High Tensibility and PH Responsive Swelling of Nanocomposite Hydrogels Containing The Positively Chargeable 2 (Dimethylamino) Ethyl Methacrylate Monomer
High tensibility and pH-responsive swelling of nanocomposite hydrogels containing positively chargeable 2-(dimethylamino)ethyl methacrylate monomer. Positively chargeable hydrogels were synthesized by in situ copolymerization of AM and DMAEMA in an aqueous suspension of hectorite clay Laponite XLS. The UV-initiated NC gels possessed a more homogeneous structure with higher
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Original Title
High Tensibility and PH Responsive Swelling of Nanocomposite Hydrogels Containing the Positively Chargeable 2 (Dimethylamino)Ethyl Methacrylate Monomer
High tensibility and pH-responsive swelling of nanocomposite hydrogels containing positively chargeable 2-(dimethylamino)ethyl methacrylate monomer. Positively chargeable hydrogels were synthesized by in situ copolymerization of AM and DMAEMA in an aqueous suspension of hectorite clay Laponite XLS. The UV-initiated NC gels possessed a more homogeneous structure with higher
High Tensibility and PH Responsive Swelling of Nanocomposite Hydrogels Containing The Positively Chargeable 2 (Dimethylamino) Ethyl Methacrylate Monomer
High tensibility and pH-responsive swelling of nanocomposite hydrogels containing positively chargeable 2-(dimethylamino)ethyl methacrylate monomer. Positively chargeable hydrogels were synthesized by in situ copolymerization of AM and DMAEMA in an aqueous suspension of hectorite clay Laponite XLS. The UV-initiated NC gels possessed a more homogeneous structure with higher
High tensibility and pH-responsive swelling of nanocomposite hydrogels
containing the positively chargeable 2-(dimethylamino)ethyl methacrylate
monomer Meina Zhu, Lijun Xiong, Tao Wang, Xinxing Liu, Chaoyang Wang, Zhen Tong * Research Institute of Materials Science, South China University of Technology, Guangzhou 510640, China a r t i c l e i n f o Article history: Received 12 November 2009 Received in revised form 21 January 2010 Accepted 23 January 2010 Available online 29 January 2010 Keywords: Nanocomposite hydrogel Hectorite clay 2-(Dimethylamino)ethyl methacrylate pH response High tensibility a b s t r a c t Positively chargeable nanocomposite hydrogels (NC gels) were synthesized by in situ copolymerization of acrylamide (AM) and 2-(dimethylamino)ethyl methacrylate (DMAEMA) in an aqueous suspension of hectorite clay Laponite XLS. The stability of the Laponite suspension containing DMAEMA was monitored by its transmittance, viscosity and zeta potential. The polymerization was initiated either by redox or UV radiation to fabricate the NC gels. Elongation at break and tensile strength decreased with increasing DMAEMA content in monomers up to 17 mol%. As expected from the protonation of DMAEMA, the NC gels containing more than 5 mol% DMAEMA showed pH-responsive swelling; the gels were swollen at pH < 4 and shrunken at pH > 4. In comparison with the redox-initiated NC gels, the UV-initiated NC gels possessed a more homogeneous structure with higher transmittance, better mechanical properties, and a larger equilibrium swelling ratio at pH < 4. 2010 Elsevier Ltd. All rights reserved. 1. Introduction Stimuli-responsive hydrogels have been intensively studied from both academic and industrial viewpoints [13], because they are promising soft materials and have potential use for biomedical purposes [46]. Conventionally, hydrogels are fabricated with or- ganic cross-linkers (OR gels), such as N,N 0 -methylenebisacryla- mide, and are usually brittle and inextensible due to their lack of toughness. Consequently, their use within many promising appli- cations is restricted. However, nano-hybrids of polymer and clay often exhibit remarkably improved mechanical and functional properties compared with those of polymer alone or conventional composites [7,8]. Haraguchi et al. reported a novel polymerclay nanocomposite hydrogel (NC gel), which was in situ polymerized with N-isopropyl- acrylamide (NIPAm) monomer in an aqueous suspension of hector- ite clay Laponite [9]. The NC gel exhibited excellent properties, such as extraordinary tensibility (elongation at break 1300%, which is 50 times higher than that of the OR gel), and high transparency [10]. The Laponite platelet serves as a multifunctional