壳聚糖在水溶液中的辐射降解反应

研究了壳聚糖在CH3COOH/NaCl缓冲溶液均相体系下的辐射降解反应,给出了H2O2、异丙醇、pH、样品初始分子量等因素对壳聚糖降解的影响,探讨了实验条件下溶液中不同自由基对壳聚糖降解的作用,并对辐照前后壳聚糖的结构进行了表征.结果表明,酸性条件下,壳聚糖的降解主要由.H和.OH自由基共同作用引起,加入H2O2或者通入N2O都能够略微提高.OH自由基浓度,对壳聚糖的降解有促进作用.加入异丙醇后,由于同时降低了.H和.OH自由基浓度,导致壳聚糖降解缓慢.当溶液的pH接近中性后,对壳聚糖的降解起主要作用的为.OH自由基,加入H2O2或者通入N2O都会增加.OH自由基的浓度,从而明显提高壳聚糖的降解速率.此外,研究发现低分子量的壳聚糖具有较快的降解速率.样品的UV、FTIR分析表明,辐照后除在壳聚糖分子链端生成羰基外,壳聚糖主链结构未见变化,脱乙酰度也没有显著改变,显示出辐射降解是一种有效的控制壳聚糖分子量方法.     

Effect of gamma radiation on dilute aqueous solutions and thin films of N-succinyl chitosan

N-Succinyl chitosan (N-SC) products with various degrees of substitution were synthesized by a direct reaction between chitosan and succinic anhydride. The susceptibility of the as-synthesized polymers to degradation upon their exposure to γ-ray radiation was investigated. The results were compared with the as-received chitosan. The size exclusion chromatographic results showed that chitosan and N-SC products in their dilute aqueous solution state were more subservient to degradation by γ-ray radiation than in their solid film state, despite the much less exposure to the radiation (i.e., 5-30 kGy for the solutions versus 20-100 kGy for the films). Increasing the radiation dose resulted in the rather monotonous decrease in the molecular weights of the polymers. Structural analyses of the irradiated polymers by Fourier-transformed infrared spectroscopy (FT-IR) and UV-visible spectrophotometry indicated the increase in the amount of carbonyl groups with the radiation dose. The formation of the carbonyl groups suggested that the radiolysis of chitosan and N-SC products occurred at the glycosidic linkages. In addition, FT-IR, elemental analysis and proton nuclear magnetic resonance spectroscopy (¹H NMR) results suggested that γ-ray radiation affected both the N-acetyl and N-substituted groups on the polymer chains.     

Synergetic degradation of chitosan with gamma radiation and hydrogen peroxide

Chitosan samples were irradiated by ⁶⁰Co γ-rays in the presence of hydrogen peroxide with radiation dose from 10 kGy to 100 kGy. The degradation was monitored by gel permeation chromatography (GPC), revealing the existence of a synergetic effect on the degradation. Structures of the degraded products were characterized with Fourier-transform infrared spectra (FT-IR), ultraviolet-visible spectral (UV-vis) analysis, and X-ray diffraction (XRD). Results showed that the crystallinity of chitosan decreases with degradation, and the crystalline state of water-soluble chitosan is entirely different from that of water-insoluble chitosan. An elemental analysis method was employed to investigate changes in the element content of chitosan after degradation. Mechanism of chitosan radiation degradation with and without hydrogen peroxide was also discussed.     

·OH对聚二甲基硅氧烷乳液辐射效应的影响

通过凝胶和溶胶分析与分子量测定的方法,研究了不同体系下,"OH对PDMS乳液γ辐射效应的影响.结果表明,"OH不仅可引发聚二甲基硅氧烷的分子间交联,也能促进其降解.对于纯PDMS乳液,在所研究的剂量范围内,"OH对其辐射交联行为影响较小.但若体系中加入H2O2、KIO4和N2O这些提高"OH生成产额的添加剂时,"OH对PDMS的促降解作用会随着吸收剂量增加而表现更明显,导致凝胶含量与纯乳液辐照情况相比下降较多.即使加入交联剂-三羟甲基丙烷三甲基丙烯酸酯(TMPTMA),在过量的"OH存在下,当吸收剂量大于40kGy以上时,TMPTMA不仅没有提高交联度,反而会与"OH协同,使PDMS的凝胶含量下降更显著,同时产生更多的小分子聚合物,并使PDMS的平均分子量分布变窄.这可能是由于交联剂首先与"OH作用,形成的产物会加快PDMS的降解.     

