In this work, poly(N‐isopropylacrylamide‐co‐acrylic acid) (poly(NIPAAm‐AA)) copolymer latex particles (microgels) were synthesized by the method of soapless emulsion polymerization. Poly(NIPAAm‐AA) copolymer microgels have the property of being thermosensitive. The concentration of acrylic acid (AA) and crosslinking agent N,N′‐methylenebisacrylamide were important factors to influence the lower critical solution temperature (LCST) of poly(NIPAAm‐AA) microgels. The effects of AA and crosslinking agent on the swelling behavior of poly(NIPAAm‐AA) microgels were also studied. The poly(NIPAAm‐AA) copolymer microgels were then used as a thermosensitive drug carrier to load caffeine. The effects of concentration of AA and crosslinking agent on the control release of caffeine were investigated. How the AA content and crosslinking agent influenced the morphology and LCST of the microgels was discussed in detail. The relationship of morphology, swelling, and control release behavior of these thermosensitive microgels was established. A new scheme was proposed to interpret the control release of the microgels with different morphological structures. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 5734–5741, 2008 相似文献
3.
Microgels consisting of poly-N,N-diethylacrylamide (PDEAAM) and copolymer microgels consisting of N,N-diethylacrylamide-co-N-isopropylacrylamide (PDEAAM-co-PNIPAM) have been synthesized via free radical polymerizations. The volume phase transition
of the microgels in aqueous solution was investigated by means of dynamic light scattering. All samples revealed a volume
phase transition upon heating and the size change was fully reversible. An unusual dependence of transition temperature on
the composition of the copolymer microgels was observed and samples were obtained with a transition temperature that was lower
than that of both corresponding homopolymer particles. This synergistic behavior could be caused by strong hydrogen bonding
between the mono- and the disubstituted acrylamide repeating units at nearly equimolar composition of the microgel. 相似文献
4.
Qin Wang Yanbing Zhao Yajiang Yang Huibi Xu Xiangliang Yang 《Colloid and polymer science》2007,285(5):515-521
In situ gelable poly(N-isopropylacrylamide-co-acrylamide) microgels were prepared by precipitation polymerization in the presence of various amounts
of N,N′-methlenebisacrylamide as a crosslinker. The diameters of microgels were in the range of 200–300 nm with narrow distributions
as determined by photo correlation spectroscopy. The equilibrium swelling ratio and thermosensitive properties of the microgels
increased with decreasing crosslinker content. The volume phase transition of microgels dispersions at high concentrations
were investigated by phase diagrams. The microgels dispersions experienced four phases when the temperature was increased:
semitranslucent swollen gel, clear flowable suspension, cloud flowable suspension, and white shrunken gel. The related phase
transition temperatures were influenced by crosslinker content and the concentration of the microgel dispersions. Herein,
the gelation temperature was changed by more than 20 °C, shrinking temperatures were slightly changed by about 3 °C, and cloud
point temperatures showed almost no change. The three phase transition temperatures of microgels dispersed in phosphate-buffered
saline solutions were lower than that in water. As drug carriers, the release rates of bleomycin from bleomycin-loaded microgel
dispersions exhibited diffusion control at human body temperature. 相似文献
5.
Thermoresponsive colloidal microgels were prepared by polymerisation of N-isopropylacrylamide (NIPAM) with varying concentration of a cross-linking monomer, N,N-methylenebisacrylamide (MBA), in water with either 0.4 or 6.7 mM concentration of an anionic surfactant, sodium dodecylsulphate (SDS). Volume phase transitions of the prepared microgels were studied in D2O by 1H-NMR spectroscopy including the measurements of spin–lattice (T1) and spin–spin (T2) relaxation times for the protons of poly(N-isopropylacrylamide) (PNIPAM) at temperature range 22–50 °C. In addition, microcalorimetry, turbidometry, dynamic light scattering and electrophoretic mobility measurements were used to characterise the aqueous microgels. The results from the different characterisation methods indicated that PNIPAM microgels prepared in 6.7 mM SDS concentration are structurally different compared to their correspondences prepared in 0.4 mM concentration. Increasing MBA concentration in the microgel synthesis appears to increase the structural heterogeneity in both cases of SDS concentration. PNIPAM structures with significantly higher molecular mobilities at temperatures above 35 °C were observed in the microgels prepared in 0.4 mM SDS concentration, as indicated by the 1H NMR relaxation times of different PNIPAM protons. We conclude that the high mobilities measured with NMR at elevated temperatures and also the clearly negative values of zeta potential are in connection to a fairly mobile surface layer with polyelectrolyte nature and a consequent high local lower critical solution temperature. 相似文献
6.
