RADIATION SYNTHESIS AND CHARACTERIZATION OF POLY(AA-co-NVP)/CLAY HYDROGELS

The pH-sensitive P(AA-co-NVP)/clay hydrogels were prepared with the monomers of acrylic acid(AA)and N-vinyl-2-pyrrolidone(NVP)based onγ-ray irradiation technique.The influence of pH values of buffer solutions and contents of clay and NVP on the equilibrium swelling ratio(SR)and compressive properties of the hydrogels was investigated in detail.The results of swelling property tests showed that,with the increase of clay content,the SR of hydrogels increases in the same buffer solution,and the SR of hydrog...     

pH敏感的聚(L-谷氨酸)-交联聚丙烯酸水凝胶的合成与性能研究

通过在聚L-谷氨酸侧链部分接枝甲基丙烯酸2-羟乙酯得到含有双键的聚(L-谷氨酸),将其与丙烯酸共聚得到由聚(L-谷氨酸)侧链接枝并交联聚丙烯酸的pH敏感水凝胶.研究水凝胶在不同pH的缓冲溶液中的溶胀性、溶胀动力学,并通过SEM观察水凝胶的微观结构.结果表明,水凝胶在低pH环境下的溶胀率明显低于高pH环境中的溶胀率,不同...     

Nanocomposite scaffolds based on gelatin and alginate reinforced by Zn2SiO4 with enhanced mechanical and chemical properties for tissue engineering

Hydrogels have been employed in regenerative treatments for decades because of their biocompatibility and structural similarity to the native extracellular matrix. Injectable hydrogels with interconnected porosity and specific internal structures are momentous for tissue engineering. Here, we develop a group of injectable hydrogels comprised of oxidized alginate (OA)/gelatin (GEL) strengthened by modifying the amount of Zn₂SiO₄ nanoparticles. The physicochemical characteristics of OA/GEL/Zn₂SiO₄ hydrogels were studied by mechanical strength, swelling ratio, and morphology. The outcomes revealed that the mechanical characteristics of hydrogels containing a higher amount of Zn₂SiO₄ (0.12 wt%) improved more than five times than the hydrogels fabricated without Zn₂SiO₄. The in vitro degradation outcomes manifested the degradation of the hydrogel comprising 0.12 wt% Zn₂SiO₄ NPs was slower than one without NPs, and remaining masses of hydrogels depend on different contents of Zn₂SiO₄ NPs. The hydrogel containing Zn₂SiO₄ NPs exhibited less cytotoxicity and good cell attachment than the hydrogels prepared without the nanoparticles. The cell viability and attachment show that the nanocomposite hydrogels are biocompatible (>96%) with great cell adhesion to osteosarcoma cell line MG63 depending on the presence of Zn₂SiO₄. The superior physical, chemical as well as mechanical characteristics of the hydrogels containing Zn₂SiO₄ NPs along with their cytocompatibility suggest that they can introduce as good candidates as scaffolds in tissue engineering.     

新型半纤维素基磁性水凝胶的制备及性能

采用H₂O₂-Vc氧化还原体系引发半纤维素衍生物,以表面修饰的Fe₃O₄粒子作为磁性组分,利用接枝共聚方法制备了新型半纤维素基磁性水凝胶. 分别用傅里叶变换红外(FTIR)光谱、X射线光电子能谱(XPS)和扫描电子显微镜(SEM)对水凝胶的结构及形貌进行了表征,利用X射线衍射(XRD)和振动样品磁强计(VSM)对水凝胶的晶型结构及磁性能进行了分析,发现Fe₃O₄粒子均匀分散在凝胶网络中,半纤维素基磁性水凝胶表现出良好的顺磁性. 考察了丙烯酸/半纤维素比例、Fe₃O₄粒子含量及交联剂用量对水凝胶溶胀性能的影响,并探讨了该水凝胶的溶胀机理,它在pH 8 缓冲溶液中的溶胀较好符合Fickian 和Schott 动力学模型. 通过SEM和溶胀性能分析表明,随着pH值的升高水凝胶的孔径增大,水凝胶的溶胀率逐渐增大. 制备的水凝胶被用于溶菌酶吸附研究,结果表明磁性凝胶的吸附量大于非磁性水凝胶,水凝胶的吸附行为符合Freundlich 和Temkin 等温模型.     

