Macroporous Poly(Acrylamide) Hydrogels: Swelling and Shrinking Behaviors

Macroporous poly(acrylamide) hydrogels have been synthesized by using poly(ethylene glycol) (PEG) with three different molecular weights as the pore‐forming agent. Scanning electron microscope graphs reveal that the macroporous network structure of the hydrogels can be adjusted by applying different molecular weights of PEG during the polymerization reaction. The swelling ratios of the PEG‐modified hydrogels were much higher than those for the same type of hydrogel prepared via conventional method. However, the swelling/deswelling ratios of the PEG‐modified hydrogels were affected slightly by the change in the amount of the PEG. Scanning electron microscopy experiments, together with swelling ratio studies, reveal that the PEG‐modified hydrogels are characterized by an open structure with more pores and higher swelling ratio, but lower mechanical strength, compared the conventional hydrogel. PAAm has potential applications in controlled release of macromolecular active agents.     

聚(4-乙酰基丙烯酰乙酸乙酯-co-丙烯酸)水凝胶的溶胀动力学以及温度敏感性研究

通过分子结构设计, 合成了疏水性单体4-乙酰基丙烯酰乙酸乙酯(AAEA), 并以该单体与丙烯酸(AA)进行自由基溶液共聚, 制备了P(AAEA-co-AA)新型温度敏感性水凝胶. AAEA的¹H NMR及FT-IR分析表明, 该单体主要以烯醇式结构存在; P(AAEA-co-AA)的FT-IR分析发现, PAAEA与PAA之间存在较强烈的氢键作用, 使得AAEA烯醇异构体中的C—O伸缩振动吸收峰移向了低波数处. 对冷冻干燥后凝胶的电镜分析发现, 当AAEA用量较高时, 由于凝胶内部分子链段的疏水聚集, 各部分溶胀度以及溶胀速度不均一而使得凝胶表面粗糙不平. 采用DSC对凝胶的体积相转变进行了研究, 结果表明, 该水凝胶的体积相转变温度(VPTT)在48.2至61.8 ℃之间, 并且随着AAEA用量的减小, 凝胶的VPTT逐渐增加. 对该新型温度敏感性水凝胶在去离子水中的溶胀动力学研究发现, 当AAEA用量高于4.6 g时, 凝胶属于Fick凝胶; 反之凝胶则属于非Fick凝胶. 该水凝胶在去离子水中具有良好的温度敏感性, 当外界温度低于VPTT时, 凝胶能保持溶胀状态; 而当外界温度高于VPTT时, 凝胶的平衡溶胀度迅速下降, 表现为温度敏感性. 进一步研究发现, 凝胶组成不仅会影响凝胶的VPTT, 而且会影响凝胶温度敏感性的强弱.     

丙烯酰胺和葡萄糖烯丙基酰胺共聚水凝胶的合成与性能

用葡萄糖内酯与烯丙基胺反应制备了葡萄糖烯丙基酰胺单体（AAG），然后与丙烯酰胺和亚甲基双丙烯酰胺共聚得到含糖结构的水凝胶，研究了交联剂浓度和单体配比对共聚合的影响，用红外光谱和热重分析对其结构和热稳定性进行了表征，并计算了干凝胶的热分解活化能，研究了温度、盐的浓度，溶液的PH值及蛋白质对水凝胶的膨胀比的影响，结果发现水凝胶的膨胀比随着温度的提高或盐浓度的增大而略有增加，在高或低的PH时膨胀比由于糖组分的水解也有一定的增加，水凝胶在蛋白质丰在时发生收缩，表明二者发生了键合作用。     

Poly (Ethylene Glycol)‐Based Hydrogels as Self‐Inflating Tissue Expanders with Tunable Mechanical and Swelling Properties

Tissue expansion is used by plastic/reconstructive surgeons to grow additional skin/tissue for replacing or repairing lost or damaged soft tissues. Recently, hydrogels have been widely used for tissue expansion applications. Herein, a self‐inflating tissue expander blend composition from three different molecular weights (2, 6, and 10 kDa) of poly (ethylene glycol) diacrylate (PEGDA) hydrogel with tunable mechanical and swelling properties is presented. The in vitro results demonstrate that, of the eight studied compositions, P6 (PEGDA 6 kDa:10 kDa (50:50)) and P8 (PEGDA 6 kDa:10 kDa (35:65)) formulations provide a balance of mechanical property and swelling capability suitable for tissue expansion. Furthermore, these expanders can be compressed up to 60% of their original height and can be loaded and unloaded cyclically at least ten times with no permanent deformation. The in vivo results indicate that these two engineered blend compositions are capable to generate a swelling pressure sufficient to dilate the surrounding tissue while retaining their original shape. The histological analyses reveal the formation of fibrous capsule at the interface between the implant and the subcutaneous tissue with no signs of inflammation. Ultimately, controlling the PEGDA chain length shows potential for the development of self‐inflating tissue expanders with tunable mechanical and swelling properties.