•OH对聚二甲基硅氧烷乳液辐射效应的影响

通过凝胶和溶胶分析与分子量测定的方法，研究了不同体系下，^•OH对PDMS乳液γ辐射效应的影响. 结果表明，^•OH不仅可引发聚二甲基硅氧烷的分子间交联，也能促进其降解. 对于纯PDMS乳液，在所研究的剂量范围内，^•OH对其辐射交联行为影响较小. 但若体系中加入H2O2、KIO4 和 N2O这些提高^•OH生成产额的添加剂时，^•OH对PDMS的促降解作用会随着吸收剂量增加而表现更明显，导致凝胶含量与纯乳液辐照情况相比下降较多. 即使加入交联剂-三羟甲基丙烷三甲基丙烯酸酯（TMPTMA），在过量的^•OH存在下，当吸收剂量大于40 kGy以上时，TMPTMA不仅没有提高交联度，反而会与^•OH协同，使PDMS的凝胶含量下降更显著，同时产生更多的小分子聚合物，并使PDMS的平均分子量分布变窄. 这可能是由于交联剂首先与^•OH作用，形成的产物会加快PDMS的降解.     

Effect of γ-irradiation on cotton-cellulose

The effect of high-energy irradiation on cotton-cellulose was studied in inert atmosphere and in the presence of oxygen. A decrease in the degree of polymerization from 1200 to 330 was measured after irradiation with a dose of 15 kGy (dose rate 100 Gy/h) and further gradual decrease was measured when the dose was increased up to 100 kGy. At lower doses a slight increase in crease recovery angle was found as compared to the unirradiated sample. In the FTIR spectra of the same sample the appearance of the absorbance of carbonyl groups (band at 1730–1750 cm⁻¹) was found as a consequence of the oxidative degradation. Cracks on the surface of the fibers were observed by scanning electron microscope on samples irradiated with doses higher than 100 kGy.     

等规聚丙烯在γ射线辐照下的链结构和结晶行为

利用凝胶渗透色谱(GPC)、傅里叶变换红外光谱(FTIR)和示差扫描量热(DSC)等手段对不同剂量γ射线辐照后等规聚丙烯(iPP)的分子链结构及结晶行为的变化进行了研究.结果表明,γ射线辐照使iPP的分子量下降,并在其分子链中产生羟基和羰基等极性基团,从而影响其结晶行为.在非等温结晶过程中,当辐照剂量≤50 kGy时,iPP的热结晶温度略有升高;增大辐照剂量,iPP的热结晶温度明显降低.iPP的熔融温度则随辐照剂量的增大而降低,且分裂成双峰.利用Avrami方程研究了辐照前后iPP的等温结晶动力学,发现辐照前后样品的Avrami指数n都在3左右,表明iPP的结晶遵循异相成核机理,且不受辐照剂量和等温结晶温度的影响,但总结晶速率随等温结晶温度和辐照剂量的升高而逐渐减小.探讨了iPP经过γ射线辐照后,分子链断裂、链结构变化和结晶速率之间的关系.     

