Flexible Cotton Fabric-Based Ionizing Radiation Dosimeter for 2D Dose Distribution Measurements over a Wide Dose Range at High Dose Rates.

This work presents an ecological, flexible 2D radiochromic dosimeter for measuring ionizing radiation in the kilogray dose range. Cotton woven fabric made of cellulose was volume-modified with nitrotetrazolium blue chloride as a radiation-sensitive compound. Its features include a color change during exposure from yellowish to purple-brown and flexibility that allows it to adapt to various shapes. It was found that (i) the dose response is up to ~80 kGy, (ii) it is independent of the dose rate for 1.1-73.1 kGy/min, (iii) it can be measured in 2D using a flatbed scanner, (iv) the acquired images can be filtered using a mean filter, which improves its dose resolution, (v) the dose resolution is -0.07 to -0.4 kGy for ~0.6 to ~75.7 kGy for filtered images, and (vi) two linear dose subranges can be distinguished: ~0.6 to ~7.6 kGy and ~9.9 to ~62.0 kGy. The dosimeter combined with flatbed scanner reading and data processing using dedicated software packages constitutes a comprehensive system for measuring dose distributions for objects with complex shapes.

Dextran Methacrylate Reactions with Hydroxyl Radicals and Hydrated Electrons in Water: A Kinetic Study Using Pulse Radiolysis.

Dextran methacrylate (Dex-MA) is a biodegradable polysaccharide derivative that can be cross-linked by ionizing radiation. It is therefore considered a potential replacement for synthetic hydrophilic polymers in current radiation technologies used for synthesizing hydrophilic cross-linked polymer structures such as hydrogels, mainly for medical applications. This work is focused on the initial steps of radiation-induced cross-linking polymerization of Dex-MA in water. Rate constants of two major transient water radiolysis products-hydroxyl radicals (•OH) and hydrated electrons (eaq-)-with various samples of Dex-MA (based on 6-500 kDa dextrans of molar degree of substitution or DS with methacrylate groups up to 0.66) as well as non-substituted dextran were determined by pulse radiolysis with spectrophotometric detection. It has been demonstrated that these rate constants depend on both the molecular weight and DS; reasons for these effects are discussed and reaction mechanisms are proposed. Selected spectral data of the transient species formed by •OH- and eaq--induced reactions are used to support the discussion. The kinetic data obtained in this work and their interpretation are expected to be useful for controlled synthesis of polysaccharide-based hydrogels and nanogels of predefined structure and properties.

Controlling the Spatiotemporal Release of Nerve Growth Factor by Chitosan/Polycaprolactone Conduits for Use in Peripheral Nerve Regeneration.

Tubular polymeric structures have been recognized in the treatment of peripheral nerves as comparable to autologous grafting. The best therapeutic outcomes are obtained with conduits releasing therapeutic molecules. In this study, a new approach for the incorporation of biologically active agent-loaded microspheres into the structure of chitosan/polycaprolactone conduits was developed. The support of a polycaprolactone helix formed by 3D melt extrusion was coated with dopamine in order to adsorb nerve growth factor-loaded microspheres. The complex analysis of the influence of process factors on the coverage efficiency of polycaprolactone helix by nerve grow factor-loaded microspheres was analyzed. Thus, the PCL helix characterized with the highest adsorption of microspheres was subjected to nerve growth factor release studies, and finally incorporated into chitosan hydrogel deposit through the process of electrophoretic deposition. It was demonstrated by chemical and physical tests that the chitosan/polycaprolactone conduit meets the requirements imposed on peripheral nerve implants, particularly mimicking mechanical properties of surrounding soft tissue. Moreover, the conduit may support regrowing nerves for a prolonged period, as its structure and integrity persist upon incubation in lysozyme-contained PBS solution up to 28 days at body temperature. In vitro cytocompatibility toward mHippoE-18 embryonic hippocampal cells of the chitosan/polycaprolactone conduit was proven. Most importantly, the developed conduits stimulate axonal growth and support monocyte activation, the latter is advantageous especially at early stages of nerve regeneration. It was demonstrated that, through the described approach for controlling spatiotemporal release of nerve growth factors, these biocompatible structures adjusted to the specific peripheral nerve injury case can be manufactured.

