Dynamic swelling performance of hydrophobic hydrogels

Conventional gels manifest monotonous swelling or shrinking performance upon immersing in solvents until reaching an equilibrium state. Recently, we discovered that the “hydrophobic hydrogels” prepared from hydrophobic polymer networks demonstrated dynamic swelling performance without equilibrium states. Upon water immersion, the gels expanded tremendously at the first stage until reaching a swelling peak; subsequently, the gels shrunk at an extremely slow rate. While this phenomenon endows the ...     

Polymeric hydrogels modified with ornithine and lysine: Sorption and release of metal cations and amino acids

A novel, convenient synthesis, using copper ions, is described for the multigram‐scale preparation of acryloyl and methacryloyl ornithine and lysine without the need to use protecting groups and chromatographic purifications. Three methods of removing the copper ions from the amino acid derivatives were examined. The obtained acryloyl and methacryloyl ornithine and lysine were copolymerized with N‐isopropylacrylamide and N,N′‐methylenebisacrylamide as crosslinking agents, resulting in a series of hydrogels with varying incorporated amino acid content. The relative content of a given amino acid was estimated from the ¹H NMR data and compared with its molar fraction used in the polymerization process. We investigated the influence of the amount of amino acid groups incorporated into the polymer network on the swelling behavior of the gels in the presence of metal ions of different ability to form complexes (Cu²⁺, Co²⁺, and Ca²⁺) with α‐amino acid groups and the sorption of copper ions. Next, the presence of α‐amino acid groups attached to the polymer network was used to bond the compounds which can cocomplex metal ions. Phenylalanine was selected for examination of its cocomplexation of Cu²⁺ with the polymer‐network amino acids and its consecutive release from the gel after appropriate change of pH. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

Preparation of poly(vinyl alcohol) hydrogels with radiation grafted citric and succinic acid groups

Ternary mixtures of PVA/Citric acid (CA)/water and PVA/Succinic acid (SA)/water were gamma irradiated to various doses in air at ambient temperature. Gelation % vs dose curves were constructed and swelling behavior of gels with maximum conversions was studied. In maximum gelled systems 80% of CA used in the feed composition was retained in the gel structure whereas this was only 20% for SA. The volume of swelling of ionic PVA gels increased from 230% to 530% for PVA/CA systems when pH was increased from 2.6 to 7.5. Less significant increase in swelling was observed for PVA/SA gels, from 250% to 330% in the same pH interval. The incorporation of SA and CA groups onto PVA networks improved remarkably the affinity of these structures for Co²⁺ and Ni²⁺ ion uptake.     

Stimuli sensitive polymers for drug delivery systems

Temperature sensitive and electric field sensitive hydrogels were prepared for use in modulated drug release systems. Crosslinked poly(N-isopropyl-acrylamide) and its networks, modified with hydrophobic components by copolymerization or by interpenetrating polymer networks (IPNs) formation, were utilized as temperature sensitive hydrogels. Indomethacin (a model solute)-release from polymer matrix and permeation through polymer membrane demonstrated “on-off” regulation with temperature fluctuation. This was the result of polymer surface properties rather than bulk swelling, as temperature was changed past the swelling transition temperature range of the polymer. The on-off regulation in an electric field was also obtained with a positively charged solute (Edrophonium chloride) release in distilled-deionized water from a matrix of crosslinked poly(2-acrylamido-2-methylpropanesulfonic acid-co-butyl methacrylate). This was attributed to the ion exchange between Edrophonium ion and protons produced at the anode. The swelling changes produced by local pH or ionic strength changes affected non-charged solute release.     

Colon-specific devices based on methacrylic functionalized Tween monomer networks: Swelling studies and in vitro drug release

Colon-targeted delivery devices based on methacrylic functionalized Tween monomer networks, useful for 5-FU or Ferulic acid site-specific release, were synthesized. The basic design consists of methacrylic functionalized Tween monomer-based networks prepared with or without acrylic acid as co-monomer. The swelling behaviour and loaded drugs release from these gels was studied as a function of pH. The devices showed a strong pH-dependent swelling behaviour, allowing a maximum release at pH 7.4. The acrylic acid introduction increased the polymeric gels pores size, as evidenced by the loading efficiency increase, but also reduced the amount of released drug in basic media compared to analogous network not containing the co-monomer. This behaviour, already found in the matrix swelling, could be attributed to a slower hydrolysis kinetics of the ester bond in functionalized Tween monomers, which implies a reduced ability to absorb water from a basic medium, resulting in a lower capacity to release the loaded drug.Since our device possesses a maximum drug release in the media at pH 7.4, it could be used for colon-targeted drug delivery of both 5-FU and Ferulic acid.     