     

Thermodynamics of Swelling of Poly(N-vinylpyrrolidone)-Poly(ethylene glycol) Complex Due to Water Sorption

The deformation of sorbent caused by the sorption is new method of quantitative investigation “in situ” of interaction in system host-quest. The deformation of PVP-PEG complex, ϕ_PEG=0.36 and ϕ_PEG=0.20 due to water sorption has been studied by the measuring of the relative elongation of the polymer samples and the isotherms of water sorption simultaneously. The investigation of the sorption deformation gives the possibility of direct estimation of polymer sample free volume and it's variation during sorption, also the variation of Gibbs energy of system due to sorption according to the vacancy solution theory. The glassy-plastic state transition of polymer during water sorption has been observed.     

Swelling Behavior of Chemically Ion-Doped Hydrogels

Summary: Poly(acrylamide-co-N,N′-methylenebisacrylamide) gels were synthesized in the presence of pyranine fluoroprobe (trisodium 8-hydroxypyrene-1,3,6-trisulfonate). Pyranine binds to polymer chains through its OH group via radical addition. Thus, the final gels were doped with the pyranines having SO ions as side groups and Na⁺ as counter-ions. The swelling behavior of gels prepared with varying amounts of pyranine and monomer concentrations were studied. The swelling ratio of the synthesized gels did not exceed 35 except the 2 M gel containing 10⁻² M pyranine which are the concentrations for the abnormal swelling behavior. At this particular concentration of monomer (acrylamide) and pyranine, the mass ratio m/m₀, the mass of the swollen gel to the mass of the dried gel, reaches about 1300; a stepwise behavior was observed in the swelling kinetics. The swelling kinetics of polyacrylamide gels containing unbound (free) pyranine were compared with the swelling behavior of the gels containing chemically bound pyranine.     

P(NIPAAm-co-Aam)共聚凝胶和PAAc/P(NIPAAm-co-Aam) IPN凝胶的溶胀与释药性能

P(NIPAAm-co-Aam)共聚凝胶和PAAc/P(NIPAAm-co-Aam) IPN凝胶的溶胀与释药性能;N-异丙基丙烯酰胺;丙烯酰胺;丙烯酸;共聚;互穿聚合物网络;水凝胶;溶胀;释药     

疏水改性pH响应型智能水凝胶P(HEMA-NaAA-DiAC16)的制备及其溶胀性能

以二烯丙基胺和1-溴代十六烷为原料合成了疏水单体N,N-二烯丙基正十六烷胺(DiAC16),用FTIR、1H NMR 和元素分析对其进行了表征。 以2-羟基甲基丙烯酸乙酯(HEMA)、丙烯酸(AA)和N,N-二烯丙基正十六烷胺为共聚单体,N,N′-亚甲基双丙烯酰胺(BIS)为交联剂,十二烷基硫酸钠(SDS)为表面活性剂,过硫酸铵-四甲基乙二胺(TMEDA)为引发体系,制得的疏水改性智能水凝胶P(HEMA-NaAA-DiAC16)具有pH敏感特性。 研究了DiAC16、NaAA、BIS用量及pH值和离子强度等因素对水凝胶P(HEMA-NaAA-DiAC16)溶胀性能的影响。 结果表明,凝胶在水中的平衡溶胀率(为78.9～163.91),随DiAC16、BIS用量的增加和NaAA用量的减少而减少,n值(一般在0.5~1.0之间)随DiAC16、NaAA和BIS用量的增加而增加,为非Fickian扩散。 水凝胶的吸水溶胀是放热过程,ΔHm在-2.09～-3.64 kJ/mol,ΔHm的绝对值随DiAC16用量的减少、NaAA用量和BIS用量的增加而增大,聚合物与水的亲和力逐渐增强。 随离子强度的增强,平衡溶胀率下降。     

