ABSTRACT
In the present paper we report for the first time the development of redox-responsive biocompatible polymer gels. Double cross-linked poly(aspartic acid) hydrogels were prepared using two different cross-linking agents simultaneously. One of the cross-linkers was diaminobutane (DAB), the other cystamine (CYS). The relative amounts of DAB and CYS molecules were varied over a wide range while the total amount of cross-linker molecules (DAB+CYS) was kept constant. DAB provides stable cross-links, whereas CYS contains disulfide bonds, which can be broken by reduction. The cleavage of disulfide cross-links results in enhanced swelling and a significant decrease in the elastic modulus of the gels. These novel types of stimuli-responsive gels are promising candidates for new swelling controlled release matrices.
Subject(s)
Cross-Linking Reagents/chemistry , Hydrogels/chemistry , Peptides/chemistry , Aspartic Acid/analogs & derivatives , Aspartic Acid/chemical synthesis , Aspartic Acid/chemistry , Butanes/chemistry , Cystamine/chemistry , Disulfides/chemistry , Elastic Modulus , Hydrogen-Ion Concentration , Hydrolysis , Kinetics , Least-Squares Analysis , Molecular Weight , Oxidation-Reduction , Particle Size , Peptides/chemical synthesis , Solutions , Spectroscopy, Fourier Transform Infrared , Stress, Mechanical , Thermodynamics , ViscosityABSTRACT
In order to obtain nontoxic functional polymer gels for biomedical applications, chemically crosslinked poly(aspartic acid) gels have been prepared using 1,4-diaminobutane as crosslinker. The presence of COOH and amino groups on the network chains renders these gels pH sensitive. Due to the specific hydrophobic-hydrophilic balance, these gels show a significant volume transition at a well-defined pH close to the pK value of uncrosslinked poly(aspartic acid). Since the magnitude of volume change critically depends on the degree of crosslinking, it is an important task to determine the topological characteristics of these networks. A novel method based on potentiometric acid-base titration has been developed to assess the crosslinking ratio, excluding physical crosslinks and entanglements. It turned out that only 25% of all crosslinker molecules forms real crosslinks between the poly(aspartic acid) chains; the rest react with one of its functional groups and forms short pendant side chains. At a nominal crosslinking ratio of 0.1, the number average molecular mass between crosslinks is found to be M(c) = 2300.
Subject(s)
Biocompatible Materials/chemistry , Cross-Linking Reagents/chemistry , Electrochemistry/methods , Gels/chemistry , Materials Testing/methods , Peptides/chemistryABSTRACT
Chemically cross-linked poly(aspartic acid) (PASP) gels were prepared by the hydrolysis of poly(succinimide) (PSI). The latter was prepared by thermal polycondensation of aspartic acid. The PSI chains were cross-linked by natural amines and amino acid derivatives such as putrescin, spermine, spermidine, lysine and cystamine to obtain biodegradable, biocompatible, amino acid-based hydrogels. The volume of the synthesized unhydrolyzed PSI gels changes abruptly at a well-defined pH that results in ring opening, while the hydrolyzed gels show a volume phase transition around the pK values of PASP. The unidirectional stress-strain behavior of the gels as well as the dependence of equilibrium swelling degree on the pH was carefully studied and the most important network parameters were determined by a modified version of the Brannon-Peppas-Peppas theory.
