Radoslaw A. Wach

Hydrogel of biodegradable cellulose derivatives. I. Radiation-induced crosslinking of CMC

Radiation crosslinking of carboxymethylcellulose (CMC) with a degree of substitution (DS) from 0.7 to 2.2 was the subject of the current investigation. CMC was irradiated in solid-state and aqueous solutions at various irradiation doses. The DS and the concentration of the aqueous solution had a remarkable affect on the crosslinking of CMC. Irradiation of CMC, even with a high DS, 2.2 in solid state, and a low DS, 0.7 in 10% aqueous solution, resulted in degradation. However, it was found that irradiation of CMC with a relatively high DS, 1.32, led to crosslinking in a 5% aqueous solution, and 20% CMC gave the highest gel fraction. CMC with a DS of 2.2 induced higher crosslinking than that with a DS of 1.32 at lower doses with the same concentration. Hence, it was apparent that a high DS and a high concentration in an aqueous solution were favorable for high crosslinking of CMC. It is assumed that; high radiation crosslinking of CMC was induced by the increased mobility of its molecules in water and by the formation of CMC radicals from the abstraction of H atoms from macromolecules in the intermediate products of water radiolysis. A preliminary biodegradation study confirmed that crosslinked CMC hydrogel can be digested by a cellulase enzyme

Hydrogels of polysaccharide derivatives crosslinked with irradiation at paste-like condition

Abstract Polysaccharides such as cellulose, starch, chitin/chitosan and their water-soluble derivatives have been known as degradable type polymers under action of ionizing radiation. Recently, we found that water-soluble polysaccharides derivatives such as carboxymethylcellulose (CMC), carboxymethylstarch (CMS) and carboxymethylchitin (CMCT), carboxymethylchitosan (CMCTS) lead to radiation crosslinking at high concentrated aqueous solution (more than 10%, paste-like state). It was proved that the crosslinking was remarkably affected by their concentration. It was assumed that radiation formation of hydrogels of these polysaccharides derivatives were mainly due to the mobility of side chains. Side-chains radicals were formed mostly via indirect effects, by the abstraction of H atoms by the intermediate products of water radiolysis. Some important characteristics of these novel hydrogels were also investigated. These hydrogels exhibited good swelling in water and possess satisfying biodegradability. In addition, the antibacterial activity against E.coli was also found in CMCTS hydrogel.

Radiation crosslinking of carboxymethylcellulose of various degree of substitution at high concentration in aqueous solutions of natural pH

AbstractCarboxymethylcellulose(CMC)hydrogelformedbyionizingradiationathighlyconcentratedaqueoussolutionswasfoundtoundergoswellingdependingonthepHoftheswellingmedia.SwellingincreasesatneutralandbasicpHduetoionizationofcarboxymethylgroupsonsidechains.Thepresenceofchargesdevelopsrepulsiveforcesbetweenpolymerchainsofthenetworkcausingitsexpansion.Hydrogelinrelaxedstateaswellasdriedgelrevealsgoodmechanicalproperties.Itwasconsideredthatintermolecularcrosslinkingreactionsoccurbyaradicalroute.RadicalsplacedonanhydroglucoserepeatingunitaswellasonsidechainsweredistinguishedfromESRspectraofCMC.Astabledoubletsignal with 2.0mT splitting constant belongs to a radical placed on the a-carbon atom of the substituent group,R–O– d CH–COO – .Itwasassumedthatthisspeciesparticipatesinintermolecularcrosslinking.r 2003ElsevierLtd.Allrightsreserved. Keywords: Carboxymethylcellulose;Hydrogels;Crosslinking;Ionizingradiation;Radicals 1. IntroductionBasicrequirementsforpolymericabsorbentsarelargefluid uptake and high mechanical strength. These twodemandsareclearlyconflicting,andasuitablecompro-mise needs to be found. A high degree of swelling inaqueous systems can be achieved by using polyelec-trolytesbecauseofmobilecounterions presentinsuchgels develop a large swelling pressure (Florry, 1953).Thus,carboxymethylcellulose(CMC),whichisthemostpopularandthecheapestcelluloseethercanbeusedforthis purpose. It is an anionic linear polymer in whichoriginal H atoms of cellulose hydroxyl groups arereplaced by carboxymethyl substituent, –CH