N,N-双(2-羟乙基)-2-氨基乙磺酸钠为扩链剂的磺酸型聚氨酯水凝胶制备及性能

以异佛尔酮二异氰酸酯(IPDI)、聚乙二醇-2000(PEG)为主要原料,二羟甲基丙酸(DMPA)和N,N-双(2-羟乙基)-2-氨基乙磺酸钠(BES-Na)为亲水性扩链剂,制备了一系列磺酸型聚氨酯水凝胶(WPUHs)。 通过X射线衍射仪、热重分析仪和电子万能测试机对凝胶的结构和性能进行了表征。 结果表明,随着BES-Na质量分数的增加,WPUHs的热稳定性逐渐增加,WPUH7(BES-Na质量分数为3.46%)的压缩强度和压缩模量比WPUH1(BES-Na质量分数为0%)分别提高了2.9倍和3.6倍。 BES-Na的质量分数对WPUHs的溶胀初期过程影响显著,WPUHs的平衡溶胀比从20.6增加至29.3。 WPUHs具有良好的温度和pH敏感性,在10~45 ℃范围内,WPUH7平衡溶胀比从17.6增大至33.8,在pH值为2~10范围内,WPUH7平衡溶胀比从21.7增大至70.6。     

Preparation and characterization of temperature- and pH-sensitive hemicellulose-containing hydrogels

In this work, a hemicellulose-containing hydrogel was synthesized. As the first step, a temperature- and pH-sensitive copolymer was synthesized from itaconic acid and N-isopropylacrylamide (NIPAAm). Then the hydrogel was prepared by reacting the copolymer with acylated hemicellulose and polyvinyl alcohol. The morphology, compressive strength, thermal stability, swelling/deswelling behavior, drug-release behavior performances of the hydrogels were investigated. The lower critical solution temperature of the hydrogels varied in 34–44°C when the NIPAAm and itaconic acid mass ratios ranged in 100/0–90/10. Both temperature and pH had a significant influence on equilibrium swelling ratio of hydrogels. The equilibrium swelling ratio increased with pH, but decreased with temperature. Cytocompatibility assay demonstrated that this hemicellulose-containing hydrogel was biocompatible. The release process of salicylic acid suggested that this hydrogel had a potential use in controlled drug release.     

PVA-PAMPS-PAA三元互穿网络型水凝胶的合成及其性能研究

以2-丙烯酰胺基-2-甲基丙磺酸(AMPS)、丙烯酸(AA)以及聚乙烯醇(PVA)为原料,制备了PVA-PAMPS-PAA三元互穿网络型(T-IPN)水凝胶.红外分析表明,PVA与PAA以及PAMPS之间形成了较强的氢键,使得PVA分子上的C—O伸缩震动吸收峰移向了低波数处.X射线衍射以及电镜分析表明,当PVA用量较低时,PVA能均匀的穿插于凝胶网络中,形成完善的互穿网络结构,当PVA用量过高时,部分的PVA结晶而使得凝胶出现相分离.研究了该三元互穿网络型水凝胶的溶胀性能,结果表明,该水凝胶的平衡溶胀比在200至340之间,并且随着AA以及AMPS用量的增加,凝胶的溶胀速率以及平衡溶胀比均升高.该三元互穿网络型水凝胶在酸性溶液中和在碱性溶液中表现出截然不同的消溶胀性能;并且随着溶液pH的升高,凝胶在pH=9.0附近出现体积突变,表现出pH敏感性.通过研究T-IPN水凝胶的抗压缩性能发现,利用线型高分子、柔性高分子网络以及刚性高分子网络制备的三元互穿网络型水凝胶能在高溶胀比下保持较高的强度.溶胀比为180的T-IPN水凝胶,其最大抗压缩强度可达12.1 MPa.进一步研究发现,凝胶的组成以及溶胀比均对凝胶的抗压缩强度和压缩应变均存在较大的影响.     

