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1.
A new class of biodegradable hydrogels, consisting of hydrophobic poly(D ,L )lactic acid (PDLLA) and hydrophilic dextran segments with a polymer network structure, was synthesized with UV photopolymerization. Unsaturated vinyl groups first were introduced onto the PDLLA and dextran polymer backbones, then followed by a crosslinking reaction of diacrylate-terminated PDLLA and dextran acrylate. The chemical crosslinking forced the hydrophobic PDLLA and hydrophilic dextran segments to mix with each other in the network hydrogels. The new polymers were characterized by standard polymer characterization methods such as NMR, Fourier transform infrared spectroscopy, and gel permeation chromatography. The effects of reaction time, temperature, and molar ratio of the reactants on the incorporation of acrylate onto the polymer backbone were examined. A series of hydrogels with different dextran/PDLLA composition ratios was prepared, and their swelling behaviors were studied. These new bicomponent network hydrogels had a wide range of hydrophilicity to hydrophobicity that was difficult to achieve in totally hydrophilic hydrogels. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 4554–4569, 1999  相似文献   

2.
Telechelic urethane acrylate anionomer (UAA) chain showed less viscosity and polyelectrolyte behavior in water than dimethyl acetamide (DMAc) because of hydrophobic aggregation. UAA networks prepared in different solvents (water and DMAc) exhibited very different swelling behaviors in the same swelling medium, which can be interpreted as due to the very different microstructures formed in the solvents. UAA networks prepared with water (UAHG networks) had microphase‐separated hydrophilic and hydrophobic domains, whereas UAA networks synthesized with DMAc (UADG networks) had relatively homogeneous network structures. The mechanical property of the UAHG and UADG networks, measured with a dynamic mechanical analyzer, was also very sensitive to the solvent type used during the crosslinking reaction. UAHG networks with a microphase‐separated structure had a higher modulus than UADG networks. The results of the mechanical property measurements showed that water was a much better solvent for the hydrophilic hard segments of UAA chain than DMAc, even though DMAc dissolved both hydrophilic and hydrophobic segments of UAA chain. © 2000 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 38: 2081–2095, 2000  相似文献   

3.
Degrading hydroxyethylmethacrylate‐grafted dextran (dex‐HEMA) hydrogels generate a relatively sudden increase in osmotic pressure upon degradation into dextran solutions. This phenomenon is currently being examined as a possible means of developing a pulsatile drug‐delivery system. Here a mathematical model based on scaling concepts is presented to describe this sudden increase in swelling pressure and to provide a framework for the rational design of pulsatile delivery systems based on this phenomena. The model provides a good fit to the swelling pressures measured for dex‐HEMA gel/free dextran mixtures that simulate degrading dex‐HEMA gels. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 3397–3404, 2004  相似文献   

4.
A series of novel multifunctional hydrogels that combined the merits of both thermoresponsive and biodegradable polymeric materials were designed, synthesized, and characterized. The hydrogels were copolymeric networks composed of N‐isopropylacrylamide (NIPAAM) as a thermoresponsive component, poly(L‐lactic acid) (PLLA) as a hydrolytically degradable and hydrophobic component, and dextran as an enzymatically degradable and hydrophilic component. The chemical structures of the hydrogels were characterized by an attenuated total reflection–Fourier transform infrared spectroscopy (ATR–FTIR) technique. The hydrogels were thermoresponsive, showing a lower critical solution temperature (LCST) at approximately 32 °C, and their swelling properties strongly depended on temperature changes, the balance of the hydrophilic/hydrophobic components, and the degradation of the PLLA component. The degradation of the hydrogels caused by hydrolytic cleavage of ester bonds in the PLLA component was faster at 25 °C below the LCST than at 37 °C above the LCST, determined by the ATR–FTIR technique. Due to their multifunctional properties, the designed hydrogels show great potential for biomedical applications, including drug delivery and tissue engineering. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 5054–5066, 2004  相似文献   