Antimicrobial properties of natural substances in irradiated fresh poultry

This study was undertaken to determine if a combined treatment (marinating in natural plant extracts or vacuum) with irradiation could have a synergetic effect, in order to reduce the dose required for complete elimination of Salmonella on fresh poultry. The effect of these combined treatments on the shelf-life extension was also evaluated. The fresh chicken legs were irradiated at 0, 3 and 5 kGy. The poultry underwent microbial analysis(mesophilic and Salmonella detection). For each treatment, the total microbial count decreased with increase of irradiation dose. The marinating treatment have a synergistic effect with irradiation treatment to reduce the total microbial count and controlling the proliferation during storage at 4°C. Irradiation of fresh chicken pieces with a dose of 3 kGy appears to be able to extend the microbial shelf-life by a factor of 2. When the chicken is marinating and irradiated at 3 kGy or when irradiated at 5 kGy without marinating, the microbial shelf-life is extended by a factor of 7 to 8. No Salmonella was found during all the experiment in the chicken in air and marinated. However, a presence of Salmonella was found in samples irradiated at 5 kGy under vacuum, in unirradiated samples and samples irradiated at 3kGy in air and under vacuum.     

水溶性低分子壳聚糖的制备

Oxidative degradation of chitosan by H2O2-NaClO mixed oxidant is studied in acidic condition.The effects of concentration of H2O2,reactive temperature and reaction time on oxidative degradation reaction are studied.The results show that the method of oxidative degradation of chitosan with H2O2-NaClO mixed oxidant is effective for preparation of water-soluble chitooligosaccharides.     

Radiation sterilization of chitosan sealant for vascular prostheses

Chitosan was used as a sealant of knitted polyester vascular grafts. Three sterilization methods for chitosan-coated prostheses were tested: sterilization with ethylene oxide, formaldehyde and irradiation with gamma rays. Radiation sterilization was found to be the most promising of tested methods. The radiation-induced changes in chitosan irradiated in solid state were investigated. Main chain scission was found as the predominant effect of irradiation. Changes in IR and UV spectra were analyzed. Existence of some post-effects was detected. It seems that the observed increase in biocompatibility of chitosan surface caused by irradiation with sterilizing dose (25 kGy) is due to some structural factor connected with a decrease in molecular weight.     

Molecular-topological and thermal properties of gamma-irradiated alternating carbon monoxide-ethylene copolymer

Gamma-irradiation to a dose of up to 2000 kGy does not lead to substantial changes in the topological structure of a carbon monoxide copolymer with ethylene, thereby suggesting it high radiation resistance. The topological structure of unirradiated and irradiated copolymer samples is polyblock in nature having four crystalline phases as the branching “junctions” in the pseudo-network structure of its amorphous block. Copolymer molecular flow begins after completion of melting of its high-melting fraction and at an onset flow temperature of 484 ± 4 K regardless of the absorbed radiation dose. The irradiated and unirradiated copolymer releases the same gaseous products upon heating, and the irradiation itself does not affect the onset temperature of effective gas evolution.     

Thermoluminescence of contaminating minerals for the detection of radiation treatment of dried fruits

Several types of dry fruits (pistachio nut, dried apricot, almond and raisins) have been investigated for detection of their radiation treatment by gamma rays or electron beam using thermoluminescence (TL) measurements. These samples were irradiated to 1.0–3.0 kGy (gamma rays) or 0.75–3.9 kGy (10 MeV electron beam). Thermoluminescence glow curves for the contaminating minerals separated from the dry fruits were recorded between the temperature range of 50°C and 500°C. In all the cases, the intensity of TL signal for the irradiated dry fruits was 1–3 orders of magnitudes higher than the TL intensity of the corresponding unirradiated control samples allowing clear distinction between the irradiated and unirradiated samples. These results were normalized by re-irradiating the mineral grains with a gamma-ray dose of 1.0 kGy, and a second glow curve was recorded. The ratio of intensity of the first glow curve (TL₁) to that after the normalization dose (TL₂), i.e. (TL₁/TL₂) was determined and compared with the recommended threshold values. These parameters, together with comparison of the shape of the first glow curve, gave unequivocal results about the radiation treatment of the dry fruit samples.     