Structurally Enhanced Hydrogel Nanocomposites with Improved Swelling and Mechanical Properties

In this work, structurally enhanced hydrogel nanocomposites based on 2-acrylamido-2 methyl propane sulfonic acid (AMPS)-acrylamide (AAM) copolymer with high hydrophilic group content were prepared by in-situ copolymerization by using different types of clay (montmorillonite, mica and halloysite). Nanocomposite hydrogels were characterized by Fourier-Transform Infrared Spectroscopy (FTIR) and X-ray diffraction (XRD) analyses and determination of swelling degrees of the samples. Mechanical properties of the samples were also investigated by determination of the compressive elastic modulus. It was also found that exfoliated or highly expanded intercalated nanocomposite structure was obtained and clay incorporation into the AMPS-AAM hydrogel structure improved its swelling capacity. The highest swelling capacity (1030 g H₂O/g) was observed for the nanocomposite sample prepared with the montmorillonite amount of 5% (w). Furthermore, mechanical strength of the hydrogels against compression forces was significantly improved by the clay addition. It was found that the type of clay, in other word filler geometry, affected the compressive elastic modulus (E) of the samples. It was concluded that halloysite, which is considered to be a one dimensional (1D) nanotubular filler was less effective to enhance the compressive elastic modulus (E) of such materials compared with the montmorillonite and mica having two dimensional (2D) platelet or disk-like shapes at a particular amount of clay.     

Graphene Oxide/Polyacrylamide/Aluminum Ion Cross‐Linked Carboxymethyl Hemicellulose Nanocomposite Hydrogels with Very Tough and Elastic Properties

Development of high‐strength hydrogels has recently attracted ever‐increasing attention. In this work, a new design strategy has been proposed to prepare graphene oxide (GO)/polyacrylamide (PAM)/aluminum ion (Al³⁺)‐cross‐linked carboxymethyl hemicellulose (Al‐CMH) nanocomposite hydrogels with very tough and elastic properties. GO/PAM/Al‐CMH hydrogels were synthesized by introducing graphene oxide (GO) into PAM/CMH hydrogel, followed by ionic cross‐linking of Al³⁺. The nanocomposite hydrogels were characterized by means of FTIR, X‐ray diffraction (XRD), and scanning electron microscopy/energy‐dispersive X‐ray analysis (SEM‐EDX) along with their swelling and mechanical properties. The maximum compressive strength and the Young's modulus of GO_3.5/PAM/Al‐CMH_0.45 hydrogel achieved values of up to 1.12 and 13.27 MPa, increased by approximately 6488 and 18330 % relative to the PAM hydrogel (0.017 and 0.072 MPa). The as‐prepared GO/PAM/Al‐CMH nanocomposite hydrogels possess high strength and great elasticity giving them potential in bioengineering and drug‐delivery system applications.     

Adsorption of Apollo reactive dyes on poly(N,N dimethylamino ethylmethacrylate) hydrogels

Poly(N,N-dimethylamino ethylmethacrylate) [P(DMAEMA)] hydrogels were prepared by irradiating the ternary mixtures of dimethylamino ethylmethacrylate (DMAEMA)/ethyleneglycol dimethacrylate (EGDMA)/water (H₂O) by γ-rays at ambient temperature. The swelling of four types of DMAEMA hydrogels in distilled water is higher than the swelling of these hydrogels in dye solutions. The value of equilibrium swelling of P(DMAEMA)1 hydrogel was 338% at pH 7.0 in distilled water, while it was 325% and 326% at pH 7.0 in Apollofix Red (AR) and Apollofix Yellow (AY) solutions, respectively. The adsorption capacity of P(DMAEMA)1 hydrogel was found to increase from 85 to 131 mg for AR g⁻¹ dry gel and from 58 to 111 mg for AY g⁻¹ dry gel with decreasing pH of the dye solutions.     