Kok H. Tan Wenjing Xu Simon Stefka Dan E. Demco Tetiana Kharandiuk Volodymyr Ivasiv Roman Nebesnyi Vladislav S. Petrovskii Igor I. Potemkin Andrij Pich 《Angewandte Chemie (International ed. in English)》2019,58(29):9791-9796
Active colloidal catalysts inspired by glutathione peroxidase (GPx) were synthesized by integration of catalytically active selenium (Se) moieties into aqueous microgels. A diselenide crosslinker (Se X‐linker) was successfully synthesized and incorporated into microgels through precipitation polymerization, along with the conventional crosslinker N,N′‐methylenebis(acrylamide) (BIS). Diselenide bonds within the microgels were cleaved through oxidation by H2O2 and converted to seleninic acid whilst maintaining the intact microgel microstructure. Through this approach catalytically active microgels with variable amounts of seleninic acid were synthesized. Remarkably, the microgels exhibited higher catalytic activity and selectivity at low reaction temperatures than the molecular Se catalyst in a model oxidation reaction of acrolein to acrylic acid and methyl acrylate. 相似文献
7.
Mirja Andersson Sirkka Liisa Maunu 《Journal of Polymer Science.Polymer Physics》2006,44(23):3305-3314
Thermoresponsive colloidal microgels were prepared by polymerization of N‐isopropylacrylamide (NIPAM) in the presence of a crosslinking monomer, N,N‐methylenebisacrylamide, in water with varying concentrations (<CMC) of an anionic surfactant, sodium dodecylsulphate (SDS). Volume phase transitions of the prepared microgels were studied in D2O by 1H NMR spectroscopy including the measurements of spin–lattice (T1) and spin–spin (T2) relaxation times for the protons of poly(N‐isopropylacrylamide) (PNIPAM) at temperature range 22–50 °C. In addition, microcalorimetry, turbidometry, dynamic light scattering, and electrophoretic mobility measurements were used to characterize the aqueous microgels. As expected, increasing SDS concentration in the polymerization batch decreased the hydrodynamic size of an aqueous microgel. Structures with high mobilities at temperatures above the LCST of PNIPAM were observed in the microgels prepared with small amount of SDS, as indicated by the relaxation times of different PNIPAM protons. It was concluded that the high mobility at high temperatures is in connection to a mobile surface layer with polyelectrolyte nature and with high local LCST. High SDS concentration in the synthesis was observed to prevent the formation of permanent, solid PNIPAM particles. The results from different characterization methods indicated that PNIPAM microgels prepared in high SDS concentrations appear to be more homogeneously structured than their correspondences prepared in low SDS concentration. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 3305–3314, 2006 相似文献
8.
Changwen Zhao Xiaoye Gao Pan He Chunsheng Xiao Xiuli Zhuang Xuesi Chen 《Colloid and polymer science》2011,289(4):447-451
A novel and facile strategy has been designed to prepare biodegradable microgels with thermo- and pH-responsive property.
The microgels were synthesized by the crosslinking of N-isopropylacrylamide with vinyl groups functionalized poly(L-glutamic acid) (PGA). The resultant microgels exhibited pH-dependent
phase transition behaviors in aqueous solutions and underwent abrupt lower critical solution temperature decrease when the
pH was reduced below the pK
a of PGA. Dynamic light scattering measurement revealed that the microgels exhibited shrinkage as the temperature increased
or the pH decreased. 相似文献
9.
Utilizing the hydrolysis and condensation of the methoxysilyl moieties, organic-inorganic hybrid poly(N-isopropylacrylamide-co-acrylamide-co-3-(trimethoxysilyl)propylmethacrylate) P(NIPAM-co-AM-co-TMSPMA) microgels were prepared via two different methods. The first method was that the microgels were post-fabricated from the crosslinkable linear P(NIPAM-co-AM-co-TMSPMA) terpolymer aqueous solutions above the lower critical solution temperature (LCST) of the terpolymer. For the second
method, the microgels were directly synthesized by conventional surfactant free emulsion copolymerization of NIPAM, AM, and
TMSPMA. The hydrodynamic diameter and stability of the resultant P(NIPAM-co-AM-co-TMSPMA) microgels strongly depend on the pH and temperature of the microgel aqueous solution. The hydrodynamic diameters
of the microgels decreased with increasing the measuring temperature. The phase transition temperature of the microgels was
found to be around 34°C, which was independent of the initial terpolymer concentration and shifted to lower temperature with
increasing the preparation temperature. Increasing the initial amount of AM will enhance the instability of the microgels
at high pH values. Moreover, the P(NIPAM-co-AM-co-TMSPMA) microgels obtained from the linear terpolymer had more homogeneous microstructures as compared with the corresponding
NIPAM/AM/TMSPMA microgels prepared by one step emulsion copolymerization as revealed by light scattering measurements. 相似文献
10.