Gel properties as a hydrogel of crosslinked poly (l-ornithine) using organic crosslinking agents

Gel formations of water-soluble cationic ornithine polypeptides were examined using organic aliphatic crosslinking agents such as dialdehydes and diketones in water systems. When 1/20-5 equivalent molar amounts of organic crosslinking agents were added to the ornithine polypeptide systems, the corresponding gels were formed. Among the organic crosslinking agents used, glutaraldehyde was the most effective for the gel formation. As a whole, the molecular weight of the samples, the amino acid compositions, the crosslinking agents used, the molar ratios between crosslinking agents and functional residues, and system pH levels were found to play roles in the gel formation. The gels formed were characterized by swelling properties and by the selective adsorption ability of some amino acids. The polyornithine gels exhibited reversible, but hysteretic swelling in a water-acetone mixed solvent. Due to the cationic δ-amino moieties which remain unreacted, the acidic amino acid, aspartic acid, was adsorbed into the gels' matrix, exhibiting the predominant adsorption. Biodegradable characteristics of the copoly (ornithine tyrosine) [copoly (Orn Tyr)] gels by chymotrypsin were also investigated.     

New neutral and ionic poly(ethylene oxide) networks by radical polymerization

New opportunities resulting from a turn to radical polymerization in the synthesis of poly(ethylene oxide) (PEO) networks are discussed and exemplified. Several series of such networks have been prepared by radical homo‐ and copolymerization in aqueous media of “macromonomers”, i.e. partly methacrylated poly(ethylene glycol) (PEG) of varied molecular weight (MW ≅ 2000‐12000) and functionality (f_n ≅ 1.25‐1.8). This family of gels as a whole has the volume swelling degree Q in the range of 10 to 200 ml/ml. The hydrogels are characterized by means of Q, elastic modulus, swelling pressure, and with the use of some probes. The swelling behaviour of neutral hydrogels of this kind is briefly resumed. The multifunctional junctions formed in the propagation reaction of methacrylate end groups determine their main peculiarity. Anomalous elastic behaviour of the swollen networks prepared at high concentration of polymer has been observed and attributed to the network chains stretching of the same nature as in polymer stars or brushes. The junctions' functionality (F ≈ 20‐300) is evaluated from these data as well as from MW of the soluble models of network junctions. The PEO networks with charged units in junctions have been obtained by copolymerization of macromonomers with some ionic (meth)acrylic monomers. These gels display all the polyelectrolyte features, e.g. enhanced Q values in water (up to 50‐70) and, contrary to neutral PEO gels, the strong dependence on salt content. However, the osmotic contribution of mobile ions into swelling is shown to be low due to localization of charges in the junctions. The hydrogels that combine PEO and polymethacrylic acid chains capable of interpolymer complexation have been prepared and studied. They show much higher swelling in pure water (Q up to 200), strong deswelling by NaCl, and very sharp drop in swelling (ca. two order in Q) at pH ≈ 4.5‐5.5 due to complexation.     