cross-linker, and the polymer chains are attached to the surface of the clay platelets in the NC gel [1120]. Laponite, which carries strong negative charges on the surface and weak positive charges on the rim, forms a clear and colorless colloidal suspension in water, which is stabilized by electrostatic interactions [21,22]. However, aggregation and gelation occur when the concentration or ionic strength of the Laponite suspen- sion becomes high [23,24]. Consequently, it is difcult to fabricate pH-responsive NC gels using Laponite suspensions of ionic mono- mers (e.g., acrylic acid) because of their increased ionic strength. Recently, Song et al. reported a temperature- and pH-sensitive NC gel with a semi-interpenetrating organic/inorganic network, which was prepared by the polymerization of NIPAm in a suspension of gel-forming grade Laponite XLG containing linear poly(acrylic acid) [25]. In addition, Mujumdar and Siegel synthesized various pH- responsive NC gels by in situ copolymerization of NIPAm and some ionizible monomers, such as 2-(dimethylamino)ethyl methacrylate (DMAEMA), sodium methacrylate (SMA) and methacrylic acid. These gels showed elongation at break lower than 900% and a ten- sile strength lower than 100 kPa [26]. In our previous work, we successfully prepared a series of poly- acrylamide + hectorite clay nanocomposite hydrogels with elonga- tion at break beyond 4000% and determined their network chain densities and relaxation exponents [27]. These results suggested that an NC gel with acrylamide (AM) monomers would have ultra- high tensibility. Therefore, we fabricated pH-responsive NC gels of AM and sodium acrylate [28] by in situ copolymerization, as well as transparent pH- and temperature-responsive NC gels of NIPAm and SMA with elongation higher than 2000% [29]. All of the reported NC gels are anionic and swell at pH > 5, ex- cept for those described by Mujumdar and Siegel, who reported 1381-5148/$ - see front matter 2010 Elsevier Ltd. All rights reserved. doi:10.1016/j.reactfunctpolym.2010.01.003 * Corresponding author. Tel.: +86 20 87112886; fax: +86 20 87110273. E-mail address: mcztong@scut.edu.cn (Z. Tong). Reactive & Functional Polymers 70 (2010) 267271 Contents lists available at ScienceDirect Reactive & Functional Polymers j our nal homepage: www. el sevi er. com/ l ocat e/ react that their NIPAm/DMAEMA NC gels started to shrink as the pH in- creased beyond eight; however, no details of the Laponite suspen- sion stability with DMAEMA addition were provided [26]. In the present work, cationic NC gels containing the positively chargeable monomer DMAEMA were in situ copolymerized in a Laponite sus- pension. The stability of the suspension containing DMAEMA was characterized by its transmittance, viscosity and zeta potential. In order to modify the mechanical properties of the NC gels, two ini- tiation methods (redox and UV radiation) were compared for reducing the heterogeneity in the gels. 2. Experimental 2.1. Materials Acrylamide (AM), potassium peroxydisulfate (KPS) and 2,2 0 - azobisisobutyramidine dihydrochloride (AIBA) were puried by recrystallization from deionized water and dried under a vacuum at roomtemperature. 2-(dimethylamino)ethyl methacrylate (DMA- EMA) was puried with a column lled with activated Al 2 O 3 (200 mesh) to remove the inhibitor, stored over CaH 2 , and then distilled under reduced pressure prior to use. N,N,N 0 N 0 -tetramethylethylene- diamine (TEMED) was used as received. Synthetic hectorite clay of sol-forming grade Laponite XLS (Rockwood Co., 92.32 wt.% Mg 5.34 Li 0.66 Si 8 O 20 (OH) 4 Na 0.66 and 7.68 wt.% Na 4 P 2 O 7 ) was kindly provided by Rockwood and used after drying at 100 C for 4 h. Milli-Q Ultrapure water was used in all experiments, and argon gas was bubbled into the water for more than 1 h prior to use. 2.2. Synthesis of nanocomposite hydrogels The NC gels were synthesized through in situ radical copolymer- ization of AM and DMAEMA in an aqueous suspension of Laponite XLS. First, we prepared a Laponite suspension by dispersing the white power in Milli-Q Ultrapure water at the desired concentra- tion with stirring for at least 4 h. Next, the AM and DMAEMA monomers were added to the Laponite suspension. Finally, a 20 mg/mL solution of the initiator KPS and catalyst TMEDA were added to the system under continuous stirring at an icewater