新型pH敏感性壳聚糖/明胶水凝胶的制备及其性能

用天然多糖壳聚糖和明胶制备了具有pH敏感性的壳聚糖/明胶水凝胶,研究了pH值对于该凝胶溶胀度的影响,采用红外光谱和电镜扫描对其结构进行了表征。结果表明,水凝胶在碱性和酸性环境中均具有pH敏感性,在酸性溶液中凝胶的溶胀比远大于碱性溶液中的溶胀比,其在pH值3.0时的溶胀度最大,在pH值9.0时的溶胀度最小,且其在不同pH 溶液中重复可逆溶胀收缩。同时,随着交联剂用量的增大,水凝胶的溶胀度减小。     

Preparation and swelling kinetics of pH-sensitive photocrosslinked hydrogel based on carboxymethyl chitosan

A series of photocrosslinkable carboxymethyl chitosans were synthesized by mixing azidobenzaldehyde and an aqueous solution of carboxymethyl chitosan. Aqueous solutions of the product were photocrosslinked via UV irradiation to afford hydrogels. The morphologies and the mechanical properties of the hydrogels were characterized. Their swelling kinetics were studied. The hydrogels displayed good pH sensitivity in pH 2.2–8.0 buffer solutions and an overshooting effect during swelling in pH <5 buffer solutions. The following three factors may contribute to this overshooting effect: firstly, because of the protonation of amide groups in the network in acidic solution, the formation of ionic bonds between amine ions and partial carboxylic ions causes the release of solvent from the swollen network; secondly, ionized carboxylic groups in the network become protonated and convert into nonionized carboxylic groups, and so the concentration of free counterions within the network gradually decreases in acidic solution, leading to solvent release; finally, hydrogen bonds gradually form between nonionized carboxylic groups on the network, which also leads to solvent release from the swollen network. In pH ≥ 5 buffer solutions, the overshooting effect disappeared and the swelling kinetics followed Schott’s second-order swelling kinetics.     

Effect of comonomer type and concentration on the equilibrium swelling and volume phase transition temperature of N‐isopropylacrylamide‐based hydrogels

The effect of incorporating a hydrophilic monomer into poly(N‐isopropylacrylamide) (polyNIPA) hydrogels on the equilibrium swelling and the volume phase transition temperature is reported here. A nonionizable monomer (acrylamide) and three ionizable monomers (itaconic acid, 2‐ethoxyethyl monoitaconate, and 2,2‐(2‐ethoxyethyl) monoitaconate) were studied. Hydrogels with larger swelling capacity than that of the polyNIPA hydrogel were obtained. With the exception of the hydrogel containing 2,2‐(2‐ethoxyethyl) monoitaconate, which did not exhibit the de‐swelling phenomena, the rest showed a volume phase transition. The hydrogels containing 85 wt % acrylamide and 15 wt % comonomer presented the higher shrinking ratio. For some compositions, the T_c of the polyNIPA hydrogel was within the desired temperature range (38–41°C) for controlled‐drug delivery in the human body. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

随机共聚高分子凝胶溶胀和体积相变行为的分子热力学模型

基于随机共聚高分子溶液的格子模型,建立了一个可以描述温度和pH双重响应的随机共聚高分子凝胶溶胀行为的分子热力学模型。该模型考虑了溶剂与不同高分子的混合、高分子网络的弹性以及包含小分子离子在凝胶内外分布的Donnan平衡和聚合物网络上的大分子离子及其反离子之间的静电相互作用的离子影响对化学势的贡献。与其他模型不同的是,该模型还考虑了高分子的组成f。该模型有两类可调的模型参数,一类是溶剂与不同高分子网络之间的相互作用能参数ε槇ij,另一类是高分子网络自身的尺寸参数Mc。研究结果表明,该分子热力学模型只需较少的模型参数就可较好地描述温度和pH双重敏感的随机共聚高分子凝胶的溶胀行为。     

Analysis of a model for pH-sensitive hydrogels

A mathematical model comprising conservation of mass, momentum, and ions for a hydrogel subject to alterations of the solution pH is derived, analyzed, validated and presented. Good agreement between model predictions and their experimental counterpart are achieved. To gain a physical insight into the deformation behavior of the pH-sensitive hydrogel, a scaling analysis coupled with a parametric study is carried out for key physical and operational parameters. The results suggest the significance of initial fixed-charge density, solution ionic strength, Poisson ratio and Young modulus in determining swelling degree of the hydrogel. In addition, it is noted that changes in acid dissociation constant and temperature lead to a notable shift in equilibrium swelling curves. Permeability and size of the hydrogel were found to significantly affect the deformation kinetics: A hydrogel with higher permeability and/or smaller size exhibits faster deformation. These findings and the characteristic scales could provide important guidelines in designing systems utilizing pH-sensitive hydrogels.     