化学改性大豆蛋白凝胶溶胀过程规律的研究

将大豆蛋白(SPI)经预热处理、EDTAD酰化和戊二醛交联,制备出改性大豆蛋白凝胶.通过红外与化学法研究了改性大豆蛋白分子的结构变化,结果表明,经EDTAD改性,大豆蛋白分子的侧链基团和分子链构象均发生变化;侧链的游离氨基与EDTAD发生酰化反应,为蛋白质分子链引入羧基;基团分析数据显示,改性大豆蛋白分子中游离氨基数减少,羧基数增加,增加的羧基数与减少的氨基数之比约为3:1.研究了改性大豆蛋白凝胶的溶胀率变化,并对溶胀数据进行数学处理,分析了不同mEDTAD:mSPI的凝胶的溶胀过程规律,结果显示,mEDTAD:mSPI为0,0.05,0.1和0.2的改性大豆蛋白凝胶在水中的溶胀率为24.2,54.01,87.27和95.87,说明分子链引入一定量的EDTAD使凝胶溶胀率增大;其溶胀特征指数为0.5,表现为Fickian扩散.研究了改性凝胶在不同pH下的溶胀过程规律,结果显示,在pH4.30和6.08时,凝胶溶胀特征指数n范围是0.5n1,表现为non-Fickian扩散,而在碱性pH10.04,凝胶特征溶胀指数为0.5,仍表现为Fickian扩散.改性大豆蛋白凝胶溶胀率对pH变化具有敏感性,其溶胀-消溶过程曲线呈"W"形,显示凝胶具形状记忆功能.     

Investigation of interpolymer complexation in swollen polyelectolyte networks using solid‐state NMR spectroscopy

Copolymer networks of poly(methacrylic acid) (PMAA) and poly(ethylene glycol) (PEG) exhibit large changes in their swelling behavior over a narrow pH range due to the reversible formation/dissociation of interpolymer complexes between the polymer chains. Intepolymer complexation occurs in copolymer gels of PMAA and PEG due to hydrogen bonding between protonated acid groups and the ether groups of the PEG. Because of their nature, these gels have been identified for use as delivery vehicles for macromolecular drugs. In this work, solid‐state, nuclear magnetic resonance nuclear Overhauser enhancement (NOE) experiments were performed to detect the molecular level complexation between PMAA and deuterated PEG in copolymer blends and crosslinked networks. For gels swollen in acidic media at room temperature or at 37 °C, strong enhancements were detected in the ¹³C resonance of the PEG carbons. The NOE was generated due to energy transfer between the rapidly rotating methyl group protons and the deuterated PEG carbons. The presence of the NOE was indicative of close packing of the polymer chains and was evidence of the presence of the intermacromolecular complexes. In basic solutions, no NOE was detected in the PEG, as the complexes were dissociated and the chains were separated in space. © 2000 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 38: 2823–2831, 2000     

Synthesis of a pair of novel receptors and their properties of enantioselective recognition for amino acid zwitterions

A pair of artificial enantiotopic receptors la and lb composed of ( S, S) or (R,R) chiral bicyclic guanidinium, azacrown ether and (t-butyldiphenylsilyloxy) methyl group for amino acid zwitterions have been synthesized. The liquid-liquid competition extraction experiments and 1H NMR studies indicate that the receptor 1a with (S, S) configuration and lb with (R,R) configuration selectively recognize L- and Z)-aromatic amino acids respectively.     

聚丙烯酸凝胶溶胀行为的研究

本文合成了一系列不同交联度的聚丙烯酸凝胶,测定了这些凝胶在不同ｐＨ值及温度下的综合溶胀行为,包括用经典的间断称重方法测定溶胀动力学曲线,用溶胀性能自动测定仪测定溶胀应力变化的动力学曲线及平衡溶胀度等。这这类环境敏感材料的应用提供了科学数据。     

Synthesis and Properties of Hydrogels Based on Chitosan and Poly(Vinyl Alcohol) Crosslinked by Genipin

Semi‐interpenetrating polymeric networks of chitosan and poly(vinyl alcohol) [PVA] were prepared by varying the ratio of the constituents. The hydrogels were crosslinked using genipin, a naturally occurring nontoxic cross‐linking agent. The swelling behavior of these hydrogels was studied by immersing the films in deionized water at various temperatures and in buffer solutions of different pH. The states of water in the hydrogels, swollen at 25°C and pH 7, were determined using Differential Scanning Calorimetry (DSC). The swelling behavior of the gels was found to be dependent on temperature and pH of the medium. The amount of freezing water in the swollen hydrogels increased, whereas the amount of nonfreezing bound water remained more or less the same with increasing PVA concentration.     