Jose M. Cornejo-Bravo Claudia D. Becerra Kenia Palomino Héctor Magaña Ignacio Rivero Eduardo López-Maldonado 《Soft Materials》2021,19(1):89-99
ABSTRACT We prepared nano/microgels by precipitation copolymerization of N-isopropylacrylamide (NIPAAm), and one of three different carboxyalkyl methacrylamides [methacryloylamido hexanoic acid (M5), 8-methacryloylamido octanoic acid (M7), and 11-methacryloylamido undecanoic acid (M10)], either in the acid forms or as carboxylates (potassium salts). The hydrodynamic diameter (Dh) of the nano/microgels prepared with the carboxylates was smaller (≈100 nm for M10 copolymers), compared to the size of homopolymeric NIPAAm microgels prepared by dispersion polymerization (around 600 nm), indicating that the carboxylates act as surfactants reducing the size of the seeds during the polymerization process. These materials presented a swollen-shrunken transition temperature (T tr) similar to the T tr of the homopolymeric NIPAAm microgels, without pH sensitivity. On the other hand, the copolymeric microgels prepared from the acid form of the comonomers have a similar or bigger size than NIPAAm microgels. For these copolymers, the T tr can be tuned by the type and proportion of acid comonomer used and present pH sensitivity. This is important for biomedical applications such as positive temperature control release. Polyelectrolyte titration demonstrates that the nano/microgels prepared with the carboxylates behave as hard spheres, while the microgels prepared with the weak acid behave as porous materials. 相似文献
11.
Shanza Rauf Khan Muhammad Ajmal Mohammad Siddiq Abbas Khan 《Journal of Dispersion Science and Technology》2013,34(10):1324-1333
Multiresponsive poly(N-isopropylacrylamide-co-methacrylic acid) microgels were synthesized by precipitation polymerization in aqueous medium. Then silver-poly(N-isopropylacrylamide-co-methacrylic acid) hybrid microgels were prepared by in-situ reduction of silver ions. Formation of microgels was confirmed by Fourier transform infrared spectroscopic analysis. pH and temperature sensitivity of microgel was studied by dynamic light scattering. Hydrodynamic radius of microgels decreases with increase in temperature at pH 8.20 and show volume phase transition temperature around 45°C. At pH 2.65, hydrodynamic radius decreases with increase in temperatures upto 35°C but further increase in temperature causes aggregation and microgel becomes unstable due to increase of hydrophobicity. With increase in pH of medium, the hydrodynamic radius of microgels increases sigmoidally. Formation of silver nanoparticles inside microgel and pH dependence of surface plasmon resonance wavelength of the hybrid microgels were investigated by ultraviolet-visible spectroscopy. The value of surface plasmon resonance band and absorbance associated with surface plasmon resonance band increases with increases in pH of the medium. The apparent rate constant of reduction of p-nitrophenol was found to be linearly dependent on volume of hybrid microgels used as catalyst. The system has a potential to be used as effective catalyst for rapid degradation of industrial pollutant. 相似文献
12.
We report the results of comparative studies of the swelling behavior of polyelectrolyte (PE) and polyampholyte (PA) microgels in response to pH, ionic strength, temperature, and solvent composition. Polyelectrolyte microgels used were cross-linked binary copolymers of poly(N-isopropylacrylamide) (polyNIPAm) and acrylic acid (AA) or vinyl imidazole (VI). The PA microgels with an excess of either cationic or anionic groups swelled at low or high pH values, respectively, analogous to PE microgels. The PA microgels with similar amounts of AA and VI groups exhibited marked swelling at both high and low pH values. All PA microgels shrank in the intermediate range of pH due to electrostatic attraction between charged AA and VI moieties. In moderately concentrated salt solutions, PA microgels underwent swelling showing antipolyelectrolyte behavior. The extent of swelling of PA microgels increased with rise in AA content. The temperature-dependent contraction of both PE and PA microgels occurred at higher temperatures when AA and VI groups were charged and hydrophilic. Ion pairing between the AA and VI groups increased the extent of the temperature-induced deswelling in PA microgels. The solvent-dependent swelling of PE and PA microgels in ethanol–water mixtures was governed by competing electrostatic and cosolvency effects.
相似文献
Eugenia KumachevaEmail: |
13.