Investigation of Parameters Influencing Tubular-Shaped Chitosan-Hydroxyapatite Layer Electrodeposition.

Tubular-shaped layer electrodeposition from chitosan-hydroxyapatite colloidal solutions has found application in the field of regeneration or replacement of cylindrical tissues and organs, especially peripheral nerve tissue regeneration. Nevertheless, the quantitative and qualitative characterisation of this phenomenon has not been described. In this work, the colloidal systems are subjected to the action of an electric current initiated at different voltages. Parameters of the electrodeposition process (i.e., total charge exchanged, gas volume, and deposit thickness) are monitored over time. Deposit structures are investigated by scanning electron microscopy (SEM) and Fourier-transform infrared spectroscopy (FTIR). The value of voltage influences structural characteristics but not thickness of deposit for the process lasting at least 20 min. The calculated number of exchanged electrons for studied conditions suggests that the mechanism of deposit formation is governed not only by water electrolysis but also interactions between formed hydroxide ions and calcium ions coordinated by chitosan chains.

Evaluation of the impact of tragacanth/xanthan gum interpolymer complexation with chitosan on pharmaceutical performance of gels with secnidazole as potential periodontal treatment.

Periodontitis consists a group of dental disorders that affect about 70 % of the world population. The therapy mainly relies on mechanical removing bacterial biofilm, nevertheless, local or systemic antibacterial agents play a key role in treating the acute conditions. Secnidazole is a newer derivative of commonly used metronidazole with high safety profile and broad spectrum of antimicrobial activity. The aim of the study was to evaluate the applicability of polyelectrolyte complex-based hydrogels composed of anionic tragacanth with addition of xanthan gum and cationic chitosan as carriers for buccal/intra pocket delivery of secnidazole. Prepared hydrogels with 5 % and 10 % (w/w) drug content were evaluated pharmaceutically towards inter alia physicomechanical, rheological and thermal properties, drug release kinetics, swelling behavior or antimicrobial activity. Cytotoxicity against human primary umbilical vein endothelial cells was also assessed with two independent method. Stable compositions with secnidazole were obtained, however, various miscibility of the drug with the polymers was noted. By adding chitosan, antibacterial activity and swelling performance of the gels were improved, nevertheless, drop of the mucoadhesiveness was also recorded. Hydrogels with 5 % secnidazole were selected as effective antimicrobial compositions with the highest cytocompatibility. They might be considered as promising for oromucosal application with special attention given to SEC as an alternative locally administered antimicrobial agent.

Carboxymethyl Chitosan Hydrogels for Effective Wound Healing-An Animal Study.

Hydrogels have various applications in medicine, for example, in systems for controlled drug release or as wound dressings, where they provide an appropriate environment for healing and constitute a barrier to microorganisms. The aim of this study was to evaluate the action of carboxymethyl chitosan (CMCS) hydrogels in wound healing therapy in vivo using a laboratory rat model. The hydrogels were formed from aqueous solutions of a CMCS biopolymer via electron beam irradiation, with the presence of a crosslinking agent of poly(ethylene glycol) diacrylate. A histopathological examination of injured tissue, using a model of a hard-to-heal wound, indicated that the CMCS hydrogel supported healing. The new gel dressing, being noncytotoxic, presents great potential in wound treatment, with positive effects on the amount of inflammatory infiltration, young collagen formation, and the degree of epidermalization. A key advantage of the current approach (i.e., using competitive radiation technology for synthesis) is that it includes only one step, with the product being sterilized as it is synthesized. The hydrogel effectively supports wound healing and can serve as a bio-based and biodegradable platform for other medical applications.

Impact of Salt on Thermal Stability and Dose Response of the Fricke-XO-Pluronic F-127 3D Radiotherapy Dosimeter.