Synthesis and properties of a novel double network nanocomposite hydrogel

A novel polyacrylamide/polyacrylic acid (PAAm/PAA) double network (DN) nanocomposite (NC) hydrogel had been synthesized by two‐step solution polymerization. The PAAm network was crosslinked by inorganic clay while the PAA network was crosslinked by a chemical crosslinker. The chemical structure of the network was confirmed by Fourier transform infrared (FTIR), X‐ray diffraction (XRD), and transmission electron microscopy (TEM). The swelling and mechanical strength properties of PAAm/PAA hydrogels were examined. The results showed that a DN hydrogel achieved both a high swelling capacity of 1219 g/g in deionized water and 124 g/g in 0.9 wt% NaCl solution and high compressive stress of 21.5 kPa in a high water content of 99.58%. Copyright © 2008 John Wiley & Sons, Ltd.     

Ultrastretchable,Tough, and Notch‐Insensitive Hydrogels Formed with Spherical Polymer Brush Crosslinker

Spherical polymer brushes, poly(acrylic acid) (PAA)‐grafted polystyrene nanoparticle (PAA@PS), are employed as the macro‐crosslinker to prepare PAA hydrogels. Benefitting from the innumerable hydrogen bonds between highly entangled PAA chains both in bulk and on the polymer brush, the PAA/PAA@PS hydrogels combine desirable stretchability, toughness, and notch‐insensitivity. The uniaxial tensile tests show a very high fracture elongation up to 9.1 × 10³% while the fracture toughness reaches 3.0 MJ m⁻³ and the maximum swelling ratio of the hydrogel can be 2.0 × 10³ as well. After being loaded with silver nanoparticles, the PAA/PAA@PS hydrogels are employed as a recyclable catalyst successfully.     

Facile synthesis of calcium carbonate/polyacrylic acid hydrogels for pH-responsive delivery of cytarabine

Cytarabine (Cyt) encapsulated calcium carbonate (CaCO₃) nanospheres were facilely synthesized through a simple co-precipitation method, and the Cyt encapsulated CaCO₃ nanospheres (CaCO₃/Cyt) were modified by polyacrylic acid (PAA) hydrogels through in situ polymerization of acrylic acid (AA) monomer on the surface of the CaCO₃/Cyt. Successful preparation of the Cyt loaded CaCO₃/PAA hydrogels were confirmed by the characterization of SEM, TEM and FT-IR. Premature release of Cyt in acidic medium (pH = 1.2) could be effectively circumvented by the introduction of the PAA hydrogels. More importantly, pH-responsive delivery of Cyt from the as-prepared CaCO₃/PAA hydrogels could be achieved due to the pH-sensitivity of the PAA. Although the highest swelling ratio of PAA was obtained at pH 7.3 (27.7), the highest cumulative release of Cyt from the carrier was achieved at pH 5.3 (86.75%), which might be attributed to the high stability of CaCO₃ at pH 7.3. That is to say, the highest cumulative release of Cyt at pH 5.3 was a compromise by considering the relatively high swelling ratio of PAA and the relatively low stability of CaCO₃.     

pH/temperature double responsive behaviors and mechanical strength of laponite‐crosslinked poly(DEA‐co‐DMAEMA) nanocomposite hydrogels

A nanocomposite (NC) hydrogel crosslinked by inorganic Laponite XLG was successfully synthesized via in situ free radical polymerization of monomers N,N‐diethylacrylamide and (2‐dimethylamino) ethyl methacrylate (DMAEMA). Polymerization was carried out at room temperature due to the accelerating effect of DMAEMA. The as‐prepared hydrogels displayed controlled transformation in optical transmittance and volume in response to small diversification of environmental factors, such as temperature and pH. The compressive strength of swollen D_6:1G₆ hydrogels was as high as 2219 kPa while compressive strain was 95%. Cyclic compression measurement exhibited good elastic properties of NC hydrogels. This work provides a facile method for fabricating stimuli‐responsive hydrogels with superior mechanical property. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2015 , 53, 876–884     