Preparation of a polyelectrolyte complex gel from chitosan and κ-carrageenan and its pH-sensitive swelling

A polyelectrolyte complex gel was prepared by mixing chitosan and k-carrageenan solutions in the presence of NaCl. To study the effect of ambient pH on the swelling behavior, the diameter of the cylindrical gel(4 mm x 8 mm) immersed in aqueous NaOH, KOH, or HCl solution was measured. In the range of pH 10–12, the diameter increased with time, and the gel reached swelling equilibrium within 6 days. In an NaOH solution of pH 10.5, the maximum swelling occurred, and the volume of the gel at equilibrium was 10.2 times as large as the initial one. At pH below 9 and at pH 13, no swelling was observed. Thus, the swelling of the complex gel prepared in this study was sensitive to a rather narrow range of pH. The swelling equilibrium in the presence of NaCl was also investigated at various pH. © 1993 John Wiley & Sons, Inc.     

Network parameters and volume phase transition behavior of poly(N‐isopropylacrylamide) hydrogels

Thermosensitive hydrogels were prepared by free radical polymerization in aqueous solution from N‐isopropylacrylamide (NIPA) monomer and N,N‐methylenebis(acrylamide) (MBAAm) crosslinker. The swelling equilibrium of the hydrogels in deionized water was investigated as a function of temperature and MBAAm content. The results indicated that the swelling behavior and temperature sensitivity of the hydrogels were affected by the amount of MBAAm content. The average molecular mass between crosslinks and polymer–solvent interaction parameter (χ) of the hydrogels were determined from equilibrium swelling values. The swelling variations were explained according to swelling theory based on the hydrogel chemical structure. The swelling equilibrium of the hydrogels was also investigated as a function of temperature in aqueous solutions of the anionic surfactant sodium dodecyl sulfate (SDS) and the cationic surfactant dodecyltrimethylammonium bromide (DTAB). In deionized water, the hydrogels showed a discontinuous volume phase transition at 32°C. In SDS and DTAB solutions, the equilibrium swelling ratio and the volume phase transition temperature (lower critical solution temperature) of the hydrogels increased, which is ascribed to the conversion of nonionic PNIPA hydrogel into polyelectrolyte hydrogels because of binding of surfactant molecules through the hydrophobic interaction. Additionally, the amount of free SDS and DTAB ions was measured at different temperatures by a conductometric method; it was found that the electric conductivity of the PNIPA–surfactant systems depended strongly on both the type and concentration of surfactant solutions. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 1756–1762, 2006     

Humic acid embedded chitosan/poly (vinyl alcohol) pH-sensitive hydrogel: Synthesis,characterization, swelling kinetic and diffusion coefficient

In the present research, humic acid (HA) embedded chitosan (CHT)-poly (vinyl alcohol) (PVA) pH-sensitive hydrogels have been synthesized using glutaraldehyde as a crosslinker. The hydrogels were characterized by Fourier-transform infrared (FT-IR), thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), and scanning electron microscopy (SEM) analysis. The effect of HA content, pH, and temperature on the equilibrium solvent uptake has been investigated. With higher HA contents, the equilibrium swelling capacity increases while lower concentrations of acid cause a decrease in the degree of the swelling. The hydrogels have been found to undergo a number of swelling/deswelling cycles when pH of the swelling medium changes from 1.5 to 11.0. Fick’s law, first-order, and second-order kinetic models were applied to the swelling ratio of hydrogels to explain the mass transfer mechanism and specify swelling kinetic parameters. The swelling parameters such as equilibrium swelling capacity, swelling rate constant, swelling exponent, initial swelling rate, diffusion coefficient, etc., have been evaluated.     