Fricke-XO-Pluronic F-127 has recently been proposed as a 3D dosimeter for radiotherapy. It contains the typical ingredients of the Fricke ionizing radiation dosimeter, which are embedded in a physical gel of poly(ethylene oxide)-block-poly(propylene oxide)-block-poly(ethylene oxide) (Pluronic F-127). The main reactions upon irradiation are the conversion of Fe+2 to Fe+3 and the formation of a colored complex with XO ([XO-Fe]+3). The study attempts to optimize the dosimeter in terms of its solution-to-gel transition temperature. In order to lower this temperature, the use of NaCl salt has been proposed. The new composition was characterized in order to obtain information on its thermal performance, storage stability, dose response to irradiation with a medical accelerator emitting different types of radiation, and tissue equivalence. The results obtained show an improvement in the sol-gel transition temperature and dose sensitivity compared to the composition without NaCl and broaden the knowledge of the Fricke-XO-Pluronic F-127.

Biocompatibility and Mechanical Properties of Carboxymethyl Chitosan Hydrogels.

Hydrogels have the properties of solid substances and are useful for medicine, e.g., in systems for the controlled release of drugs or as wound dressings. They isolate the wound from the external environment and constitute a barrier to microorganisms while still being permeable to oxygen. In the current study, hydrogels were formed from concentrated aqueous solutions of carboxymethyl chitosan (CMCS) via electron beam irradiation, with the presence of a crosslinking agent: poly(ethylene glycol)diacrylate. The aim of the study was to compare the properties and action of biopolymer CMCS hydrogels with commercial ones and to select the best compositions for future research towards wound-dressing applications. The elasticity of the gel depended on the component concentrations and the irradiation dose employed to form the hydrogel. Young's modulus for the tested hydrogels was higher than for the control material. The Live/Dead test performed on human fibroblasts confirmed that the analyzed hydrogels are not cytotoxic, and for some concentrations, they cause a slight increase in the number of cells compared to the control. The biocompatibility studies carried out on laboratory rats showed no adverse effect of hydrogels on animal tissues, confirming their biocompatibility and suggesting that CMCS hydrogels could be considered as wound-healing dressings in the future. Ionizing radiation was proven to be a suitable tool for CMCS hydrogel synthesis and could be of use in wound-healing therapy, as it may simultaneously sterilize the product.

Influence of chitosan average molecular weight on degradation and stability of electrodeposited conduits.

Tubular chitosan-based hydrogels, obtained in an electrodeposition process, are subject of degradation and stability studies. The implants are prepared from polymer with different average molecular weight. This approach allows fabricating structures that vary in mass and wall thickness. The obtained implants are incubated in phosphate buffered solution (pH 7.4) with or without lysozyme up to 56 days at 37 °C. Subsequently, chemical, physical as well as mechanical properties of implants are evaluated. Although the initial physicomechanical properties are different, they change upon incubation and remain similar over its period. Finally, in vitro biocompatibility of implants is proven after assessing their action towards mHippoE-18 embryonic hippocampal cells and THP1-XBlue™ monocytes. Since dimensions of nerves and the gap length differ across the body and injury, respectively, the possibility to control properties of chitosan applied gives a tool to prepare implants with wall thickness adjusted to the specific peripheral nerve injury case.

Examination of THPC as an oxygen scavenger impacting VIC dosimeter thermal stability and comparison of NVP-containing polymer gel dosimeters.

This work reports on the impact of tetrakis(hydroxymethyl)phosphonium chloride (THPC) on the properties of a VIC gel dosimeter (VIC is an abbreviated acronym of VIPARCT). THPC was used as a substitute oxygen scavenger in VIC (17% N-vinylpyrrolidone, 8% N,N'-methylenebisacrylamide, 12% tert-butyl alcohol, 7.5% gelatine, 0.02% hydroquinone and an oxygen scavenger of 0.007% ascorbic acid and 0.0008% CuSO4 × 5H2O). THPC reduced the gelation time of VIC from hours to minutes. The best composition (VIC-T) contained 14 mM THPC and a reduced gelatine concentration (5%) with respect to VIC, which allowed for gelation in about 3 min. VIC-T was characterised by the same dose sensitivity (0.176 ± 0.003 Gy-1 s-1 for VIC-T and 0.171 ± 0.002 Gy-1 s-1 for VIC), dose threshold (0.5 Gy) and dynamic dose range (0.5‒50 Gy) as VIC, and a lower linear dose range (20 Gy for VIC-T, 30 Gy for VIC) (0.47 T NMR measurements). VIC-T was stable for at least 10 days after irradiation, and 3D dose distribution was stable for over 4 months after irradiation. The dose response of VIC-T was independent of the radiation dose rate, type and energy of radiation for 6 and 15 MV photons and 12 MeV electrons. This is an improvement with respect to VIC which showed a different dose response for 6 MV photons than for 12 MeV electrons and 15 MV photons. Raman spectroscopy showed similarity in the rate of radiation-induced conversion of monomers in VIC and VIC-T, indicating interaction of THPC with gelatine in VIC-T, and showed ageing of gelatine in both dosimeters. Differential scanning calorimetry showed VIC-T stability at 0 °C-80 °C (VIC: 0 °C‒29.5 °C). The chemical polymerisation and crosslinking of gelatine with THPC is reported, the mechanism of which was analysed in detail. A comparison of N-vinylpyrrolidone-containing dosimeters is presented in this work.