Radiation crosslinking of methylcellulose and hydroxyethylcellulose in concentrated aqueous solutions

Abstract The effects of ionizing radiation on aqueous solutions of cellulose ethers, methylcellulose (MC) and hydroxyethylcellulose (HEC) were investigated. The well-established knowledge states that cellulose and its derivatives belong to degrading type of polymers. However, in our study intermolecular crosslinking initiated by gamma rays or electron beam leaded to the formation of insoluble gel. This is an opposite effect of irradiation to the degradation. Paste-like form of the initial specimen, i.e. concentration 20–30%, when water plasticizes the bulk of polymer; and a high dose rate were favorable for hydrogel formation. Gel fraction up to 60% and 70% was obtained from solutions of HEC and MC, respectively. Produced hydrogels swell markedly in aqueous media by imbibing and holding the solvent. Radiation parameters of irradiation, such as yields of degradation and crosslinking and the gelation dose, were evaluated by sol–gel analysis on the basis of Charlesby–Rosiak equation. Despite of the crosslinked structure, obtained hydrogels can be included into the group of biodegradable materials. They undergo decomposition by the action of cellulase enzyme or microorganisms from compost.

Hydrogel of radiation-induced cross-linked hydroxypropylcellulose

Hydroxypropylcellulose (HPC) hydrogel being a material of natural origin, combines the properties of a polymer, which make up the network, with biodegradability. In this report the effects of high energy radiation on the ether of cellulose-HPC are presented. The polymer irradiated in its solid state or in dilute aqueous solution underwent mainly degradation, induced by the cleavage of glycosidic bonds in its main chain. Irradiation of HPC in aqueous solutions at moderate concentrations resulted in the formation of hydrogels. Chemical cross-links bond the chains of polymer, turning it to an insoluble macroscopic gel. We have found that in addition to concentration, dosage and dose rate can affect the results of irradiation. Electron beam irradiation gave higher gel fraction, up to 90%, than gamma irradiation, which has a maximum gel fraction of 65%. Swelling of the cross-linked hydrogels was related to the density of cross-links and was the highest at low irradiation doses. HPC hydrogels displayed thermally reversible character in their swelling. The volume of gel underwent continuous deswelling with an increase of the solution temperature, with the deswelling rate increasing rapidly over 40°C. At elevated temperatures the hydrogel collapsed, lost its transparency and changed color to translucent white. This transition was fully reversible when the gel was placed in the medium of low temperature. The hydrogel demonstrated superior mechanical properties. Despite of the stable three-dimensional cross-linked network, the gels underwent biodegradation under controlled conditions when enzyme was used.

Hydroxyl radical-induced crosslinking and radiation-initiated hydrogel formation in dilute aqueous solutions of carboxymethylcellulose

Ionizing radiation causes chain scission of polysaccharides in the absence of crosslinking agents. It has been demonstrated before that degradation of carboxyalkylated polysaccharides may be prevented, despite presence of strong electrostatic repulsing forces between chains, at very high polymer concentration in water (paste-like state) when physical proximity promotes recombination of radiation-generated polymer radicals. In such conditions, crosslinking dominates over chain scission and covalent, macroscopic gels can be formed. In an approach proposed in this work, neutralizing the charges on carboxymethylcellulose (CMC) by lowering the pH results in retracting the electrostatic repulsion between chain segments and thus allows for substantial reduction of polymer concentration required to achieve gelation due to domination of crosslinking reactions. Electron-beam irradiation of aqueous solutions of low pH containing 0.5-2% CMC results in hydrogel formation with 70% yield, while both concentration and dose determine their swelling properties. Time-resolved studies by laser flash photolysis clearly indicate strong pH influence on decay kinetics of CMC radicals.