5.
Novel chitosan‐based polymeric networks were synthesized and characterized by FTIR, UV and C13 NMR. A naturally occurring crosslinking reagent—genipin, which has been used in herbal medicine and in the fabrication of food dyes, was used to prepare crosslinked chitosan hydrogel. The heterocyclic compound of genipin crosslinked chitosan was formed by a nucleophilic attack by amino group on the olefinic carbon atom at C‐3 of deoxyloganin aglycone, followed by opening of the dihydropyran ring and attack by the secondary amine group on the intermediate aldehyde group. Additional, secondary amide linkages could be established in the genipin crosslinked chitosan network by the reaction of ester group of genipin with amino group of chitosan. This bifunctional linkages of genipin with amino group of chitosan leads to form crosslinked networks. Genipin reacted with nucleophilic reagent such as chitosan could further go through a polymerization to form oligomer‐bridge in the crosslinked network. The finally formed chitosan networks are blue color, elastic and exhibits pH‐dependent swelling characteristics. The swelling ratio of the chitosan hydrogel increased at pH lower than 3 and higher than 11 due to the hydrolysis of amide linkage in the genipin crosslinked chitosan network by acid or alkaline, followed by the protonation of amine group or ionization of carboxyl acid group in the network. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 2804–2814, 2000  相似文献   

6.
Poly(acrylic acid)‐l‐polytetrahydrofuran (PAA‐l‐PTHF) and poly(methacrylic acid)‐l‐polytetrahydrofuran (PMAA‐l‐PTHF) networks were synthesized by the free‐radical copolymerization of hydrophobic polytetrahydrofuran diacrylates with hydrophilic acrylic acid and methacrylic acid. Their swelling behavior was studied. Both PAA‐l‐PTHF and PMAA‐l‐PTHF networks had four solubility parameters, which indicated that they exhibited not only the properties of both hydrophobic and hydrophilic segments but also the combined properties of these two segments. The swell of these two series of networks was composition‐dependent in organic solvents and water. The relationship between the equilibrium swelling ratio (SRe) in nonpolar solvents and the composition of the networks [the weight fraction of the PTHF segment (PTHF%)] may be expressed with a linear equation: SRe = A × PTHF% + B. A and B are parameters that relate to the interaction of hydrophilic and hydrophobic segments with nonpolar solvents and to the properties of the networks, respectively. Because of the presence of a ? COOH group, these two network series were pH‐sensitive when the content of hydrophilic segments was higher. The pH sensitivity of networks could be controlled not only by the composition of the networks but also by the hydrophobic degree of the hydrophilic segments. © 2001 John Wiley & Sons, Inc. J Polym Sci Part B: Polym Phys 39: 1784–1790, 2001  相似文献   

7.
A series of novel amphiphilic polyacrylamide‐l‐polytetrahydrofuran (PAm‐l‐PTHF) networks were prepared by the free‐radical copolymerization of hydrophobic ditelechelic polytetrahydrofuran acrylate (PTHFDA) with hydrophilic acrylamide. PTHFDA was synthesized by acrylation of the corresponding hydroxycapped PTHF with acrylic acid in cyclohexane. After acrylation, there was no significant difference in the molecular weights and molecular weight distributions between the original PTHF and the resulting PTHFDA. Network structures and compositions were characterized by elemental analyses, Fourier transform infrared, differential scanning calorimetry, scanning electron microscopy, and swelling data. The networks can swell both in organic solvents and in water, which indicates that they are amphiphilic. The swelling of the networks in different solvents is composition‐dependent. According to differential scanning calorimetry, scanning electron microscopy, and swelling tests, the networks have a microphase‐separated and bicontinuous morphology. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 3812–3820, 2000  相似文献   

8.
A pH and reduction dual‐stimuli‐responsive PEGDA/PAMAM injectable network hydrogel containing “acetals” as pH‐sensitive groups and “disulfides” as reducible linkages was designed and synthesized via aza‐Michael addition reaction between PAMAM and PEGDA diacrylates. The pore size and swelling ratio of hydrogels was varied from 14 ± 3 to 19 ± 4 μm and 214 ± 13 to 300 ± 19 μm, respectively, with varying ethylene glycol repeating units in diacrylates. The swelling ratio of PEGDA/PAMAM network hydrogel increased with increase in the molecular weight of PEG and with decrease in pH. The presence of different cationizable amino‐functionalities in PEGDA/PAMAM network hydrogel helped to enhance the swelling ability of hydrogel under the acidic conditions. The continuous increase in metabolically active live HeLa cells with time in MTT assay implied biocompatibility/noncytotoxicity of the synthesized PEGDA/PAMAM injectable network hydrogel. Furthermore, the prepared PEGDA/PAMAM hydrogel showed higher degradation at lower pH and at higher concentration of DTT. The burst release of doxorubicin from PEGDA/PAMAM hydrogel under the environment of the lower pH and in presence of DTT compared to the release at normal physiological pH and in absence of DTT suggested the potential ability of this model hydrogel system for targeted and selective anticancer drug release at tumor tissues. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2018 , 56, 2080–2095  相似文献   

