层状水凝胶仿生软骨的制备与性能

采用超声分散、高压加热共融、冷冻-熔融和γ射线辐照交联成型工艺制备层状水凝胶仿生软骨材料, 系统讨论了PVP添加量和辐照剂量对材料的凝胶含量、晶态结构及抗压缩弹性模量的影响, 观察和研究了层状水凝胶的微观结构. 研究结果表明, 随着PVP的质量分数(0-40%)和辐照剂量(0-60 kGy)的增加, 层状水凝胶的凝胶含量呈上升趋势; 其晶态结构在质量分数为20%的PVP和10 kGy辐照剂量下最完善; 其力学性能在质量分数为20%的PVP和20 kGy辐照剂量下最佳; PVP的加入改善了水凝胶的微观形貌, 有利于材料表面润滑性能的提高; 层状水凝胶层间渗透结合, 自然过渡, 形成结构良好的仿生软骨材料.     

辐射接枝共聚合反应及其在有机生物医用材料制备中的应用

γ-射线辐射高分子材料表面接枝共聚合是一种绿色的、重要的有机生物材料合成制备方法. 综述了γ-射线辐射接枝共聚反应的原理、特点, 阐述了预辐射接枝共聚和共辐射接枝共聚的方法, 介绍了当前γ-射线辐射接枝共聚反应在改善有机生物医用材料的表面亲水性、生物相容性等方面的应用. 对辐射接枝共聚合制备功能药物载体研究进行了简要介绍.     

辐照交联法制备锂离子电池用凝胶聚合物电解质及其性能

采用γ-射线辐照交联法制备了具有网络结构的聚偏氟乙烯-六氟丙烯/新戊二醇二丙烯酸酯(PVDF-HFP/NPGDA)基凝胶聚合物电解质(GPE). 考察了不同辐照剂量对凝胶电解质形貌结构、热稳定性和电化学性能的影响以及不同辐照剂量和不同温度下电导率的变化. 结果表明, 随辐照剂量的增加, 凝胶电解质的固化程度提高, 电导率下降. 电导率随温度的变化符合VTF方程. 当辐照剂量为5 kGy 时, 制备的凝胶电解质具有较高的离子电导率和电化学稳定窗口, 室温下分别为7.8×10-3 S·cm-1和4.7 V(vs Li/Li+). 以其为电解质制备的LiMn2O4∣GPE∣Li聚合物锂离子电池具有较好的循环性能.     

多壁碳纳米管-环氧树脂纳米复合材料的γ-射线固化行为

通过γ-射线辐射固化制备了多壁碳纳米管-环氧树脂复合材料.采用索氏提取法、傅里叶变换红外光谱(FT-IR)和差示扫描量热法(DSC)测试了多壁碳纳米管-环氧树脂复合体系的凝胶含量、转化率及热流曲线等固化动力学参数.采用扫描电子显微镜(SEM)表征了复合材料的微观组织.结果表明:通过γ-射线辐射固化的复合体系的凝胶含量随着辐射剂量、光引发剂含量的增加而增加;由于多壁碳纳米管对活性反应中心的影响,转化率随着多壁碳纳米管加入量的增加呈先下降,后增加的趋势.复合体系中多壁碳纳米管含量较高时易发生团聚,团聚会对复合体系的固化行为产生一定影响.     

利用60Coγ-射线制备微生物聚谷氨酸类吸水剂及其吸水性能研究

对地衣芽孢杆菌(Bacillus licheniformis)NK-03发酵合成的聚γ-谷氨酸(γ-PGA)进行了60Coγ-射线辐射交联,制备了γ-PGA水凝肢.确立了最适辐射总剂量为10kGy;最适γ-PGA溶液浓度为6%;且在辐射剂量率为1.0kGy/h～4.0kGy/h的范围内,剂量率对凝胶中特定水含量影响不大.在最适条件下形成的水凝胶中特定水含量为2052倍.干凝胶可以吸收1450倍去离子水,378倍人工血、131倍人工尿和198倍0.9%NaCl溶液.在pH值9.0时具有较强的溶胀能力.具有一定的耐温保水性能和较强的耐压保水性能.     