ESR investigation on gamma-irradiated methylcellulose and hydroxyethylcellulose in dry state and in aqueous solution

Two derivatives of cellulose were investigated by ESR method after gamma-irradiation. Irradiation of methylcellulose (MC) and hydroxyethylcellulose (HEC) results in formation of radicals on these polysaccharides. Their transformations cause main-chain scission or to the opposite effect, crosslinking of polymer. It was proposed that radicals placed on anhydroglucose repeating unit contribute to degradation reactions, and those located on side chains of derivatives, i.e., methoxy group, -O-CH3 and hydroxyetyl ether group, -O-CH2-CH2-OH participate in crosslinking.

Biocompatibility of Modified Bionanocellulose and Porous Poly(ϵ-caprolactone) Biomaterials

Biocompatibility of modified bionanocellulose (BC) and porous poly(ϵ caprolactone) (PCL) were compared to UHMWPE. For all the materials lack of cytotoxic effect to mouse fibroblasts was observed in vitro. In vivo study, subcutaneous implantations in Wistar rats, lasted for seven, 14, and 30 days. Subsequently the composition of surrounding tissue and explants surface changes was evaluated. No symptoms of acute inflammation were observed. Surrounding tissue thickness, the number of granulocytes, lymphocytes, macrophages, and blood vessels differed in time and revealed regular healing process. It is concluded that investigated PCL and BC are the materials with superior biocompatibility with high application potential.

In Vitro Degradation of β-Tricalcium Phosphate Reinforced Poly(L-Lactic Acid)

Poly (L-lactic acid) (PLLA) and composite of PLLA with osteoconductiveβ-tricalcium phosphate fine powder (PLLA/TCP) compression moulded specimens were subjected to in vitro biodegradation up one year. Samples were investigated in terms of physical-chemical evaluation after several periods of incubationin simulated body fluid solution. Reduction in PLLA molecular weights occurred during thermal processing of compounding of the polymer with TCP. 3-point bending measurements revealed some decay in the flexural strength and increase in stiffness after incorporation of the inorganic particles into the polymer. Those parameters remained nearly stable during the biodegradation period despite constant drop of polymer molecular weight. Thermal properties of both kinds of samples did not changed significantly, however degree of crystallinity of PLLA matrix was increasing slowly in pure PLLA samples. Despite no mass loss,extent of surface deteriorationincreased steady during the incubation. Current study is intended to develop material for implants, mainly fusion cages targeted for spinal applications.

The influence of selected NSAIDs on volume phase transition in poly(2-(2-methoxyethoxy)ethyl methacrylate) hydrogels

Hydrogels exhibiting Volume Phase Transition (VPT) are considered as useful biomaterials for the preparation of various drug delivery systems. Such hydrogels are commonly based on thermo-responsive polymers, such as poly(2-(2-methoxyethoxy)ethyl methacrylate) (PMEO2MA), that have lower critical solution temperature (LCST) in aqueous solutions. In this work, PMEO2MA hydrogels were used as model systems to study the influence of encapsulated drugs, such as ibuprofen and salicylate sodium salts, on the temperature and dynamics of the VPT. Both thermo-optical analysis and differential scanning calorimetry have shown that the VPT becomes broader and shifts towards higher temperatures with increasing drug concentration. Three regimes of VPT in PMEO2MA gels were distinguished. The first two, related to the breaking of the strong water-polymer interactions and to the network collapse, slow down with increasing drug concentration. The last regime, corresponding to the slow diffusion of a residual solution from a collapsing network, becomes visible only for systems with high content of drug. Raman spectroscopy studies show that the observed effect is not connected to direct interactions between polymers and drugs. This suggests that the drug molecules are able to stabilise water-polymer interactions in thermo-responsive hydrogels. Consequently, they are able to modulate VPT and have a significant influence on the delivery process.