Phase Transition of Acrylamide‐Based Polyampholyte Gels in Water

The swelling behavior of acrylamide (AAm)–based polyampholyte hydrogels in water and in aqueous salt (NaCl) solutions was investigated. [(Methacrylamido)propyl]trimethyl‐ammonium chloride (MAPTAC) and acrylic acid (AAc) were used as the ionic comonomer in the hydrogel preparation. Three sets of hydrogels containing 70 mol% AAm and 30 mol% ionic comonomers of varying mole ratios were prepared. The variations of the hydrogel volume in response to changes in pH, and salt concentration were measured. As pH increases from 1, the hydrogel volume V _eq in water first increases and reaches a maximum value at a certain pH. Then, it decreases again with a further increase in pH and attains a minimum value around the isoelectric point (IEP). After passing the collapsed plateau region, the gel reswells again up to pH=7.1. The reswelling of the collapsed gels containing 10 and 4% MAPTAC occurs as a first‐order phase transition at pH=5.85 and 4.35, respectively, while the hydrogel with 1% MAPTAC reswells continuously beyond its IEP. Depending on pH of the solution, the hydrogels immersed in salt solutions exhibit typical polyelectrolyte or antipolyelectrolye behavior. The experimental swelling data were compared with the predictions of the Flory‐Rehner theory of swelling equilibrium including the ideal Donnan equilibria. It was shown that the equilibrium swelling theory qualitatively predicts the experimental behavior of polyampholyte hydrogels.     

Swelling Behavior and Metal-Ion Uptake Capacity of pH-Responsive Hydrogels of Poly(N-acryloyl-N′-ethylpiperazine)

New hydrogels based on N-acryloyl-N′-ethylpiperazine (AcrNEP) and N,N-methylene bisacrylamide (MBA) were prepared by thermal initiated solution polymerization. The hydrogels swelled extensively in buffer solutions of low pH due to protonation of the amine functions of the monomers, while the swelling was less significant in buffer solutions of high pH. The increased swelling of the gel in low pH is due to the development and interaction of fixed charges within the gel network. As a result of the electrostatic repulsion between the charges the elastic constraint of the gel is modified which leads to pronounced swelling and hence to high water uptake. Water transport in the hydrogel both in buffer solutions of pH 2.6 and pH 8.4 was non-Fickian due to polymer relaxation (anomalous process). The gels demonstrated good uptake of divalent metal ions such as Ni²⁺, Co²⁺, and Zn²⁺, with high selectivity for Ni²⁺ ions due to the formation of a more stable ligand-metal complex. The metal uptake capacity increased with increase in pH of the solution, while an increase in the crosslinker amount of the hydrogel reduced its metal uptake capacity. In the presence of metal ions the swelling of the hydrogel reduced considerably due to the formation of additional physical crosslinks within the hydrogel network. The metal ion loaded hydrogels could be stripped and regenerated with 1 M sulfuric acid without any loss in swelling or metal uptake capacities.     

Dynamic Growth of Macroscopically Structured Supramolecular Hydrogels through Orchestrated Reaction-Diffusion

Living organisms are capable of dynamically changing their structures for adaptive functions through sophisticated reaction-diffusion processes. Here we show how active supramolecular hydrogels with programmable lifetimes and macroscopic structures can be created by relying on a simple reaction-diffusion strategy. Two hydrogel precursors (poly(acrylic acid) PAA/CaCl₂ and Na₂CO₃) diffuse from different locations and generate amorphous calcium carbonate (ACC) nanoparticles at the diffusional fronts, leading to the formation of hydrogel structures driven by electrostatic interactions between PAA and ACC nanoparticles. Interestingly, the formed hydrogels are capable of autonomously disintegrating over time because of a delayed influx of electrostatic-interaction inhibitors (NaCl). The hydrogel growth process is well explained by a reaction-diffusion model which offers a theoretical means to program the dynamic growth of structured hydrogels. Furthermore, we demonstrate a conceptual access to dynamic information storage in soft materials using the developed reaction-diffusion strategy. This work may serve as a starting point for the development of life-like materials with adaptive structures and functionalities.     