Xiaomei Ma Jingyu Xi Xian Zhao Xiaozhen Tang 《Journal of Polymer Science.Polymer Physics》2005,43(24):3575-3583
Two monomers containing functional ? OH groups with different hydrophilic long side chains (viz., triethyleneglycol methacrylate (TREGMA) and polyethyleneglycol methacrylate (PEGMA)) were selected to modify the swelling/deswelling behavior of poly(N‐isopropylacrylamide) (pNIPAM) microgels. Dynamic scattering technique, turbidimetric method, and differential scanning calorimetry (DSC) were employed to investigate the deswelling behavior of the microgels. Experimental results show that the two series of microgels are identical in that incorporation of hydrophilic chains containing ? OH groups causes the volume‐phase transition temperature (VPTT) of pNIPAM microgels to shift to higher temperature; the more hydrophilic the side chains, the more the VPTTs shift. Although PEGMA are more effective in elevating the VPTTs of pNIPAM microgels than TREGMA, p(NIPAM‐co‐TREGMA) microgels show better deswelling properties than p(NIPAM‐co‐PEGMA) microgels, i.e., they have much larger deswelling ratios (α) and display less continuous volume‐phase transition. The VPTTs of the modified microgels can be modulated to well close to the normal body temperature of human beings. These characteristics along with the functional ? OH groups they contain make the microgels competitive candidates for biomaterials. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 3575–3583, 2005 相似文献
14.
Surfactant-free, radical precipitation copolymerization of N-isopropylmethacrylamide and the cationic co-monomer N-(3-aminopropyl) methacrylamide hydrochloride (APMH) was carried out to prepare microgels functionalized with primary amines.
The morphology and hydrodynamic diameter of the microgels were characterized by atomic force microscopy and photon correlation
spectroscopy, with the effect of NaCl concentration and initiator type on the microgel size and yield being investigated.
When a 2,2′-azobis (2-amidinopropane) dihydrochloride (V50)-initiated reaction was carried out in pure water, relatively small
microgels (∼160 nm in diameter) were obtained in low yield (∼20%). However, both the yield and size increased if the reaction
was carried out in saline or by using ammonium persulfate as initiator instead of V50. Stable amine-laden microgels in the
range from 160 to 950 nm in diameter with narrow size distributions were thus produced using reaction media with controlled
salinity. Microgel swelling and electrophoretic mobility values as a function of pH, ionic strength, and temperature were
also studied, illustrating the presence of cationic sidechains and their influence on microgel properties. Finally, the availability
of the primary amine groups for post-polymerization modification was confirmed via modification with fluorescein-N-hydroxysuccinamide. 相似文献
15.
Chia‐Lung Lin Wen‐Yen Chiu 《Journal of polymer science. Part A, Polymer chemistry》2006,44(5):1648-1659
The electrically conductive polypyrrole/dodecylbenzene sulfonic acid/poly(N‐isopropylacrylamide‐co‐acrylic acid) (PPy/DBSA/poly(NIPAAm‐co‐AA)) composite microgels were synthesized by a chemical oxidation of pyrrole in the presence of DBSA as the primary dopant, and poly(NIPAAm‐co‐AA) microgels as the polymeric codopant and template, in which APS was used as the oxidant. It was proposed to prepare “intelligent” polymer microgel particles containing both thermosensitive and electrically conducting properties. The polymerization of pyrrole took place directly inside the microgel networks, leading to formation of composite microgels and the morphology was observed by transmission electron microscope. PPy particles interacted strongly with microgels, as the acid groups of microgels acted as the polymeric codopant. The composite microgels thus formed showed electrically conducting behavior dependent on humidity and temperature. At temperatures lower than lower critical solution temperature, the conductivity decreased with increasing the humidity and a small hysteresis phenomenon was observed. The hysteresis became indistinct when temperature was near volume phase transition temperature. However, after the treatment of high temperature and high humidity, the conductivity increased surprisingly due to the structure reorganization inside the composite microgels. The distinctive functionality of the PPy composite microgels was expected to be utilized in many attractive applications. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 1648–1659, 2006 相似文献
16.