Comparative Study on the Collapse Transition of Poly(N-isopropylacrylamide) Gels and Magnetic Nanoparticles Loaded Poly(N-isopropylacrylamide) Gels

A novel polymer gel exhibiting simultaneous temperature and magnetic field sensitivity has been prepared and studied. Poly(N-isopropylacrylamide) (PNIPA) and magnetic nanoparticles (magnetite, Fe₃O₄) loaded PNIPA gel beads with mm size and monolith gels with cm size were prepared. The dependence of swelling degree on the temperature has been studied. The effects of cross-linking density and the presence of magnetic nanoparticles on the equilibrium swelling degree as well as on the collapse transition have been investigated. Swelling kinetic measurements were also made. By comparing the equilibrium swelling properties of PNIPA and magnetite loaded PNIPA gels it was found that the built in magnetic nanoparticles do not modify the temperature sensitivity of these gels. Within the experimental accuracy the temperature of the collapse transition was not sensitive to the presence of magnetic particles. We have compared the swelling behaviour of mm size gel beads to the cm size monolith gels in order to study the influence of surface skin layer on the swelling equilibrium. It was established that the extent of surface skin formation was decreased by the presence of magnetic particles.     

The use of hydrophobic spacers in the development of new temperature- and pH-sensitive polymers

The preparation and characterization of two series of methacrylic acid derivative polymers is described. One series contains aliphatic spacers with one to ten methylene units, while the other series includes an aromatic ring with changes in the position of the acid, as spacer. Both series of polymers were obtained as methoxy-ester protected acid polymers and as polymers containing free acid groups in different amounts. pH-sensitive gels and temperature-sensitive N-isopropylacrylamide (NIPAAm) copolymers were prepared by using some of the monomeric structures described. The pH of the swelling transition of the gels changed from 3.5 up to 9.0 as a function of the spacer length and type. The lower critical solution temperature (LCST) of NIPAAm copolymers in water was lowered from 33.6°C to 6°C as a function of the co-monomer content and type. The observed changes in the pH of the swelling transition of gels and in the LCST of NIPAAm copolymers can only be explained if hydrophobic-hydrophobic and hydrogen-bonding interactions are considered in connection with the specific chemical structure of the monomers used.     

Phase transition in swollen gels 31. Swelling and mechanical behaviour of interpenetrating networks composed of poly(1-vinyl-2-pyrrolidone) and polyacrylamide in water/acetone mixtures

Swelling and mechanical behaviour of interpenetrating positively charged polymer networks (IPNs), composed of poly(1-vinyl-2-pyrrolidone) (PVP) networks and polyacrylamide (PAAm) networks, was investigated in water/acetone mixtures. The first PVP networks were prepared by radiation polymerization at room temperature; after that the PVP networks were swollen in PAAm aqueous solutions and the networks were prepared by thermal copolymerization at 65 °C. The IPNs were prepared with various amounts of the two charged comonomers (quaternary ammonium salts) in the presence of crosslinkers. Two transition regions, detected in the dependence of swelling ratio X on acetone concentration a, suggest that a two-phase structure was formed. The first transition, located between 44 and 60 vol% of acetone, corresponds to PAAm networks, while the second transition, located at 75 vol% of acetone, corresponds to PVP networks. Depending on the amount of positive charges bound to chains, both transitions exhibit continuous or discontinuous character; this fact indicates that intermolecular interactions between the two components occur with the formation of IPNs (e.g., more polar, charged PVP component increases the extent of hydrogen bonding and makes acetone less effective solvent for IPNs at the PAAm transition). The dependences of log G on log X are roughly the same regardless of charge concentrations; this means that the mechanical behaviour is predominantly determined by the degree of swelling for all gels.     

Kinetics of shrinking of polymer gels induced by ultracentrifugal fields

The kinetics of the shrinking of polymer gels induced by ultracentrifugal fields is investigated. A theory is proposed to describe the diffusion process of polymer networks under centrifugal fields. The initial shrinking rate is proportional to the ratio of the centrifugal force to the frictional force of networks. The shrinking attains the stationary state as a result of the balance between the centrifugal force and the swelling force of networks. The characteristic time for shrinking is of the order of a2/D where a and D are the stationary displacement and diffusion constant, respectively. We also present the experimental data for the shrinking of the poly(acrylamide) (PAAm) gels under ultracentrifugal fields. The shrinkage increases linearly with time in the initial stage whereas it reaches the steady state in the long time limit as expected by the theory. Each of longitudinal elastic modulus and friction coefficient of the PAAm gels is evaluated from the data on the basis of the theory.     