辐射接枝医用水凝胶的研究Ⅰ.硅橡胶辐射接技N-乙烯基吡咯烷酮

采用填加SiO_2增强的甲基乙烯基硅橡胶混炼压片。通过~(60)Co-γ射线引发辐射硫化,利用共辐照方法,将N-乙烯基吡咯烷酮接枝到该硅橡胶上,制备了高纯度医用水凝胶。本文较系统地研究了接枝单体浓度、辐照剂量率、剂量、温度和接枝试片厚度等因素对接枝共聚反应的影响。建立了接枝速率与单体浓度、剂量率之间的动力学关系式:R_g=k[M]~(4/5)D~(1/2)。讨论了反应机制和接枝区域。     

聚丙烯酰胺-g-聚苯胺的导电水凝胶的制备及性能研究

通过两步聚合得到既具有良好力学强度又具有优良导电性能的聚丙烯酰胺-g-聚苯胺复合水凝胶.首先,丙烯酰胺和N-(4-氨苯基)丙烯酰胺在钴源γ-射线辐照下共聚形成聚丙烯酰胺水凝胶;然后,苯胺在具有微观多孔结构的聚丙烯酰胺凝胶中吸附,在过硫酸铵的作用下与凝胶的苯胺侧基发生接枝聚合,得到聚丙烯酰胺-g-聚苯胺水凝胶,并形成聚苯胺连续导电通道.改变辐照时间和辐照剂量率,所获得的聚丙烯酰胺水凝胶的凝胶分数随着辐照剂量的增加逐渐增大,而溶胀率随着辐照剂量的增加呈先增后减的趋势,表明凝胶的交联程度随辐照剂量呈规律性变化;辐照交联聚合的单体浓度对凝胶的性能,如溶胀率、微观结构和机械性能等也有影响.酸掺杂后,聚丙烯酰胺-g-聚苯胺复合凝胶的电导率达到9 S/m.     

辐射交联制备改性CMC水凝胶的溶胀行为研究

利用丙烯酰胺 (AAm)接枝改性纤维素 ,然后进行羧甲基化反应得到高取代度的丙烯酰胺 羧甲基纤维素钠 (AAm CMC Na) .对该材料进行γ射线辐照制备出新型改性CMC水凝胶 .研究了这种水凝胶的溶胀动力学、交联动力学以及温度、pH值和无机盐浓度对水凝胶溶胀行为的影响 ,并与CMC Na水凝胶进行了比较 .结果表明 ,该水凝胶和CMC Na水凝胶相比 ,优点在于辐照交联所用的剂量下降 ,而且所需的CMC浓度减少 .AAm CMC Na水凝胶的溶胀度随温度升高而增大 ,在pH为 6～ 8范围内达到最大值 ,并随无机盐浓度与吸收剂量增加而下降 ,表现出较好的温度敏感性和pH敏感性 ,可望作为吸水材料和水保持剂     

PP/EPDM共混体系的辐射效应

聚丙烯和三元乙丙橡胶(EPDM)的γ辐射效应及辐射后的聚丙烯熔体流动速率的测定表明,在限定空气中聚丙烯随着辐照剂量的增加,熔体流动速率急剧下降,而三元乙丙橡胶随辐射剂量的增加,凝胶含量逐渐增加。在20kGy的剂量辐照下,凝胶含量为22．7％,加入2％的三聚异氰酸三烯丙酯,在相同的剂量辐照下,凝胶含量达到68％。在低剂量下辐照对共混物的拉伸强度影响不大,对冲击强度有很大的影响。在20kGy的剂量辐照下,加入50％EPDM的聚丙烯的缺口冲击强度由1．95kJ／m^2提高到30kJ／m^2,维卡软化温度由85．9℃提高到97．0℃。     