Leuco crystal violet-Pluronic F-127 3D radiochromic gel dosimeter.

This work reports results related to the manufacturing and optimisation of a leuco crystal violet (LCV)-Pluronic F-127 radiochromic gel dosimeter suitable for 3D radiotherapy dosimetry. A feature of this gel is that the natural gelatine polymer, which is most often used as a matrix in 3D dosimeters, is substituted with Pluronic F-127 synthetic copolymer (poly(ethylene oxide)-block-poly(propylene oxide)-block-poly(ethylene oxide). Pluronic F-127 ensures a higher transparency than gelatine, which may be beneficial for optical computed tomography readout, and improves the thermal properties in the temperature range above ~30 °C at which the gelatine physical gel converts to a solution. The optimal composition obtained comprises 2 mM LCV, 4 mM 4-(1,1,3,3-tetramethylbutyl)phenyl-polyethylene glycol (Triton X-100), 17 mM trichloroacetic acid (TCAA) and 25% Pluronic F-127. Its main dose-response features are 4‒150 Gy linear dose range (150 Gy was the maximal dose applied to gels in this work), 0.0070 Gy-1 cm-1 dose sensitivity (derived from absorbance (600 nm) = f (dose) for 6 MeV electrons, 0.88(3) Gy s-1 and 0.0156 Gy-1 cm-1 derived from optical density (Δµ) = f (dose) for 6 MV x-rays, 0.1010 Gy s-1), low initial colour (initial absorbance = 0.0429) and a diffusion coefficient of crystal violet (CV) in LCV-Pluronic of 0.054 ± 0.023 mm2 h-1. Raman spectroscopy was used to characterize LCV-Pluronic chemical changes after irradiation. Differential scanning calorimetry (DSC) revealed that LCV-Pluronic is stable in temperatures between approximately 11 °C and 56 °C. Irradiation of LCV-Pluronic gel impacts on its first sol-gel transition temperature and the thermal effect of this process-both increased with absorbed dose, which might be related to the degradation of Pluronic. LCV-Pluronic is a promising 3D dosimeter for ionising radiation applications. Further work is needed to improve LCV-Pluronic response in the low dose region, and characterize potential effects of pH, temperature during irradiation, and radiation quality/dose rate on dose response characteristics.

Substituting gelatine with Pluronic F-127 matrix in 3D polymer gel dosimeters can improve nuclear magnetic resonance, thermal and optical properties.