Swelling behaviors, tensile properties and thermodynamic studies of water sorption of 2-hydroxyethyl methacrylate/epoxy methacrylate copolymeric hydrogels

A series of copolymeric hydrogels based on 2-hydroxyethyl methacrylate (HEMA) and epoxy methacrylate (EMA) were synthesized by bulk polymerization. Swelling behaviors and tensile properties of hydrogels were studied. Dynamic swelling behaviors of copolymeric hydrogels indicate that the swelling process of these polymers follows Fickian behavior. The equilibrium water content (EWC) decreased and volume fraction of polymer in hydrogel (?₂) increased with EMA content increasing due to its hydrophobicity. The increase of ionic strength of swelling medium or temperature results in a decrease in EWC and an increase in values of ?₂. Young’s modulus and tensile strength of hydrogels, as well as effective crosslink density (v_e), increased as EMA content increased or ionic strength of swelling medium increased, attributing to increasing interaction between hydrophobic groups and polymer-polymer interaction with an increase in EMA content or in ionic strength. The polymer-solvent interaction parameter χ reflecting thermodynamic interaction was also studied. As EMA content, ionic strength of swelling medium or temperature increased, the values of χ increased. The values of χ and its two components χ_H and χ_S varied with increasing T. The negative values and trend of the enthalpy and entropy of dilution derived from values of χ_S and χ_H, could be explained on the basis of structuring of water through improved hydrogen bonding and hydrophobic interaction.     

An enhanced immobilization of BSA biomolecule on anionic hydrogels: swelling and adsorption modeling

The three-dimensional structure of hydrogels plays a leading role in several areas of applications. The hydrogels are more and more used as systems of immobilized and controlled release of biomolecules in biotechnology and bio-pharmacy industries. To improve protein adsorption capacity in poly(acrylamide) hydrogels, maleic acid co-monomer was included into the reaction mixture during hydrogel synthesis. So, hydrogels of poly(acrylamide) and its copolymers with diprotic maleic acid were prepared by copolymerization and chemical crosslinking with N,N′-methylene bis-acrylamide. Swelling behavior in distilled water, in physiological saline and in bovine serum albumin (BSA) solutions was studied. Influence of initial BSA concentration on hydrogel swelling and BSA adsorption was investigated. The high amount of maleic acid present in the hydrogels has a significant effect on the swelling behavior and BSA adsorption. Results showed that the pH sensitivity of hydrogels resulted in the high amount of adsorbed BSA. The adsorption isotherms were described by Langmuir and Freundlich models. The thermodynamic parameter (ΔG _ads ⁰ ) was determined for all obtained hydrogels. We demonstrated the favorable character and reversibility of the BSA adsorption process.     

PAMPS/SiO_2杂化水凝胶的合成及电场敏感性研究

以2-丙烯酰胺-2-甲基丙磺酸(AMPS)为有机原料,正硅酸乙酯(TEOS)为无机原料,过硫酸钾为引发剂,N,N'-亚甲基双丙烯酰胺为交联剂,通过原位-凝胶水溶液聚合法合成了一系列不同二氧化硅含量和不同聚离子浓度的聚(2-丙烯酰胺-2-甲基丙磺酸)/二氧化硅杂化电场敏感性水凝胶.通过扫描电子显微镜(SEM)表征凝胶的结构,研究水凝胶在去离子水以及氯化钠溶液中的溶胀和消溶胀行为.结果表明,系列凝胶的平衡溶胀度介于224.9至325.6之间,复合凝胶的溶胀速率随TEOS用量的增加而降低;除理想杂化凝胶外,随着聚离子浓度的升高,凝胶在氯化钠溶液中的消溶胀速率逐渐减小.对凝胶的电场敏感性研究表明,当聚离子浓度大于氯化钠溶液浓度时,凝胶进一步溶胀,反之则消溶胀,其中杂化凝胶的再溶胀性能减弱,而消溶胀行为变得更为明显.同时制得的理想杂化凝胶,较纯有机凝胶具有更为理想的力学性能,最大抗压缩强度可达23.4 MPa.