Polymerization of calcium caseinates solutions induced by gamma irradiation

Solutions of calcium caseinate (5%) combined with propylene glycol (PG) or triethylene glycol(TEG) (0, 2.5% and 5%) and used for the development of edible films and coatings, were irradiated at doses between 0 to 128 kGy. Solutions were chromatographed through toyopearl HW 55F resin to observe the effect of irradiation on cross-link reactions. In unirradiated calcium caseinate solutions, two peaks could be observed (fractions 30 and 37) while samples irradiated at 64 kGy and 128 kGy showed one shifted peak at fraction 32 and 29 respectively. No effect of the plasticizers was observed. According to proteins standards of knowed molecular weights, the molecular weight of calcium caseinate increased approximately 10 times when irradiated at 128 kGy and 5 times when irradiated at 64 kGy. The physico-chemical properties of bio-films prepared with the irradiated solutions, demonstrated that tensile strength at break increased with increase of irradiation dose. A maximum dose was obtained at 16 kGy.     

Physicochemical and functional characteristics of radiation-processed shrimp chitosan

The effects of gamma irradiation on chitosan samples were determined in terms of physicochemical and functional properties. Shrimp chitosan was extracted from shell using a chemical process involving demineralization, deproteinization, decolorization and deacetylation. Commercial snow chitosan was also used. Samples (in a solid state) were given irradiation dose of 25 kGy at a dose rate of 1.1013 kGy/h in air and 0 kGy samples were used as controls. Results showed that moisture contents were between 8.690% and 13.645%. There were no significant differences (P>0.05) in the degree of deacetylation of the chitosan samples. Significant differences (P<0.05) were observed in the viscosity and viscosity-average molecular weight of the chistosan samples. Viscosity and molecular weight decreased when the samples were given the irradiation dose of 25 kGy. Chitosan samples had low antioxidant activity compared with BHT. Water binding capacity ranged from 582.40% to 656.75% and fat binding capacity was between 431.00% and 560.55%. Irradiation had a major effect on the viscosity and the viscosity-average molecular weight of the chitosan samples.     

LOW MOLECULAR WEIGHT O-CARBOXYMETHYLATED CHITOSANS DERIVED FROM IRRADIATED CHITOSAN AND THEIR ANTIBACTERIAL ACTIVITY

INTRODUCTIONChitin is the second most naturally abundant biopolymer and is found in a variety of organisms, including fungalcell walls, the exoskeleton of crustaceans, skeletal tissue of mollusks and the integument of insects.When treated with alkali, chitin can be deactylated and turned into chitosan, which is a linear binaryheteropolysaccharide composed of (1-4) linked 2-acetamido-2-deoxy-β-D-glucopyranose and 2-amino-2-deoxy-β-D-glucopyranose residues. Chitosan has a wide variety of …     

Effect of gamma irradiation on linear low density polyethylene/magnesium hydroxide/sepiolite composite

Radiation crosslinking is generally used to improve the thermo-mechanical properties of the composites. A study has been carried out to investigate the effect of gamma radiation on the thermo-mechanical properties of linear low density polyethylene containing magnesium hydroxide (MH) and sepiolite (SP) as non-halogenated flame retardant additives. The developed composites are irradiated at different doses upto maximum of 150 kGy. Infrared spectra of the irradiated composites reveal the reduction in the intensity of O-H band with increase in the absorbed doses, thus indicates a distinct structural change in MH at higher doses. The thermogravimetric analysis results of unirradiated and composites irradiated at low doses (≤75 kGy) show two steps weight loss, which is changed to single step at higher doses with lower thermal stability. The melting temperature (T_m) and crystallization temperature (T_c) of irradiated composites are lowered with irradiation whereas Vicat softening temperature (VST) is increased. The increasing trend in gel content with increase in the absorbed dose confirms the presence of crosslinked network. The mechanical properties, results show significant improvement in the modulus of irradiated composites. The results also confirm that MH gradually loses its OH functionality with irradiation.     