This work discusses the substitution of a gelatine physical gel matrix with a matrix made of poly(ethylene oxide)-block-poly(propylene oxide)-block-poly(ethylene oxide) (Pluronic F-127) in five 3D radiotherapy polymer gel dosimeters: MAGAT, PAGAT, NIPAM, VIPARnd (VIP) and VIPARCT (VIC). The current research outcomes showed that not each polymer gel dosimeter could be manufactured with Pluronic F-127. Two of the polymer gel dosimeters (PAGAT and VIP) containing the Pluronic F-127 matrix allowed for some proper dose response for radiotherapy dosimetry (a response to a dose range of e.g. 0‒50 Gy). The new best performing Pluronic-based polymer gel dosimeters were characterised by improved nuclear magnetic resonance properties, when being compared to gels with gelatine matrix at the same monomer content. These are: (i) a ~33% higher dose sensitivity; (ii) a comparable or slightly higher linear and dynamic dose range and (iii) a lower (new VIP composition, VIP3) or equivocal (new PAGAT composition, PAGAT2-Pluronic) dose threshold. However, there might be optimised gelatine based polymer dosimeters demonstrating even better sensitivity. UV-vis spectrophotometry measurements revealed that Pluronic matrices ensure six-times lower (VIP3-Pluronic) and eight-times lower (PAGAT2-Pluronic) absorbance (at 400 nm) of non-irradiated gels compared to gelatine matrices, which makes the new polymer gel dosimeters optically improved in comparison to their corresponding gelatine-based compositions. The differences in absorption reduce for higher wavelengths. Differential scanning calorimetry measurements revealed the following temperature stability ranges for the gels: (i) VIP with gelatine matrix: 0 °C‒26 °C, (ii) VIP3 with Pluronic matrix: 13.8 °C-55.2 °C, (iii) PAGAT2 with gelatine matrix: 0 °C-80 °C and (iv) PAGAT2 with Pluronic matrix: 21.4 °C-55.2 °C. In conclusion, Pluronic F-127 is an attractive co-polymer to serve as a substitute for the gelatine matrix in some 3D polymer gel dosimeters.

On the Mechanisms of the Effects of Ionizing Radiation on Diblock and Random Copolymers of Poly(Lactic Acid) and Poly(Trimethylene Carbonate).

This article demonstrates that ionizing radiation induces simultaneous crosslinking and scission in poly(trimethylene carbonate-co-d-lactide) diblock and random copolymers. Copolymer films were electron-beam (EB) irradiated up to 300 kGy under anaerobic conditions and subsequently examined by evaluation of their structure (FT-IR, NMR), molecular weight, intrinsic viscosities, and thermal properties. Radiation chemistry of the copolymers is strongly influenced by the content of ester linkages of the lactide component. At low lactide content, crosslinking reaction is the dominant one; however, as the lactide ratio increases, the ester linkages scission becomes more competent and exceeds the crosslinking. Electron paramagnetic resonance (EPR) measurements indicate that higher content of amorphous carbonate units in copolymers leads to a reduction in free radical yield and faster radical decay as compared to lactide-rich compositions. The domination of scission of ester bonds was confirmed by identifying the radiolytically produced alkoxyl and acetyl radicals, the latter being more stable due to its conjugated structure.

Experimental reconstruction of an abdominal wall defect with electrospun polycaprolactone-ureidopyrimidinone mesh conserves compliance yet may have insufficient strength.

PURPOSE: Electrospun meshes mimic the extracellular matrix, which may improve their integration. We aimed to compare polycaprolactone (PCL) modified with ureidopyrimidinone (UPy) electrospun meshes with ultra-lightweight polypropylene (PP; Restorelle) reference textile meshes for in vivo compliance. We chose UPy-PCL because we have shown it does not compromise biomechanical properties of native tissue, and because it potentially can be bioactivated. METHODS: We performed ex vivo biomechanical cyclic loading in wet conditions and in vivo overlay of full-thickness abdominal wall defects in rats and rabbits. Animals were sacrificed at 7, 42 and 54 days (rats; n = 6/group) and 30 and 90 days (rabbits; n = 3/group). Outcomes were herniation, mesh degradation and mesh dimensions, explant compliance and histology. High failure rates prompted us to provide additional material strength by increasing fiber diameter and mesh thickness, which was further tested in rabbits as a biomechanically more challenging model. RESULTS: Compliance was tested in animals without herniation. In both species, UPy-PCL-explants were as compliant as native tissue. In rats, PP-explants were stiffer. Contraction was similar in UPy-PCL and PP-explants. However, UPy-PCL-meshes macroscopically degraded from 30 days onwards, coinciding with herniation in up to half of animals. Increased fiber and mesh thickness did not improve outcome. Degradation of UPy-PCL is associated with an abundance of foreign body giant cells until UPy-PCL disappears. CONCLUSION: Abdominal wall reconstruction with electrospun UPy-PCL meshes failed in 50%. Degradation coincided with a transient vigorous foreign body reaction. Non-failing UPy-PCL-explants were as compliant as native tissue. Despite that, the high failure rate forces us to explore electrospun meshes based on other polymers.

