Reentrant conformation transition in poly(N,N-dimethylacrylamide) hydrogels in water-organic solvent mixtures

Conformational changes in poly(N,N-dimethylacrylamide) (PDMA) networks swollen in aqueous solutions of organic solvents are studied both experimentally and theoretically. PDMA hydrogels of various charge densities were prepared by free-radical crosslinking copolymerization. Swelling behavior of the hydrogels was investigated in aqueous organic solvent mixtures as functions of solvent species and the concentration. With increasing volume fraction ? of acetone, tetrahydrofuran, or 1,4-dioxane in the aqueous solution, PDMA hydrogels exhibit reentrant conformation transition. During this transition, the gel first deswells in the range of ? between 0.4 and 0.9, and then rapidly reswells if ? is monotonically increased. The reswelling of the collapsed PDMA gel occurs in a narrow of ? above ?=0.97. It was shown that the reentrant transition in PDMA gels requires moderate hydrogen bonding organic solvents, so that the hydrophobic interactions between PDMA and the organic solvent dominate the swelling process. The results were interpreted using the theory of equilibrium swelling. The interaction parameters in the gel system as well as the partition parameter of the organic solvent between the gel and the solution phases were calculated.     

Functionalization of hydrocolloids: principal component analysis applied to the study of correlations between parameters describing the consistency of hydrogels

This work was part of a pure research project on the functionalization of three families of hydrocolloids: cellulose derivatives, carrageenates, and alginates. Principal component analysis (PCA), a powerful statistical method, was used to demonstrate the relations existing among these different parameters that describe the consistency of hydrogels and their spreadability. This approach therefore provides a basis for modeling hydrogel consistency. PCA also afforded a classification of hydrogels that demonstrated the remarkable adhesiveness of very stiff gels based on cellulose derivatives and sodium or potassium alginates. The corresponding semifluid gels and all the gels based on carrageenates and mixed sodium-calcium alginates, whatever their spreadability, were found to be very poorly adhesive. Generalized to all the many colloids currently marketed, this approach can be used to set up a databank for the formulation of mucoadhesive excipients.     

Unveiling the self-assembly behavior of copolymers of AAc and DMAPMA in situ to form smart hydrogels displaying nanogels-within-macrogel hierarchical morphology

Stimulus responsive hydrogels are being considered as one of the most crucial biomaterials of current generation. A new technique has been established for developing hydrogels based on Acrylic acid (AAc) and N-[3-(Dimethylamino)propyl]-methacrylamide (DMAPMA), and relevant mechanism has been delineated. Aqueous redox copolymerization of different molar ratios of AAc and DMAPMA at 41 ± 1 °C, leading to the formation of interlocked nanogels of ∼300 nm diameter, which acted as the building blocks of a series of superabsorbent hydrogels having robust, honey-comb type three-dimensional architecture. Monomer composition, monomer feed ratio and water content in feed has been found to be important factors in the development of the stable poly(AAc-co-DMAPMA) hydrogel membranes (PADMAs) without any active crosslinking agent. At the cues of pH change from 7.0 to 3.5, pulsatile swelling-deswelling behavior varied, ranging from ∼5900% to ∼60% (mass) respectively, underlining smart hydrogel characteristics needed for specific biomedical applications. Elastic modulus of the gels, equilibrated at pH 7.0, is recorded to be >15 kPa under uniaxial compression. Underlying mechanism of the formation of such robust three-dimensional structures in poly(AAc-co-DMAPMA) hydrogel membranes, and the origin of hierarchical ‘nano-to-macro’ scale morphological features has been proposed.     

Dual-network hydrogels based on chemically and physically crosslinked chitosan/chondroitin sulfate

The formation of a novel type of hydrogel that combines chemically and physically crosslinked networks in a dual-network approach is presented here. Chitosan (CHT) and chondroitin sulfate (CS) were chemically modified with glycidyl methacrylate (GMA) and then crosslinked. The chemical hydrogels (CHT- and CS-gel) were deposited in different vials filled with CS or CHT stock solutions to form the dual-network hydrogels. FTIR, TGA and XRD analyses were used to characterize the chemical and the dual-network hydrogels. The percentages of CS or CHT complexed to the CHT- and CS-gel networks were calculated from the HPLC data. SEM images and swelling assays indicated that the formation of a secondary network by polyelectrolyte complexation changes the morphologies and liquid uptake capacities of the chemical hydrogels. Hence, the data and discussion presented here enable the formation of dual-network hydrogels with very interesting properties, such as the ability to interact with charged specimens (i.e., drugs, proteins or metal ions), a desirable feature for a wide range of applications.     

Synthesis and characterization of UV photocrosslinkable hydrogels with poly(N-vinyl-2-pyrrolidone): Determination of the network mesh size distribution

Hydrogels of poly(n-vinyl-2-pyrrolidone) were produced by UV irradiation of aqueous solutions of the polymer in presence of hydrogen peroxide, used as initiator. The mechanical and the nanostructural properties of the gels were characterized by a combination of experimental techniques including rheology, low field nuclear magnetic resonance spectroscopy (LF-NMR), and small angle X-ray scattering. Different irradiation doses as well as polymer and initiator concentrations were tested in the characterization. The study elucidates the relationship between different methods to estimate the mesh size of the gel polymeric network. Moreover, a novel correlation model was developed based on Chui and Scherer theories for the interpretation of LF-NMR dataset of polymer solutions and networks.     

Hydrogels Formed by Cross-Linked Polyvinylalcohol as Colon-Specific Drug Delivery Systems

Polyvinylalcohol (PVA) of different molecular weights was cross-linked with succinyl, adipoyl, or sebacoyl chloride to obtain hydrogel-forming polymers and to determine their suitability as colon-specific drug delivery systems. Diclofenac sodium, propranolol hydrochloride, and vitamin B6 hydrochloride were used as hydrophilic model drugs with colon-specific release that should yield high concentrations in the large intestine, minimizing release in the upper part of the gastrointestinal tract. Spray-dried mixtures of the drugs and the polymer (at a 1 : 2 w/w ratio) were prepared, and the release of the drugs from the mixtures was evaluated in vitro at pH 2.0, 5.5, and 7.4. The results indicated the ability of the cross-linked polymers to slow the release of the drugs analyzed with respect to the pure drug dissolution at each pH. The lengthening of the cross-linker acyl chain was noted to decrease drug release further.