聚乙烯醇的强化辐射交联

通常γ-辐照裂解的聚乙烯醇(PVA)在N·N’-甲基丙烯酰胺(BAM)存在下可以辐射交联。BAM/PVA体系的辐射效应可大致依辐照剂量的增加划分为三个阶段:强化辐射交联为主区,强化辐射交联与辐射裂解相抵区和辐射裂解优势区。强化辐射交联区的溶胶分数S与辐照剂量D的关系可表示为: S=(1 (1/(1-K))D_g~(2=K))-(D_g/(1-K))D~(1-K) =A-BR~(1-K)式中,D_g为凝胶化剂量;K是与BAM含量相关的常数。     

Three-dimensional polymer gel dosimetry: basic physical properties of the dosimeter

This study concentrated on assessment of the basic physical properties of a polymer gel dosimeter evaluated by NMR. For this, BANG-2 type polymer gel was prepared. The dosimeters were irradiated by ⁶⁰Co gamma photons and by 4, 6 and 18 MV X-ray photons for doses in the range 0–50 Gy. The multi-echo CPMG sequence was used for the evaluation of T₂-relaxation times in the irradiated gel dosimeters. Dependence of 1/T₂ in terms of the following factors was studied: absorbed dose, energy of applied radiation, temperature during NMR evaluation, time between irradiation and NMR evaluation and strength of the magnetic field. An exponential dependence of the 1/T₂ response on absorbed dose in the range 0–50 Gy was observed, while in the range 0–10 Gy the data could be fitted by a linear function. This paper also describes the dependence of 1/T₂ response on: radiation energy, strength of magnetic field and time from irradiation of the dosimeters to NMR evaluation. Increase of gel dosimeter 1/T₂ response with the decrease of the temperature during NMR evaluation has been qantitatively described. The polymer gel dosimetry system used in this study proved that it is a reliable system for three-dimensional dose distribution measurement.     

A new label dosimetry system based on pentacosa-diynoic acid monomer for low dose applications

The dosimetric characteristics of γ-radiation sensitive labels based on polyvinyl butyral (PVB) and a conjugated diacetylene monomer, 10,12-pentacosa-diynoic acid (PCDA) have been investigated using reflectance colorimeter. Two types of labels (colourless and yellow) based on PCDA monomer were prepared using an Automatic Film Applicator System. Upon γ-ray exposure, the colourless label turns progressively blue, while the yellow colour label turns to green then to dark blue. The colour intensity of the labels is proportional to the radiation absorbed dose. The useful dose range was 15 Gy-2 kGy depending on PCDA monomer concentration. The expanded uncertainty of dose measurement of the colourless label was 6.06 (2σ).     

New chemical Fricke gel radiation dosimeter

Dosimetric gel is used in several measurements due to its linearity, low cost, and possibility for 3D measurements. This work brings a new possibility to apply the Fricke Xylenol Gel recipe in the diagnostic measurements region. The Fricke Xilenol Gel (FXG) dosimeter is associated with the Fe(II) to Fe(III) oxidation, when irradiated, being the final ion concentration proportional to the absorbed dose. To achieve the scope, the former dosimeter was modified through the benzoic acid addition in the original recipe forming a new dosimeter, the Benzoic Xylenol Gel (BFXG). The results obtained with this new dosimeter demonstrated a higher sensibility for low absorbed dose values, bringing down the absorbed dose inferior limit from 0.1 to 0.006 Gy, that is more adequate for radiodiagnostic absorbed dose measurements. This result shows the possibly of BFXG dosimeter to be used for measurements in the radiodiagnostic region, as for tomography and mammography techniques.     