K-型卡拉胶/聚乙烯吡咯烷酮共混水凝胶的辐射合成

采用辐射技术合成了K 型卡拉胶 (KC) /聚乙烯吡咯烷酮 (PVP)共混水凝胶 ,研究了天然高分子KC、单体N 乙烯基吡咯烷酮 (N VP)、交联剂二甲基丙烯酸十四甘醇酯 ( 1 4G) ,辐照剂量以及剂量率等对辐射合成的KC/PVP共混水凝胶性质的影响 .实验发现 ,KC与适当比例的N VP共混后在一定剂量范围内辐照可得到高强度、高溶胀行为的KC/PVP共混水凝胶 ,随着共混凝胶内KC含量的相对增加 ,凝胶强度及溶胀性的能均显著提高 ,但合成该共混凝胶的最佳剂量却相对提前 ;加入 1 4G后降低了KC/PVP共混凝胶辐射合成最佳剂量 ,同时使KC/PVP共混凝胶的强度进一步提高 ;剂量、剂量率对KC/PVP共混凝胶的性质亦有很大的影响 .分析表明 ,KC与N VP共混后 ,在较低剂量下KC的降解被抑制 ,从而获得一种由物理交联的KC和化学交联的PVP形成的互穿网络 (IPN)凝胶     

Identification of irradiated pulses by thermoluminescence of the contaminating minerals

Thermoluminescence (TL) response of contaminating minerals from six samples of pulses commonly consumed in Pakistan has been studied for identification of irradiation treatment. The samples were irradiated by Co-60 gamma rays at 0.3, 0.5 and 1.0 kGy, or by 10 MeV electrons using an accelerator at 0.75 and 2.2. kGy. Generally, the TL intensity for minerals separated from irradiated samples was higher than for unirradiated samples. To normalize the results, separated minerals deposited on stainless steel discs were re-irradiated by a normalizing dose and TL response was redetermined. The ratio of the area of the first glow curve to the second glow curve was more than 0.8 for all irradiated samples and less than 0.33 for most of the unirradiated samples. For those unirradiated samples where the ratio of the glow curves was more then 0.03, the shapes of the glow curves were compared. Taking this criterion into consideration, all 21 unirradiated and irradiated samples of pulses were identified correctly. Therefore, a normalization procedure by re-irradiation of minerals and analysis of TL glow curve shapes lead to unequivocal identification of radiation treatment of pulses.     

Radiation effect studies on anticancer drugs, cyclophosphamide and doxorubicin for radiation sterilization

Two anticancer drugs, cyclophosphamide (CPH) and doxorubicin hydrochloride (DOXO), in powder form were exposed to a range of doses of ⁶⁰Co gamma and electron beam radiation to study the effects of ionizing radiation. Pharmacopoeia tests, discolouration, degradation products, effect of irradiation temperature and dose rate were investigated. CPH undergoes less than 2% degradation at 30 kGy. Chromatographic studies revealed formation of several trace level degradation products, discolouration and free radicals in the irradiated CPH. N,N-bis (2-chloroethyl) group in the molecule is particularly sensitive to radiation degradation. Irradiation to 5 kGy at low temperature (77 K) did not result in significant changes. DOXO was observed to be quite radiation resistant and did not undergo significant changes in its physico-chemical properties and degradation product profile. It can be radiation sterilized at normal sterilization dose of 25 kGy.     

Degradation behavior of poly (l-lactide-co-glycolide) films through gamma-ray irradiation

Gamma-ray irradiation is a very useful tool to improve the physicochemical properties of various biodegradable polymers without the use of a heating and crosslinking agent. The purpose of this study was to investigate the degradation behavior of poly (l-lactide-co-glycolide) (PLGA) depending on the applied gamma-ray irradiation doses. PLGA films prepared through a solvent casting method were irradiated with gamma radiation at various irradiation doses. The irradiation was performed using 60Co gamma-ray doses of 25–500 kGy at a dose rate of 10 kGy/h.The degradation of irradiated films was observed through the main chain scission. Exposure to gamma radiation dropped the average molecular weight (M_n and M_w), and weakened the mechanical strength. Thermograms of irradiated film show various changes of thermal properties in accordance with gamma-ray irradiation doses. Gamma-ray irradiation changes the morphology of the surface, and improves the wettability. In conclusion, gamma-ray irradiation will be a useful tool to control the rate of hydrolytic degradation of these PLGA films.