pH快速响应PNIPAAm-co-PAAc水凝胶的制备及溶胀动力学

pH快速响应PNIPAAm-co-PAAc水凝胶的制备及溶胀动力学;N-异丙基丙烯酰胺;pH敏感性;溶胀历史     

非离子聚(N-乙烯基-2-吡咯烷酮)凝胶在线型聚(丙烯酸)溶液中的溶胀特性

研究了在线型聚 (丙烯酸 ) (PAA)溶液中链长、pH、离子强度和水 /二甲亚砜混合溶剂组成对非离子聚 (N-乙烯基 - 2 -吡咯烷酮 ) (PVP)水凝胶溶胀特性的影响 .发现聚酸浓度的变化引起凝胶显著的体积相变 ,这是因为凝胶和聚合物通过氢键形成了大分子间凝胶 -聚合物复合物 .凝胶的溶胀特性取决于聚酸的链长而不是离子强度 .随着pH值和水 /二甲亚砜混合溶剂组成的变化 ,凝胶的溶胀率 (SR)发生变化     

Sorption and Swelling of Poly(D,L-lactic acid) and Poly(lactic-co-glycolic acid) in Supercritical CO2

Summary: The equilibrium sorption and swelling behavior in supercritical CO₂ of poly(D,L-lactic acid) and poly(lactic-co-glycolic acid) has been studied at a temperature of 35 °C and at pressures up to 200 bar. Sorption was measured through a gravimetric technique and swelling by visualization. From these data, the behavior of the different polymers can be compared. In terms of partial molar volume of CO₂ in the polymer matrix, all the polymers exhibit a behavior typical of rubbery systems. The experimental results have been modeled using the Sanchez-Lacombe equation of state, which is able to represent the actual behavior of the polymer-CO₂ systems with reasonable accuracy.     

Synthesis and Swelling Properties of Thermosensitive Hydrogels based on Terpolymerization

Novel thermosensitive hydrogels based on polymerization of N-isopropyl acrylamide, Sodium acrylate, and diacetone acrylamide were synthesized, The swelling ratio and dynamic swelling were investigated. The results indicated that the hydrogels exhibited high water uptake and themosensitivity. The swelling properties and volume phase transition temperature could be adjusted by contents of the comonomers in the gels.     

Swelling Behaviour of Isotropic Poly(n-butyl acrylate) Networks in Isotropic and Anisotropic Solvents

Summary: The swelling properties of photochemically crosslinked poly(n-butyl acrylate) (PABu) networks in isotropic and anisotropic solvents were investigated experimentally. The purpose of this study was to examine the swelling kinetics of PABu networks in isotropic solvents and to compare the results obtained which those observed in the case of the low molecular weight liquid crystal 4-cyano-4′-n-pentyl-biphenyl known as 5CB. The phase diagrams were established in terms of composition and temperature for isotropic solvents, as toluene, acetone, cyclohexane, and methanol, and 5CB, using the plateau values corresponding to equilibrium states of swelling. The polymer networks were prepared via free radical polymerization/crosslinking processes by ultraviolet (UV) radiation of initial mixtures made up from a monomer, a crosslinker, and a photoinitiator. PABu networks with several crosslinking densities were formed using different quantities of difunctional monomer hexanedioldiacrylate (HDDA). Immersion of these networks in excess solvent allows measuring the solvent uptake by determination of the weight in isotropic solvents and diameter in an anisotropic solvent (5CB). Swelling data were rationalized by calculating weight and diameter ratios considering swollen to dry network states of the samples.     

Poly(Urethane)-Crosslinked Poly(HEMA) Hydrogels

Abstract

Hydrogels have been prepared from 2-hydroxyethyl methacrylate polymerized in the presence of isocyanate-terminated poly(ethylene glycol) (PEG) crosslinking agents. PEGS of molecular weights 200, 400, and 1000 were investigated. The crosslinked nature of the hydrogels was demonstrated by their insolubility in solvents which normally dissolve poly(HEMA). Hexamethylene diisocyanate (HDI) was mainly used as the isocyanate. The molecular weight of the PEG and the crosslinker content significantly influenced the equilibrium water sorption and mechanical properties of the saturated networks. It was observed that as the molecular weight of the PEG increased, the water sorption increased and the nominal modulus decreased. However, for higher levels of cross-linker, water sorption decreased and modulus increased at low molecular weight PEG; for PEG 1000, water absorption increased as crosslinker content increased. These results are explained by the competing effects of flexibility, crosslink density, and hydrophobicity contributed by the various constituents of the hydrogels.     