新型胶原基pH敏感水凝胶的制备及性能

在紫外光辐照下,以H2O2为引发剂,采用接枝共聚法制备胶原/聚乙烯吡咯烷酮/丙烯酰胺（Collagen/PVP/AM）pH敏感水凝胶。考察了原料配比和干燥方法对凝胶溶胀性能的影响,研究了其pH敏感性及pH溶胀-退胀特性。制备的水凝胶具有较快的溶胀速率,在5 min时的吸水率可达94％左右。所制备的水凝胶有明显的pH敏感性且pH溶胀-退胀的可逆性良好。傅里叶变换红外光谱法（FTIR）和示差扫描量热法（DSC）结果表明,在保持胶原三股螺旋结构的同时,材料间发生了化学交联,材料的热稳定性显著提高,从而扩大了材料的应用范围。     

Studies on preparation and swelling properties of the N-isopropylacrylamide/chitosan semi-IPN and IPN hydrogels

Semi-interpenetrating network (semi-IPN) polymer gels and interpenetrating network (IPN) polymer gels with thermosensitivity were prepared by introducing a biodegradable polymer, chitosan, into the N-isopropyacrylamide (PNIPAAm) gel system. The swelling behavior, temperature sensitivity, pH sensitivity, gel strength, and drug-release behavior of PNIPAAm/chitosan semi-IPN and IPN hydrogels were investigated. The results indicated that the NIPAAm/chitosan semi-IPN and IPN hydrogels exhibited pH and temperature-sensitivity behavior and could slow drug release and diffusion from the gels. From the stress–strain curves of the hydrogels, the compression moduli of IPN gels containing crosslinked chitosan were higher than those of semi-IPN gels. This is because IPN gels have a more compact structure. The morphology of PNIPAAm/chitosan hydrogels was also investigated. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 2487–2496, 2001     

大孔性pH响应丙烯酸/淀粉水凝胶的合成及表征

以二过碘酸合铜(DPC)为氧化剂,可溶性淀粉为还原剂,组成氧化还原体系,在可溶性淀粉的羟基上引发丙烯酸钠和交联剂亚甲基双丙烯酰胺进行聚合反应制备pH响应淀粉水凝胶,研究了引发剂浓度、反应时间和反应温度等因素对凝胶效率的影响,考察了淀粉水凝胶对pH的响应性。得到了最佳溶胀比的反应条件:引发剂和交联剂的浓度分别为3.12×10-4mol/L,0.0324g/mL,pH值7.01,致孔剂0.08g。     

Effect of polymer solution concentration on the swelling and mechanical properties of glycol chitosan superporous hydrogels

This study examined the effect of the polymer solution concentration on the swelling and mechanical properties of glycol chitosan (GCS) superporous hydrogels (SPHs). GCS SPHs were synthesized using a gas blowing method using glyoxal as the crosslinking agent at different polymer solution concentrations. A small change in the GCS solution concentration resulted in a remarkable change in compression strength and swelling kinetics without any significant loss in equilibrium water imbibing capacity. The increase in mechanical strength accompanied by the decrease in swelling kinetics was caused by the generation of smaller pores during the gelation process of the reactant systems associated with a higher polymer solution viscosity. The apparent diffusion coefficients for a variety of GCS/simulated gastric fluid solution systems were determined from the theoretical fitting of experimental dynamic swelling data, explaining the effects of the solution concentration and crosslinking density on the swelling kinetics. The diffusion coefficients determined in this study are expected to be used as the basic information in estimating the swelling kinetics of samples in different dimension. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Effect of sodium hexametaphosphate concentration on the swelling and controlled drug release properties of chitosan hydrogels

An ionically crosslinked polymer network composed of chitosan and sodium hexametaphosphate (SHMP) was synthesized to determine their swelling and ascorbic acid release kinetics at various SHMP concentrations. The chitosan/SHMP hydrogels were synthesized using an acetic acid aqueous solution (1% v/v). Ionization constants (pK_b) of the SHMP were obtained by potentiometric titration. The results show that the SHMP was hydrolyzed in acidic medium forming orthophosphate and trimetaphosphate. The swelling percentages were measured at different swelling media pH's; the higher swelling capacities were for the systems that were swollen in neutral solution. Also, it was studied the ionic crosslinking degree by turbidimetric titration, comparing the electrostatic interactions between the chitosan and the SHMP; the results shows that electrostatic interactions between the amine groups of the chitosan and the anionic groups of the SHMP are dependent of the swelling medium pH. The ascorbic acid diffusion inside the hydrogel follows the second law of Fick, and the diffusion coefficients were obtained for different SHMP concentrations. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Preparation and swelling of polymeric hydrogels

Hydrogel polymers find extensive biomedical applications combining the properties of hydrophilic and crosslinked materials. In this work, poly(methacrylic acid) hydrogels were prepared by the copolymerization of methacrylic acid with varying amounts of 1,4-butanediol dimethacrylate. The polymerization reaction was followed by viscometric measurements and the swelling properties of the samples prepared were also investigated. Alkaline treatment of the hydrogels was performed, to define the changes induced. Finally, a correlation between swelling data, derived from loosely crosslinked samples, led to the determination of the interaction parameter of the system poly(methacrylic acid)–water.     