temperature. The polymerization was allowed to proceed at 20 C for 72 h. The NC gel was prepared in glass vessels having two dif- ferent shapes: a rod of 4.5 mm diameter 120 mm length for the tensile measurements and a strip of 1.0 mm diameter 5.0 mm length for the swelling measurements. The in situ copolymerization was also initiated with UV radia- tion, and the corresponding NC gels are referred to as UVNC gels. The Laponite suspension was prepared with the monomers in the same way as described above. Next, a 50 mg/mL solution of the ini- tiator AIBA was added to the suspension with stirring at icewater temperature in a dark environment. Finally, the solution was trans- ferred to glass vessels, and UV-induced polymerization was initi- ated with a radiation wavelength of 365 nm at 20 C in an incubator for 4 h. A UV lamp of 5 W was used, and the distance be- tween the UV source and glass vessels was about 15 cm. The shapes of the UVNC gel samples were the same as those fabri- cated by redox initiation. In all cases, the total monomer concentration was xed at 20 w/ v%, the clay content in all the NC gels was 6 w/v%, and the mole percent of DMAEMA in all monomers was varied from 3.2 to 16.7 mol%. The initiator was 1 wt.% of the total monomers for the NC gels and 0.1 wt.% for the UVNC gels. The NC gels initiated by KPS and TEMED are referred to as NCm gels, and those initiated with UV radiation are designated as UV-NCm gels, where m stands for the mole percent of DMAEMA in all monomers. For example, NC7.14 indicates an NC gel containing 7.14 mol% DMAEMA in all monomers (xed at 20 w/v%), with the Laponite XLS (xed at 6 w/v%) initiated by KPS and TEMED. UV-NC16.7 indicates an NC gel containing 16.7 mol% DMAEMA in all monomers (20 w/v%), with Laponite XLS (6 w/v%) initiated by UV radiation with AIBA. 2.3. Mechanical measurements Tensile strength was measured on the as-synthesized NC gel samples of 4.5 mm diameter 120 mm length with a Zwick Roell testing system at 20 C. The sample length between the jaws was 25 mm, and the crosshead speed was 100 mm/min. The tensile strain was taken as the length change relative to the initial length of the specimen, and the tensile stress was evaluated on the area of the initial cross section. 2.4. Swelling experiment The swelling experiments were performed at 20 C by immers- ing the NC gels (initial size of 1.0 mm diameter 5.0 mm length) in buffers having different pH values, from 2 to 10, at a constant io- nic strength of I = 0.01 M. The buffer solution was refreshed every two days. The swelling was followed by monitoring the diameter of the sample using a microscope with a micro-ruler. When the diam- eter ceased to change, we concluded that the swelling equilibrium was reached. The swelling ratio was dened as the gel volume at the swelling equilibrium V relative to its original volume V 0 of the as-prepared gel (not the dried gel). This denition did not change its meaning because the water content in all of the as-pre- pared NC gels was kept at 74 wt.%. Assuming isotropic swelling, the swelling ratio V/V 0 was calculated from V/V 0 = (d/d 0 ) 3 , where d and d 0 denote the corresponding diameters of the gel sample. 2.5. Characterization The transparency of the suspension and the NC gel was detected with a UV/Vis spectrophotometer (Hitachi U-3010) at 600 nm and 20 C. The viscosity of the suspension was measured with an AR-G2 stress-controlled rheometer using parallel plates with a diameter of 60 mm at 20 C. A water seal was used at the top of the xture to prevent water evaporation. The zeta potential f of the suspen- sion was determined at 20 C with a Zetasizer Nano-ZS90 (Malvern Instruments) instrument. The suspension was ltered through a 0.45-lm Millipore lter before the measurement. The zeta poten- tial values are reported as the averages of at least three successive measurements. The Smoluchowski relation, f = ug/e, was em- ployed, where u is the electrophoretic mobility, g is the solution viscosity and e is the solution permittivity, although the suspen- sion viscosity was used in calculating f instead of the water viscosity. 