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.

In vivo evaluation of nerve guidance channels of PTMC/PLLA porous biomaterial.

INTRODUCTION: Peripheral nerve disruptions, frequently occurring during limb injuries, give rise to serious complications of patients recovery resulting from limitations in neural tissue regeneration capabilities. To overcome this problem bridging techniques utilizing guidance channels gain their importance. Biodegradable polymeric tubes seem to be more prospective then non-degradable materials - no necessity of implant removal and possibilities of release of incorporated drugs or biologically active agents that may support nerve regeneration process are the main advantages. MATERIAL AND METHODS: Polymer blend of commercial poly(L-lactic acid) (PLLA) and in-house synthesized poly(trimethylene carbonate) (PTMC) were processed in an organic solvent - phase inversion process on a supporting rod - to form a guidance porous tube of 1.1 mm inner diameter. In vivo experiments on rat's cut femoral nerve by using either the tubes or end-to-end suturing (control group) involved 22 and 19 rats, respectively. Motor recovery of operated limbs, neuroma occurrence and histopathology of explanted nerves were evaluated after 30, 60 and 90 days of implantation. RESULTS: Motor recovery of the limbs was of similar rate for the two animal groups. The neuroma formation was evident in over 90% control specimens, while for the bridging group it was less than 40% of all evaluable samples (p = 0.0022). Biocompatibility of applied materials was affirmed by moderate tissue response. CONCLUSIONS: Application of the biodegradable PLLA/PTMC polymeric tubes effectively supports regeneration of discontinued nerves. The applied material prevents neuroma formation, by reducing the scar tissue formation time and, thus, accelerating the process of neural tissue restoration.

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.

Laser photolysis of carboxymethylated chitin derivatives in aqueous solution. Part 2. Reaction of OH* and SO4*- radicals with carboxymethylated chitin derivatives.

The reactions of OH* or SO4*- radicals with carboxymethyl chitin (CM-chitin) and its deacetylated product, carboxymethyl chitosan (CM-chitosan), were investigated in aqueous solutions using a laser photolysis technique. The rate constants of the reactions of OH* and SO4*- radicals with CM-chitosan are always higher than those for CM-chitin, indicating that the amino-group could increase the reactivity of carboxymethylated chitin derivatives. The rate of the reactions of CM-chitin and CM-chitosan with OH* radical was found to decrease at lower pH when polymers chains tend to the coiled conformation. In comparison, the rate constant of the reaction of SO4*- radicals with CM-chitin or CM-chitosan decreased with pH, indicating that CM-chitin or CM-chitosan has a higher reactivity with the SO4*- radical at low pH due to the protonation of the amino group.

Laser photolysis of carboxymethylated chitin derivatives in aqueous solution. Part 1. Formation of hydrated electron and a long-lived radical.

Laser photolysis experiments on carboxymethylated chitin derivatives, such as carboxymethyl chitin (CM-chitin) and carboxymethyl chitosan (CM-chitosan), in aqueous solution by a 248 nm excimer laser were carried out for the first time. The transient absorption spectra of photolyzed CM-chitin or CM-chitosan solutions revealed a strong band with the maximum at 720 nm, which was assigned to the hydrated electron (eaq-). In the presence of argon, the eaq- decays by reacting with CM-chitin or CM-chitosan, and the rate constants are (6.1 +/- 0.1) x 10(7) M(-1) s(-1) and (3.7 +/- 0.1) x 10(7) M(-1) s(-1), respectively. Long-lived radicals with relatively weak absorption intensity were detected in the near-UV region. The absorption band was not notably characteristic and showed only an increasing absorption toward shorter wavelengths. It is similar to the signal of *CM-chitin or *CM-chitosan macroradicals formed by the reaction of CM-chitin or CM-chitosan with an OH* radical. It was assigned to *CM-chitin- or *CM-chitosan- macroradicals formed by eaq- + CM-chitin or CM-chitosan reaction. CM-chitin aqueous solutions were further examined by pulse radiolysis in order to confirm the site of the long-lived radical.