Preliminary investigation of a new type of propylene based gel dosimeter (DEMBIG)

Radiotherapy widely uses the polymer gel dosimeter. The advantage of polymer gel dosimetry is the mapped 3D absorbed dose distribution that other dosimeters cannot achieve. The Acrylamide (AAm) is a frequently used monomer; however, the extreme toxicity of Acrylamide (ORL-RAT LD50: 124 mg/kg) raises a concern. Therefore, this study developed a new type of Propylene acid based gel dosimeter, named DEMBIG gel. The following outlines the aim of this study: (1) using two-point formulation to find the optimal scan parameter of MRI according to the best sensitivity and linearity (correlation coefficient) of DEMBIG gel, (2) using the optimal scan parameter of MRI to observe the properties of DEMBIG gel, and (3) verifying the three-dimensional (3D) dose distributions of radiotherapy. This study obtained three major results: 1. The scan protocol of MRI was established. 2. The preliminary results of DEMBIG gel were: (1) The range of absorbed dose of DEMBIG gel: 0–20 Gy. (2) The sensitivity and correlation coefficient of DEMBIG gel at verification as slope: 0.181 sGy^?1, R ²:0.997. (3) There is no energy dependency of the DEMBIG gel. 3. The dose difference was 3% in the three-dimensional (3D) isocenter dose in clinical radiotherapy. These data show that DEMBIG gel is a potential candidate for the 3D dosimeter.     

Dosimetric characteristics of different types of saccharides: An EPR and UV spectrometric study

The time stability and dose response of the free radicals produced in various types of “less-studied” mono- and disaccharides by γ-radiation is studied by EPR (Electron Paramagnetic Resonance) and UV spectrometry. The time evolution of the shape of the EPR spectra of irradiated saccharides is investigated from 5 min to 5 months after irradiation. The intensity of the stable EPR signal is studied as a function of the absorbed γ-dose in the range 0.5–20 kGy. Aqueous solutions of irradiated solid saccharides exhibit a UV absorption maximum in the range 250–290 nm. A linear dependency is found between the magnitude of the UV absorption maximum and the absorbed γ-dose. The time stability of the UV absorption maximum is also studied for every saccharide. The results are compared with those obtained for irradiated sucrose.     

Dosimetric characteristics of aqueous solution of crystal violet for applications in food irradiation

Aqueous solution of crystal violet has been evaluated spectrophotometrically as a gamma-ray chemical dosimeter. The response of the chemical dosimetric system has also been investigated under different environmental conditions, such as light and temperature. In the present study the response has been measured at two wavelengths; 588 nm (λ_max of the irradiated solution) and 500 nm. The response of the crystal violet dosimeter was linear in the dose range of 50–550 Gy at pH 5.6 when absorption measurements were made at 588 and 500 nm. The response of the crystal violet dosimeter during post-irradiation storage at room temperature in dark showed slight decrease in absorbance at 588 and 510 nm but the response was almost stable at 460 nm. For higher doses, the change in the response was greater as compared to the low doses. Post-irradiation stability during diffused sunlight showed significant decrease in the response for higher dose at 588 and 510 nm and slower decrease in the response for lower dose at the above mentioned wavelengths. However the response was almost stable up to 97 days at 460 nm for higher and lower doses. At 4 °C, the decrease in the absorbance was slower at 588 and 510 nm while the response was almost constant at 460 nm. At higher temperatures, such as 40 °C, the decrease in the absorbance was greater at 588 and 510 nm while at 460 nm the absorbance was almost constant for about 3 months.     

Selfcalibrated alanine/EPR dosimeters: A new generation of solid state/EPR dosimeters

Alanine/EPR dosimeters are well established as secondary, reference dosimeters for high-energy radiation. However, there are various sources of uncertainty in the evaluation of absorbed dose. This arises primarily from the necessity to calibrate each EPR spectrometer and each batch of dosimeters before their use. In order to overcome this disadvantage, a new generation alanine/EPR dosimeter has been developed, and its possibilities as a radiation detector are reported. Principally, it is a mixture of alanine, some quantity of EPR active substance, and a binding material. The EPR active substance, acting as an internal EPR standard, is chosen to have EPR parameters which are independent of the irradiation dose. The simultaneous recording of the spectra of both the sample and the standard under the same experimental conditions and the estimation of the ratioI _alanine/I _Mn as a function of the absorbed dose strongly reduces the uncertainties. The response of these dosimeters for⁶⁰Co γ-radiation exhibits excellent linearity and reproducibility in the range of absorbed dose, 10²−5·10⁴ Gy.     