3. Results and discussion 3.1. Stability of Laponite suspension with monomer DMAEMA In the present work, the positively chargeable monomer DMA- EMA was added into an aqueous suspension of Laponite XLS with the neutral monomer AM. The pH of the suspension at 20 C was about 9.6 and increased to 11.0 with increasing DMAEMA concen- tration (Fig. 1). The stability of the suspension was characterized for its transmittance, viscosity, and zeta potential. The transmit- tance as a function of the retention time is shown in Fig. 2 for 6 w/v% Laponite XLS aqueous suspensions containing different DMAEMA contents at 20 C, and these values are compared to those of the Laponite suspension. All of the suspensions were transparent (transmittance 90%) for 1800 s. A slight increase in 268 M. Zhu et al. / Reactive & Functional Polymers 70 (2010) 267271 the transmittance with the addition of the monomers was proba- bly due to reduced clay platelet aggregation by a mild interaction with the AM monomer overlaid on the platelets [12]. By comparing curves ac, the transmittance decreased with increasing DMAEMA concentration. When the DMAEMA content was low (a of 3.2 mol% and b of 7.14 mol%), the suspension transmittance was constant over all retention times, indicating that a small amount of DMA- EMA did not cause instability in the Laponite suspension. However, when the DMAEMA content in all monomers was high (c of 10 mol% and d of 50 mol%), the transmittance decreased slightly with the retention time, suggesting that slight aggregates devel- oped in the Laponite suspension. Fig. 3 depicts the relationship between the viscosity change and retention time at 20 C. By considering a viscosity of 10 3 Pa s for pure water at 20 C, the viscosity of the Laponite suspension (2.4 10 3 Pa s) was very low and did not depend on the shear rate, suggesting that no aggregate structure was formed in the suspension at 6 w/v%. The viscosity slightly increased with the increasing mole percent of DMAEMA in the monomers (3.3 10 3 Pa s for 45 mol%) because of the hydrogen bonding be- tween the monomers. The clay suspension was stabilized by the electrostatic repul- sion among the clay platelets. Consequently, we monitored the zeta potential to detect the stability of the Laponite suspensions containing the AM and DMAEMA monomers. Fig. 4 presents the decreasing absolute value of zeta potential with increasing DMA- EMA monomer in the suspension; however, the zeta potential then leveled off at about 5 mol% of DMAEMA. The suspension viscosity was used in calculating the zeta potential. The dielectric constant of water was employed due to the minute effect of such a small amount of DMAEMA on the dielectric constant of water. The adsorption of DMAEMA by the Laponite platelets seemed to reduce their negative charges. 3.2. Tensibility of NC gels Fig. 5 demonstrates the stressstrain curves for the as-prepared NC and UVNC gels containing different amounts of DMAEMA. The 0 2 4 6 8 10 12 14 16 18 9.5 10.0 10.5 11.0 11.5 Laponite XLS 6 w/v% (DMAEMA + AM) 20 w/v% 20 o C p H DMAEMA / mol% Fig. 1. pH of an aqueous Laponite suspension as a function of the DMAEMA content in all of the monomers. 0 500 1000 1500 2000 70 80 90 100 T r a n s m i t t a n c e
/
% Time / s a b c d e Laponite XLS 6 w/v% DMAEMA + AM 20% 20 o C Fig. 2. Transmittance of Laponite aqueous suspensions with different monomer concentrations: (a) (DMAEMA + AM) 20 w/v% with 3.2 mol% DMAEMA; (b) (DMA- EMA + AM) 20 w/v% with 7.14 mol% DMAEMA; (c) (DMAEMA + AM) 20 w/v% with 10.0 mol% DMAEMA; (d) (DMAEMA + AM) 20 w/v% with 50.0 mol% DMAEMA; and (e) without any monomers. 0 500 1000 1500 2000 10 -3 10 -2 10 -1 Laponite XLS 6 w/v% (DMAEMA+AM) 20 w/v% 20 o C 0 7.14 16.7 33.3 40 45 V i s c o s i t y
/
P a
s Time / s DMAEMA / mol% Fig. 3. Retention time dependence of viscosity for the Laponite suspensions with the indicated DMAEMA concentrations. 0 5 10 15 20 25 -100 -80 -60 -40 -20 Z e t a - p o t e n t i a l
/
m V DMAEMA / mol% Laponite XLS 6 w/v% (DMAEMA + AM) 20 w/v% 20 o C Fig. 4. Zeta potential of the Laponite suspension plotted against the DMAEMA mol% in the total monomers. M. Zhu et al. / Reactive & Functional Polymers 70 (2010) 267271 269 DMAEMA content dependence of the elongation at break and ten- sile strength is displayed in Fig. 6 All of the as-prepared NC gels showed an ultrahigh tensibility, even higher than 1700% of the strain at break. Both the elongation at break and tensile strength for these gels decreased with increasing DMAEMA content in the monomers. The addition of DMAEMA to the suspension induced a change from a PAM homopolymer gel to