9.
We describe an investigation of fluorescence correlation spectroscopy into the diffusion of fluorescein‐tagged dextran (FDEX) in a poly(methacrylic acid) (PMAA) hydrogel. The temperature dependence of FDEX diffusion is shown to follow Zimm behavior in pure water, and the decrease in the diffusion coefficient when in the PMAA hydrogel has been modeled. The addition of acid and alkali (HCl and NaOH, respectively) not only control the swelling and collapse of the hydrogel but also reveal a strong pH dependence of the dextran diffusion coefficient, which shows a (nonmonatonic) increase with pH. The addition of NaCl and CaCl2 salts similarly showed evidence of network swelling, most notably at low salt concentration, but also that the diffusion coefficient within the gel at these low concentrations is larger than that in the equivalent solution without the hydrogel, indicating that the combination of hydrogel and salt works to increase the diffusion coefficient above that in pure water. © 2012 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2012  相似文献   

10.
Hydrophobic poly(lactic acid) nanospheres were fabricated and used as an additive during the polymerization and gelation process of temperature‐sensitive poly(N‐isopropylacrylamide) (PNIPAAm) hydrogels. The influence of hydrophobic additive on properties of PNIPAAm hydrogels was examined. The interior morphology studied by scanning electron microscopy revealed that the hydrophobic additive induced a macroporous structure in the resulting PNIPAAm hydrogels. Results demonstrate that the hydrophobic additive acts as a pore‐forming agent like conventionally used hydrophilic additive does during the gelation process. Because of the macroporous network and incorporated additives, the temperature‐sensitive characteristics, particularly the equilibrium swelling ratio at room temperature and shrinking rate upon temperature increase of modified PNIPAAm hydrogels, are significantly improved. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 5490–5497, 2005  相似文献   

11.
A new PNIPA hydrogel was synthesized by carrying out the polymerization in the gelated corn starch aqueous solution. This PNIPA hydrogel has an improved surface property and does not form the disadvantageous bubbles during the shrinking process. This change is due to the hydrogen bonds between the corn starch and the hydrophilic side groups of the PNIPA chains, which let the starch act as the long graft-like chains of the PNIPA hydrogel. During the reswelling process, this PNIPA hydrogel exhibits a sigmoidal swelling pattern. This hydrogel with improved surface property may be very useful for the potential applications of the temperature-sensitive hydrogel. Copyright 2000 Academic Press.  相似文献   

12.
In this study, sodium humate/poly(acrylamide‐co‐methacrylic acid)/kaolin semi‐interpenetrating polymer network hybrid hydrogel was synthesized as an effective adsorbent for the removal of methylene blue. The morphological and structural properties, and swelling behavior in distilled water and various environments of hybrid hydrogel were investigated with different analyses and tests. The equilibrium swelling percent of hybrid hydrogel reached to 37,000% in 240 min. The parameters (agitation time, concentration, dose, temperature, and pH) affecting adsorption process for methylene blue were optimized using Taguchi method. The data obtained in optimum conditions were well fitted to Langmuir adsorption isotherm and maximum adsorption capacity was determined as 833. 33 mg/g. In the light of the results, the utilization of hybrid hydrogel with high swelling capacity is foreseen as a favored adsorbent in several separation processes. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019 , 57, 1070–1078  相似文献   