Poly (N-isopropylacrylamide) microgel based assemblies for organic dye removal from water: microgel diameter effects 总被引:1,自引:0,他引:1
Deepika Parasuraman Edmund Leung Michael J. Serpe 《Colloid and polymer science》2012,290(11):1053-1064
Poly (N-isopropylacrylamide)-co-acrylic acid (pNIPAm-co-AAc) microgel based assemblies (aggregates) were synthesized from microgels of various diameters via polymerization of the crosslinker N,N′-methylenebisacrylamide (BIS) in the presence of microgels in solution. We investigated the ability of the respective aggregates to remove the organic, azo dye molecule 4-(2-hydroxy-1-napthylazo) benzenesulfonic acid sodium salt (Orange II) from water at both room and elevated temperatures. The results from the microgel aggregates made from 1.1-μm-diameter [Parasuraman and Serpe. ACS Applied Materials & Interfaces, 2011] microgels were compared to aggregates synthesized from 321-nm and 1.43-μm-diameter microgels. Aggregates made from the same size microgels showed increased uptake efficiency as the concentration of BIS in the aggregates was increased, while for a given BIS concentration, the uptake efficiency increased with increasing microgel size in the aggregate. We attribute this to the “nature” of the aggregates; aggregates have void space between the microgels that can serve as reservoirs for Orange II uptake—the void spaces are hypothesized to increase with larger diameter microgels. By exploiting the thermoresponsive nature of the microgels, and microgel based aggregates, 85.3 % removal efficiencies can be achieved. Finally, all uptake trends for the aggregates, at room temperature, were fit with a Langmuir sorption isotherm model. 相似文献
17.
Summary: Microgel particles have received an increasing interest in the biomedical field. Temperature-sensitive microgels gained particular interest due to their potential use as controlled drug delivery systems. With the objective to produce new thermoresponsive biocompatible microgels, the synthesis and characterization of two families of microgel particles obtained by using N-vinylcaprolactam (VCL) as main monomer and N,N′-methylenbisacrylamide (BA) or poly(ethylene glycol) diacrylate (PEGDA) as crosslinkers are described. Evidence of hydrolysis VCL during polymerization is also presented. 相似文献
18.
Shanshan Bian Jin Zheng Wuli Yang 《Journal of polymer science. Part A, Polymer chemistry》2014,52(12):1676-1685
The synthesis and characterization of a new photocleavable crosslinker is presented here. Dual stimuli‐responsive P(VCL‐co‐NHMA) microgels were prepared by precipitation polymerization of vinylcaprolactam (VCL) with N‐hydroxymethyl acrylamide (NHMA) and the new crosslinker. The microgels had distinct temperature sensitivity as observed in the case of PVCL‐based particles and their volume phase transition temperature (VPTT) shifted to higher temperature with increasing NHMA content. Photolytic degradation experiments were investigated by irradiation with UV light, which led to microgel disintegration caused by cleavage of the photolabile crosslinking points. The degradation behavior of the microgels was conducted with respect to degradation rates by means of the relative turbidity changes. Hence, the microgels could totally degrade into short linear polymers by UV light, thus representing a great potential as new light and temperature dual responsive nanoscale materials. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014 , 52, 1676–1685 相似文献
19.
Thomas A. Vilgis 《Macromolecular theory and simulations》1998,7(1):59-63
In this note microgels with and without excluded volume interactions are considered. Based on earlier exact computations on Gaussian mircogels, which are formed by self-crosslinking (with M crosslinks) of polymer chains with chainlength N, Flory type approximations are used to get first insight to their behavior in solution. It is shown that two different types of microgels exist: A special type of branched polymer whose size scales as R ∝ N2/5/M−1/5, instead of R ∝ N1/2. The second type are c*-microgels whose average mesh sizes r are swollen and form self avoiding walks with a scaling law of the form r = a(N/M)3/5. 相似文献
20.
Virginia Sáez Martínez Leyre Pérez Álvarez Estíbaliz Hernáez Teresa Herrero Issa Katime 《Journal of polymer science. Part A, Polymer chemistry》2007,45(17):3833-3842
Poly(p‐nitrophenylacrylate‐co‐methacrylamide) and poly(p‐Nitrophenylacrylate‐co‐N,N′‐isopropylacrylamide) reactive microgels were synthesized by precipitation polymerization. The process was followed qualitatively by infrared spectroscopy (ATR‐FTIR) and microgels composition was determined by nuclear magnetic resonance (1H NMR). Scanning electron microscopy of obtained colloidal particles showed strictly spherical morphologies with a moderate polydispersity. The average hydrodynamic particle diameter and particle size distributions were measured by quasi‐elastic light scattering and the particle size distributions obtained ranged from 100 to 600 nm. Several synthetic parameters affect the particle size of these materials and thus, indirectly, their properties and future applications. In this article, we report the influence of different polymerization reaction conditions in the final microgel dimensions. For example, we observed that the different solvent‐comonomer affinity induced a significant change in swollen particle size of the copolymeric microgels. On the other hand, the crosslinking density limited the particle sizes, but an excess of crosslinker content in the reaction mixture resulted in the opposite effect. Finally, we also studied the influence of initiator content in the mean particle size. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 3833–3842, 2007 相似文献