PVA/淀粉共混物的动态流变行为和相转变

用复合增塑剂在哈克流变仪上制备了热塑性聚乙烯醇(PVA)/淀粉共混物,研究了共混体系的动态流变行为,观察了共混物的微观结构.结果表明: PVA/淀粉共混物熔体的动态流动行为与其组分的熔体类似,都表现为类固态行为,显示出假塑性流体的流动特征; PVA/淀粉熔体随着组成的变化存在一次相逆转,其复数黏度、储能模量和损耗模量均随着淀粉含量的变化出现了正-负偏差,这说明共混体系出现了相转变,转变点在淀粉质量分数为80% 处.     

Synthesis and characterization of citric acid-based pH-sensitive biopolymeric hydrogels

Biocompatible hydrogels based on citric acid (CA) with varying glycol unit, viz., ethylene glycol (EG), diethylene glycol and triethylene glycol were prepared along with acrylic acid. The formations of various hydrogels were confirmed using spectral techniques such as FT-IR and ¹H NMR. Thermal stability (thermogravimetric analysis, DTA and differential scanning calorimetry) and morphology (SEM) of the synthesized hydrogels were investigated. Swelling studies of hydrogels at various pH values ranging from 4.0 to 10.0 were also investigated. The results of swelling studies show that the percentage of swelling is comparatively higher at higher pH than lower pH. Swelling equilibrium for various hydrogels was also found. Increased composition of CA in hydrogels at different pH values of 4.0, 6.0, 7.4, 8.0 and 10.0 enhanced the swelling equilibrium.     

Stiffness xanthan hydrogels: synthesis,swelling characteristics and controlled release properties

Summary  New xanthan hydrogels were synthesized at 90 C in water acid media using adipic acid dihydrazide (ADH) as crosslinking agent, in the presence of 1-ethyl-3[3-dimethyl amino] propyl carbodiimide hydrochloride (EDCI) as reagent. In these conditions, xanthan chains are in a predominantly helical conformation and through rheological measurements the influence of the temperature over the helix-coil transition was assessed. Xanthan hydrogels with different concentration in polysaccharide and ADH were obtained and characterised by elemental analysis and swelling properties. High concentration of xanthan (i.e. 25gL^-1) is needed to obtain gel due to the low available carboxylic functions in the helical conformation. During the swelling analysis, it was noted that high temperature (i.e. 90 C) favoured the conformational transitions within the network. The drug loading and releasing properties were estimated using methylene blue as model molecule and different experimental pH and ionic strength conditions.     

Temperature and pH sensitive hydrogels composed of chitosan and poly(ethylene glycol)

Summary Chitosan based semi-interpenetrating polymer network (semi-IPN) hydrogels containing different amounts of poly(ethylene glycol) (PEG) were prepared. The crosslinking of the hydrogels was achieved by using a naturally occurring nontoxic cross-linking agent genipin. The swelling behaviour of these hydrogels was studied by immersing the films in deionized water at 25, 37 and 45 °C and in media of different pHs at 37 °C. Swelling was found to be dependent on temperature, pH of the medium and the amount of PEG in the gel. States of water in the hydrogels swollen in deionized water at 37 °C were determined using Differential Scanning Calorimetry (DSC). The equilibrium water content and the amount of freezing water in the swollen hydrogels increased with the increase in PEG concentration in the gels.     

HES-HEMA nanocomposite polymer hydrogels: swelling behavior and characterization

Organophilic sodium montmorillonite (Na-MMT) and Laponite-RD clays were incorporated into photopolymerizable hydroxyethyl starch (HES) modified with 2-hydroxyethyl methacrylate (HEMA). Swelling, mechanical properties and thermal stability of obtained crosslinked nanocomposite polymers were evaluated. A camphorquinone-amine system was used as photoinitiating system in visible light. The interaction between nano-sized filler particles and polymer hydrogel was evaluated by FT-IR spectroscopy and the platelet distribution was investigated by SEM. An increased thermal stability of nanocomposite polymers upon addition of clay was observed by thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC) indicating interaction between the clay platelets and the polymer chains. The crosslinking density for HES-HEMA/MMT nanocomposite hydrogels as investigated by swelling measurements increases with increasing the organo-clay content. The mechanical properties of virgin hydrogels were improved by the introduction of organo-clay as evidenced by oscillation rheology measurements. Whereas, the increase in crosslink density and storage modulus with clay content for laponite was found to be increasing for all concentrations investigated, for MMT there is an optimum content of ca. 1.5 wt%.