13.
Tailor‐made urethane acrylate anionomer (UAA) chains show higher viscosity and polyelectrolyte behavior in dimethyl sulfoxide (DMSO) than in water and toluene. Water is a nonsolvent for the hydrophobic soft segment but a good solvent for the hydrophilic hard segments, so hydrophobic segments are aggregated and form particles in the water phase, resulting in a smaller viscosity. Also, the fact that the viscosity of UAA chains is lowest in toluene can be interpreted as a result of ionic aggregation due to the nonpolarity of toluene. The structures of UAA networks dramatically change with the nature of the solvents used (i.e., the interaction between the UAA chains and the solvents used changes); this is confirmed by the results of tensile property, morphology, and wide‐angle X‐ray scattering data. Ionic aggregation formed in UAA/toluene (UATG networks) and hydrophobic aggregation formed in UAA/water (UAAG networks) are locked in by a chemical crosslinking reaction and result in a greater modulus and X‐ray scattering intensity. The greater elongation and swelling ratio in methylene chloride of UATG networks prepared in a UAA/toluene solution indicates that toluene is a better solvent than DMSO for the hydrophobic segments of UAA chains. Also, the greater swelling ratio in a pH 11 buffer solution and greater modulus of UAAG networks show that water is a better solvent than DMSO for hydrophilic ionic segments. © 2000 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 38: 1903–1916, 2000  相似文献   

14.
Poly(vinyl amine) (PVAm)‐based amphiphilic glycopolymers were synthesized by a two‐step method, that is dextran molecules (Dex, Mw = 1500) were attached to the PVAm backbone by reacting amine groups with dextran lactone, and then, hexanoyl groups (Hex) were attached by reacting the PVAm free amine groups with N‐(hexanoyloxy)succinimide. By adjustment of the feed ratios of Dex/Hex, amphiphilic comb‐like glycopolymers with various hydrophilic and hydrophobic balances were prepared, and their structures were characterized by 1H NMR. Surface activity of the amphiphilic glycopolymers at the air/water interface was demonstrated by reduction in water surface tension. Adsorption of the amphiphilic glycopolymers at the solid/water interface was examined on octadecyltrichlorosilane (OTS)‐coated coverslips by water contact angle measurements. The results show that the amphiphilic glycopolymers need about 20 mol % of dextran attachment to make an effective hydrophilic coating. In comparison with the one‐step reaction by addition of dextran lactone and alkyl succinimide simultaneously, the two‐step approach can attach Dex on PVAm as high as possible in the first step, and offers quantitative advantages in controlling the ratio of hydrophilic and hydrophobic chains along the PVAm backbone, resulting in increased water solubility for the final amphiphilic glycopolymers. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 192–199, 2006  相似文献   

15.
彭宇行  徐坚 《合成化学》1999,7(4):329-333
以具有良好柔性和生物相容性的聚四氢呋喃(PTHF)为疏水链段,具有pH敏感性的聚丙烯酸(PAA)为亲水链段,通过PTHF双端基大分子单体与丙烯酸自由基共聚,首次合成了聚丙烯酸-l-聚四氢呋喃(PAA-l-PTHF)两亲聚合物网络,并对网络的结构、组成以及交联点密度进行了表征。两亲聚合物网络溶胀行为研究表明,PAA-l-PTHF既能在水中溶胀又能在有机溶剂中溶胀,在水中的溶胀度随网络亲水链段PAA含  相似文献   

16.
A series of novel biodegradable hydrogels were designed and synthesized from four types of unsaturated poly(ester amide) (UPEA) and poly(ethylene glycol) diacrylate (PEG‐DA) precursors by UV photocrosslinking. These newly synthesized biodegradable UPEA/PEG‐DA hydrogels were characterized by their gel fraction (Gf), equilibrium swelling ratio (Qeq), compressive modulus, and interior morphology. The effect of the precursor feed ratio (UPEAs to PEG‐DA) on the properties of the hydrogels was also studied. The incorporation of UPEA polymers into the PEG‐DA hydrogels increased their hydrophobicity, crosslinking density (denser network), and mechanical strength (higher compressive modulus) but reduced Qeq. When different types of UPEA precursors were coupled with PEG‐DA at the same feed ratio (20 wt %), the resulting hydrogels had similar Qeq values and porous three‐dimensional interior morphologies but different Gf and compressive modulus values. These differences in the hydrogel properties were correlated to the chemical structures of the UPEA precursors; that is, the different locations of the >C?C< double bonds in individual UPEA segments resulted in their different reactivities toward PEG‐DA to form hydrogels. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 3932–3944, 2005  相似文献   