CMC/PNIPAAm半互穿网络水凝胶的溶胀动力学研究

以羧甲基纤维素钠(CMC)和N-异丙基丙烯酰胺(NIPAAm)为原料,制备了具有温度和pH敏感性的半互穿网络(CMC／PNIPAAmsemi-IPN)水凝胶,并研究了水凝胶在不同温度和pH值条件下的溶胀行为。结果表明：在弱碱性(pH-7．4)条件下,凝胶的溶胀速率和溶胀度都随着凝胶中CMC含量的增加而增大;而在酸性(pH-1．O)条件下则相反。在弱碱性条件下,水分子在凝胶中的扩散行为都可用non-Fickian扩散来描述,水分子在凝胶中的扩散系数D随着凝胶溶胀速率的增大而增大;在酸性条件下,20℃时凝胶的溶胀过程符合non-Fickian扩散规律,而37℃时凝胶的溶胀过程符合Fickian扩散规律,但水分子的扩散系数D相差不大。     

Thermodynamics of Swelling of Polyacrylamide and Poly(methacrylic acid) Lyophilized Xerogels in Water

The structure and thermodynamic functions of water mixing with polyacrylamide and poly(methacrylic acid) xerogels prepared via drying of chemically crosslinked hydrogels equilibrium swollen in water are studied by methods of scanning electron microscopy, low-temperature nitrogen adsorption, differential scanning calorimetry, isothermal interval sorption of water vapor, and microcalorimetry. The liquid-phase drying in air at 70°C and solid-phase lyophilic drying under vacuum are used. Samples dried by different methods have dissimilar structures, which significantly affects the thermodynamics of the interaction of xerogels with water. The Flory–Huggins parameter of interaction of polyacrylamide and poly(methacrylic acid) with water and also its enthalpy and entropy components are independent of the procedure of xerogel preparation. The influence of the latter component manifests itself only in the thermodynamics of the relaxation of the nonequilibrium glassy structure of polymer.     

Modeling of Swelling Behaviors of Acrylamide-Based Polymeric Hydrogels by Intelligent System

Hydrogels based on acrylamide (AAm) were synthesized by free radical polymerization in an aqueous solution using N,N’-methylenebisacrylamide (MBAAm) as crosslinker. To obtain anionic hydrogels, 2-acrylamido-2-methylpropanesulfonic acid sodium salt (AMPS) and acrylic acid (AAc) were used as comonomers. The swelling behaviors of all hydrogel systems were modeled using an artificial neural network (ANN) and compared with a multivariable least squares regression (MLSR) model and phenomenal model. The predictions from the ANN model, which associated input parameters, including the amounts of crosslinker (MBA) and comonomer, and swelling values with time, produce results that show excellent correlation with experimental data. The parameters of swelling kinetics and water diffusion mechanisms of the hydrogels were calculated using the obtained experimental data. Model analysis indicated that the ANN models could accurately describe complex swelling behaviors of highly swellable hydrogels.     

羧甲基纤维素与丙烯酸接枝共聚凝胶的溶胀动力学及过溶胀平衡特性的研究

采用接枝共聚合成了羧甲基纤维素钠、丙烯酸与N,N′-亚甲基双丙烯酰胺的交联凝胶, 研究了这类凝胶在不同pH值的缓冲溶液中的溶胀行为, 发现在酸性介质中凝胶的溶胀动力学行为表现出过溶胀平衡特性(overshooting effect), 即凝胶先发生溶胀到最大值, 然后再逐渐消溶胀到平衡. 这种现象可归因于凝胶溶胀过程中羧基之间通过氢键所产生的协同物理交联. 较之凝胶的组成, 缓冲溶液的pH值对过溶胀平衡现象的影响更为显著. 前者是因为凝胶羧基的总摩尔分数并不随两组分结构单元摩尔数的改变而改变, 羧基之间通过氢键形成的物理交联程度在交联剂摩尔分数接近的条件下变化不大; 后者是由于溶液的pH值显著影响凝胶羧基的质子化程度, 进而影响羧基之间通过氢键形成的物理交联程度. 凝胶在酸性介质中的溶胀过程符合E. Díez-Peña等提出的溶胀动力学定量模型, 理论曲线与实验数据有较好的相关性. 凝胶在pH≥5.0的缓冲溶液中的溶胀不产生过溶胀平衡现象, 这一现象归因于完全离子化的羧基之间不能形成物理交联. 凝胶的溶胀过程遵循Schott二级溶胀动力学.