Radiation synthesis of acrylic acid/polyethyleneimine interpenetrating polymer networks (IPNs) hydrogels and its application as a carrier of atorvastatin drug for controlling cholesterol

Gamma irradiation was used to form interpenetrating polymer networks structure (IPNs) hydrogels based on different ratios of acrylic acid monomer (AAc) and polyethyleneimine (PEI). The property-behavior was characterized by IR spectroscopy, gel content, thermogravimetric analysis (TGA) and swelling in water at room temperature and different pH values. The AAc/PEI hydrogels were used as a carrier for atorvastatin drug, in which the uptake-release character was studied. The results showed that the gel content of AAc/PEI hydrogels decreased greatly with increasing the ratio of PEI in the initial feeding solution. The AAc/PEI hydrogels displayed pH-sensitive character. The drug uptake-release study indicated that AAc/PEI hydrogels possessed controlled release behavior and that the release process depends on pH. In this respect, the release of atorvastatin drug was significant in acidic medium.     

Enhancement of acid tolerance in Zymomonas mobilis by a proton-buffering peptide

A portion of the cbpA gene from Escherichia coli K-12 encoding a 24 amino acid proton-buffering peptide (Pbp) was cloned via the shuttle vector pJB99 into E. coli JM105 and subsequently into Zymomonas mobilis CP4. Expression of Pbp was confirmed in both JM105 and CP4 by HPLC. Z. mobilis CP4 carrying pJB99-2 (Pbp) exhibited increased acid tolerance (p<0.05) in acidified TSB (HCl [pH 3.0] or acetic acid [pH 3.5]), glycine-HCl buffer (pH 3.0), and sodium acetate-acetic acid buffer (pH 3.5) in comparison to the parent strain (CP4) and CP4 with pJB99 (control plasmid). Although the expression of Pbp influenced survival at a low pH, the minimum growth pH was unaffected. Growth of Z. mobilis in the presence of ampicillin also significantly increased acid tolerance by an unknown mechanism. Results from this study demonstrate that the production of a peptide with a high proportion of basic amino acids can contribute to protection from low pH and weak organic acids such as acetic acid.     

Determination of the parameters controlling swelling of chemically cross-linked pH-sensitive poly(N-vinylimidazole) hydrogels

The number of variables controlling the behavior of ionic gels is large and very often some of them are unknown. The aim of this work is to interpret quantitatively the swelling behavior of pH sensitive gels, with the minimum number of simplifying assumptions. With this purpose, the equilibrium degree of swelling (S) and protonation (alpha) of chemically cross-linked poly(N-vinylimidazole) (PVI) immersed in aqueous salt solutions were measured as a function of the ionic strength (mu), in the whole range of pH. In acid solutions with pH in the range 0 to 4, imidazole moieties become protonated, and PVI behaves as a polyelectrolyte gel: S decreases upon increasing mu both for NaCl and for CaCl(2), with HCl as protonating acid. In aqueous solutions with larger pH, between 4 and 12, the hydrogel is practically neutral, and S increases as mu rises, showing a salting-in effect. From the quantitative analysis of these results, the following facts emerged. Protonation induces chain stiffness (as measured by the non-Gaussian factor) and worsening of the solvent quality of the aqueous media (as measured by the polymer-solvent interaction parameter). For alpha below 33%, swelling seems to be governed by the excess of mobile counterions inside the gel with respect to the bath, with a minor but still significantly negative contribution of the osmotic swelling pressure due to polymer-solvent mixing. Above 33% protonation, it is necessary to consider Manning counterion condensation to get parameters with physical meaning. The crossover between polyelectrolyte and salting-in effects corresponds to alpha and mu values with the same ionic and mixing contributions to the osmotic swelling pressure. The formation of ionic nonpermanent cross-links, with H(2)SO(4) as the protonating acid, was discarded.