17.
Dual responsive cyclotriphosphazene (CTP)‐based hydrogels have been synthesized for a controlled release of FU, a hydrophilic drugs. These hydrogels composed of mono (methacryloyl‐2‐ethoxy)‐pentakis(N1,N1‐dimethylpropane‐1,3‐diamino)‐cyclotriphosphazene (HEMA (DMPDA)5CP), acryl amide and pectin were synthesized by free radical polymerization method using methylenebisacrylamide cross linker. The CTP hydrogels were characterized to understand the structure, drug nature in the network and morphology by FTIR, DSC, XRD and SEM, respectively. In this paper, the swelling (dynamic and equilibrium) properties of cyclotriphosphazene hydrogels were investigated, showing dual (pH and thermo) responsiveness and large variation in the swelling capacity. Based on these results the structural parameters of the hydrogel networks such as the average molecular weight between cross‐links (Mc) and polymer–solvent interaction parameter (χ) were determined. The CTP hydrogels has high FU loading efficiency 65 ± 0.5. In‐vitro FU release of these hydrogels was controlled for about 24 hr also hydrogel showed a distinct initial burst. The CTP hydrogels are bearing both hydrophilic groups of pectin and hydrophobic groups of CTP exhibited dual responsive behaviors with pH and temperature. Copyright © 2015 John Wiley & Sons, Ltd.  相似文献   

18.
Enzymatically cleavable and light‐degradable hybrid nanogels were prepared by free radical inverse miniemulsion copolymerization of acrylamide (AAm) with a newly synthesized functional dextran crosslinker containing acrylate moieties attached to the backbone via a photolabile linker, that is, dextran‐photolabile linker‐acrylate (Dex‐PL‐A). The Dex‐PL‐A/AAm feed ratio was systematically varied to investigate the influence of the particle composition on the gel properties. The resulting hydrogel nanoparticles were examined with regard to their degradation behavior upon the appliance of the two orthogonal stimuli by turbidity measurements in combination with dynamic light scattering. Although continuous photolytic cleavage of the photolabile linkers between polyacrylamide chains and dextran molecules was found to proceed fast and quantitatively yielding completely disintegrated networks, stepwise irradiation resulted in partial degradation of crosslinking points. Thus, nanogels of a desired specific degree of swelling (DGS) can be obtained by adjusting the irradiation time accordingly. Partial enzymatic cleavage of the dextran backbones of the Dex‐PL‐A crosslinking molecules resulted in an increase in the DGS of the nanogels up to a constant value. Subsequent irradiation of those swollen hydrogel particles was used to fully degrade the network structure in a second step. Hence, a two‐step degradation profile was realized by the combination of the two orthogonal stimuli. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012  相似文献   

19.
A series of hydrophobic poly(oxypropylene) (POP)‐backboned and hydrophilic poly(oxyethylene)‐backboned amidoacids and imidoacids were prepared through the reaction of poly(oxyalkylene) diamines and trimellitic anhydride (TMA) under mild conditions. The synthesized copolymers were characterized with nuclear magnetic resonance and Fourier transform infrared. Their ability to lower the water surface tension and toluene/water interfacial tension was measured and correlated with the hydrophobic/hydrophilic balance with multiple sodium carboxylate functionalities. The specific POP2000/TMA copolymers, consisting of a 2000 g/mol POP segment and multiple amidoacid functionalities, enabled the demonstration of a strong surfactant tendency and a critical micelle concentration at 0.1 wt %. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 646–652, 2006  相似文献   

20.
A new kind of copolymeric hydrogel adsorbent containing hydrophilic groups that both provides swelling in water and chelates with uranyl ions was synthesized, and its adsorptive ability for recovering uranium from aqueous media was investigated. The uranyl adsorption capacities of poly(2‐hydroxyethyl methacrylate/maleic acid) hydrogels were determined with a polarographic technique to be 3.2–4.8 (mg UO/g dry gel) from a 15‐ppm uranyl nitrate solution at pH, 6 depending on the molar content of maleic acid in the hydrogel. Adsorption studies showed that other stimuli, the temperature, and the ionic strength of the solution also have important roles in the uranyl‐ion adsorption capacity of these hydrogels. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 39: 277–283, 2001  相似文献   

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