a AM-DMAEMA copoly- mer gel. Consequently, this heterogeneous composition was caused in the copolymer NC gels due to the different monomer reactivity ratios of these two monomers (though the exact values are unknown). The photos in Fig. 7 illustrate that the copolymer NC gel became more opaque with higher DMAEMA content, though the suspension was transparent before the polymerization (Fig. 2). This heterogeneity in the NC gels likely led to the decreased elon- gation and strength with increasing DMAEMA content. When the polymerization was initiated by KPS and TEMED, the DMAEMA amino group served as an accelerator, which resulted in the rapid formation of the NC gel in 23 min, with more heteroge- neity. By contrast, when the polymerization was initiated by UV radiation with AIBA, the reaction occurred more slowly and the gel formed after 40 min, leading to a reduced heterogeneity in the UVNC gels. The transmittance of the UV-NC10 gel was 71%, while that of the NC10 gel was only 49.6%, conrming the higher heterogeneity in the NC gels initiated by redox compared to those initiated by UV radiation (Fig. 7). Therefore, the UVNC gel exhib- ited higher elongation at break and strength than the redox-initi- ated NC gels. 3.3. pH-responsive swelling behavior Fig. 8 illustrates the equilibrium swelling ratio V/V 0 of the NC (A) and UVNC gels (B) as a function of pH at an ionic strength of 0.01 M and 20 C. Both NC gels exhibited a pH-responsive swell- ing behavior. The swelling ratio of the NC gels containing DMEMA abruptly decreased as the pH was increased to 34, consistent with the swelling behavior of the PDMAEMA gels [30,31]. The average pKa value is 8.4 for the DMAEMA monomer, 7.8 for 4 kD PDMA- EMA, and 7.4 for 550 kD PDMAEMA [32], slightly decreasing with increasing molecular weight. These changes were due to the inter- ference in deprotonation of the amine group from the neighboring amine groups, as reported for other polymers [33], and they be- came more signicant in chemically cross-linked PDMAEMA hydrogels [31]. When the DMAEMA content was higher than 5 mol% in the monomers, the pH-responsive swelling became more distinct. The higher the DMAEMA content in the gel, the higher the 0 500 1000 1500 2000 2500 0 50 100 150 NC10 NC3.2 UV-NC10 UV-NC3.2 S t r e s s
/
k P a Strain / % Laponite XLS 6 w/v% (DMAEMA + AM) 20 w/v% 20 o C Fig. 5. Stressstrain curves for the indicated NC and UVNC gels at 20 C. 2 4 6 8 10 12 14 16 18 60 80 100 120 140 500 1000 1500 2000 2500 NC gel UV-NC gel S t r e n g t h
/
k P a B DMAEMA / mol% E l o n g a t i o n
/
% UV-NC gel NC gel A Fig. 6. DMAEMA content dependence of the elongation at break (A), and the tensile strength (B) for the NC gels and UVNC gels at a constant total monomer concentration (20 w/v%). Fig. 7. Photos of the NC and UVNC gels with different DMAEMA contents: (a) NC0, (b) UV-NC0, (c) NC5, (d) UV-NC5, (e) NC10, and (f) UV-NC10. All gels were polymerized at 20 C with 6 w/v% of Laponite and 20 w/v% of the total monomers. 270 M. Zhu et al. / Reactive & Functional Polymers 70 (2010) 267271 equilibrium swelling ratio became at low pH (23). These results indicated that the NC gels containing DMAEMA were weak poly- electrolytes, which were charged at pH < 4 and neutral at pH > 4 due to the protonation and deprotonation of the amine groups. By contrast, when the DMAEMA content was lower than 5 mol%, e.g., NC5, NC3.2 and NC0 gels, the swelling ratio was low and al- most pH independent. By comparison with the NC gels initiated by redox, the UVNC gels (Fig. 8B) showed a similar swelling behavior, but a higher swelling ratio than that initiated by redox, especially for those containing more than 5 mol% DMAEMA, be- cause of the lower heterogeneity in the UVNC gels, as mentioned above. 4. Conclusions Positively chargeable nanocomposite gels with high tensibility (elongation >1000%) were fabricated by in situ copolymerization of monomers AM and DMAEMA in an aqueous suspension of Lap- onite XLS. Redox or UV radiation initiation was used, and the latter produced more homogeneous NC gels with better mechanical properties due its gentler reaction process. As expected from pro- tonation of the DMAEMA monomer, the gels containing more than 5 mol% DMAEMA showed pH-responsive swelling and were swol- len at pH < 4 and shrunken at pH > 4. 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