热敏性功能材料聚N-乙烯基己内酰胺的辐射聚合

具有低临界相变温度（LCST）的温度敏感性高聚物是一类特殊热性能的高聚物。当环境温度低于LCST时,其在溶液中的溶解性会随着温度升高缓慢降低。但一旦温度升高到LCST附近很小范围里,其溶解性会突然降低,出现热沉降,而且这种变化是可逆的。这类高聚物中研究较多也最具代表性的是聚N－异丙基丙烯酰胺（PNIPAAm）和聚N-乙烯基己内酰胺（PNVCL）,因为这两种聚合物的LCST都处于生理温度范围内（30－40℃）,使它们的系列高聚物在生物和医药材料中有极其广泛的应用前景^[1,2]。相比而言,PNVCL的研究与应用不PNIPAAm开展得早和完善,但其具有比PNIPAAm更好的生物相容性。所以近年来在生物大分子的分离、浓集、固定化以及药物的包埋和缓释等方面对PNVCL的研究也逐渐开展起来^[3,4,5]。目前,热敏性PNVCL高聚物主要采用化学法合成^[6,7],辐射合成几乎未见报道。为此,本文采用γ辐射聚合聚N－乙烯基己内酰胺（PNVCL）的可溶性链状高聚物。研究辐射条件对其热敏性、平均分子量等的影响。     

Post-irradiation stability of response of an aqueous coumarin dosimeter

Aqueous solution of coumarin (-benzopyrone) has been evaluated spectrophotometrically as a -ray dosimeter. In the present study measurements have been made at peak wavelength of 347 nm as well as at two other wavelengths (i. e. 360 and 370 nm). The response of the dosimeter with respect to absorbed dose is linear in the range of 0.05 to 0.5 kGy when absorption measurements are made at 347 nm. However, this dose range can be increased up to 0.8 kGy if analyzed at longer wavelengths of 360 and 370 nm. Postirradiation stability at room temperature in the dark show that the response increases gradually till 6 d. Afterwards the response is almost stabilized up to 42 d at all the wavelengths studied.     

On the Development of the VIPAR Polymer Gel Dosimeter for Three-Dimensional Dose Measurements

Summary: The new polymer gel dosimeter, based on the modification of the VIPAR gel composition, is described for the purpose of radiation dose distribution measurement in radiotherapy. It features increased concentration of the two VIPAR substrates: N-vinylpyrrolidone (8%) and gelatine (7.5%) (N,N′-methylenebisacrylamide was maintained at 4%), and the addition of copper sulphate (0.0008%) and ascorbic acid (0.007%) in order to facilitate the preparation through elimination of the need for deoxygenation of the gel. Following the exposure to ionizing radiation, polymerisation and cross-linking of the new gel monomers occurs retaining the spatial distribution of absorbed dose and causing opacity of the gel. Quantitative parameters of the new gel dose response were studied using magnetic resonance imaging to relate polymerisation induced physicochemical changes of the gel to dose. The dose threshold is found significantly lower than that of the original VIPAR gel. The linear part of measured spin-spin relaxation rate R₂(D) ( = 1/T₂(D)) reaches up to 35 Gy. Its slope and an intercept are slightly higher relative to the original VIPAR. The efficiency of the new polymer gel-magnetic resonance imaging dosimeter was also tested for dose verification of a 3D dose distribution planned by a commercially available treatment planning software (Eclipse External Beam v.6.5) and delivered by a 6 MV medical linear accelerator. The new polymer gel is proposed to be called, VIPAR^nd (after VIPAR-normoxic-double).