Effect of kappa-carrageenan on the properties of poly(N-vinyl pyrrolidone)/kappa-carrageenan blend hydrogel synthesized by γ-radiation technology

A series of hydrogels in the form of rods were prepared from kappa-carrageenan (KC) and poly (N-vinyl pyrrolidone) (PVP) by gamma radiation with ⁶⁰Co γ source at room temperature. The properties of the prepared hydrogels, such as the gel strength, gel fraction and swelling behavior were investigated. Incorporation of KC into the PVP/water system increased obviously the gel strength and equilibrium degree of swelling (EDS) of PVP hydrogel. The experimental analyses showed that the crosslinking reaction of PVP was quicker than the degradation of KC at a low dose (less than 30 kGy), and the degradation of KC was inhibited in the PVP/KC mixture system. So an interpenetrating polymer network (IPN) hydrogel composed of PVP (a chemical crosslinking network) and KC (a physical crosslinking network) was proposed here. The existence of different classes of water in this IPN system was shown by water melting curves using DCS.     

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     

Stretched exponential survival statistics for microorganisms in radiation field

The so-called concave or tailed survival curves are reported both for multi and single species bacterial populations. Taking as an example Bacillus pumilus, frequently encountered in decontamination studies, it is shown that the tailed survival curves are adequately described by stretched (0<<1) exponential SF=exp[−(D/D₀)], where SF denotes the fraction of species surviving the irradiation dose D, D₀ is the effective dose, and is the dispersion parameter interpreted phenomenologically in terms of radiation sensivity distribution for single species population under the given experimental conditions.     

Radiation preparation of PVA-g-NIPAAm in a homogeneous system and its application in controlled release

Thermosensitive PVA-g-NIPAAm copolymers were prepared by graft copolymerization of N-isopropylacrylamide (NIPAAm) onto poly (vinyl alcohol) (PVA) in homogeneous system of dimethyl sulfoxide (DMSO) by ⁶⁰Co-γ irradiation at room temperature. The factors of affecting the grafting yield, such as radiation dose, dose rate, acid concentration, were investigated. It was found that the grafting yield was increased with dose up to 30 kGy, but decreased slightly with dose rate from 61.2 to 50.1 Gy/min. The acid concentration also had influence on the grafting yield. Then the hydrogel of PVA-g-NIPAAm copolymer was made through a freezing–thawing process. The PVA-g-NIPAAm hydrogel exhibited obvious thermal sensitivity, which was observed from the differences of swelling behavior in water at different temperatures (below or above LCST). In addition, the release of Methylene Blue (MB) from this kind of hydrogel was studied. The release rate of MB from PVA-g-NIPAAm copolymer hydrogel at 48°C was faster than that at 15°C due to the shrinkage of the hydrogel at 48°C.     

Characterization of gamma irradiated carboxymethyl cellulose (CMC) films loaded with metal salts and fertilizers

Carboxymethyl cellulose (CMC) films loaded with different metal ions and fertilizers have been successfully prepared by the solution casting technique. The prepared films were subjected to different doses of gamma radiation at room temperature. The preparation conditions such as effect of type of metals, fertilizers and radiation dose on gel fraction (%) and swelling (%) were investigated. The maximum value of gel fraction was obtained at 10 kGy radiation dose. The formation of CMC/metal complexes was confirmed by X-ray diffraction (XRD), infrared spectroscopy and scanning electron microscope (SEM) which confirm the existence of possible interaction between CMC and metal ions. The loading of various metal ions to CMC films were found to enhance the mechanical properties of the prepared films. The results provided confirmation that metal coordination between the metal cation and the carboxylate group of CMC occurred.     

Interfacially formed poly(N,N-dimethylaminoethyl methacrylate)/polysulfone composite membranes for CO2/N2 separation

Interfacially formed poly(N,N-dimethylaminoethyl methacrylate)/polysulfone (PDMAEMA/PSF) composite membranes were developed for CO₂/N₂ separation. A layer of PDMAEMA was deposited on a microporous PSF substrate by the solution coating technique, followed by crosslinking with p-xylylene dichloride (XDC) at the interface between the PDMAEMA solid layer and the crosslinking solution. The hydrophilicity and surface free energy of the membranes were analyzed by contact angle measurements with different probe liquids. The permselectivity of the membrane was shown to be affected by the PDMAEMA deposition time, interfacial crosslinking reaction time, and the PDMAEMA and XDC concentrations in the polymer coating solution and the crosslinking solution, respectively. The composite membrane showed a CO₂ permeance of 85 GPU and a CO₂/N₂ ideal separation factor of 50 at 23 °C and 0.41 MPa of CO₂ feed pressure.     

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     

Cl-、Br-、I-的反相色谱研究

本文用萃取剂^[1.2]N₂₆₃或N₂₃₅为固定液,以硝酸钠溶液为流动相,在HPIEC仪器上研究了分离卤素离子的条件。32分钟完全分离了Cl^-、Br^-、I^-,测定了一些样品,结果良好。讨论了卤素离子在高分子胺上的色谱行为,提出了用热力学参数及实验条件估算其保留值的经验公式。     

On the kinetics of polymer degradation in solution—XII. Radiolysis of poly(2,2,2-trichloroethyl methacrylate)

The title compound (PTCMA) was irradiated in O₂-free dioxane solution by ⁶⁰Co-γ-rays or by 100 nsec-pulses of 16 MeV electrons. At concentrations below ca 0.04 base mol/l, main-chain scission occurred as was concluded from the decrease of the light scattering intensity (LSI). G(S) = 3.7 ± 0.4 was independent of the polymer concentration and equal to G(S) observed with solid PTCMA. This result indicates that in dilute solution main-chain scission is induced by the direct action of radiation on the polymer. The free radical [presumably ---C(CH₃)---(CH₂)---] giving rise to main-chain scission has a lifetime of 2.6 msec. It reacts with ethane thiol (k = 6.6 × 10⁴M⁻¹sec⁻¹). At concentrations above 0.04 base mol/l, the polymer crosslinked (gel formation, increase of the LSI according to 2nd order kinetics). It is assumed that crosslinking is due to the combination of radicals of the type ---CH₂---C(CH₃)(COOCH₂CCl₂)--- formed via dissociative electron capture processes involving mainly electrons in spurs that otherwise recombine with parent ions. This conclusion was inferred from the finding that [(τ_1/2)₁]⁻¹ ∞ (c_polymer)²[(τ_1/2)₁): 1st half-life of LSI increase after the pulse, c_polymer: polymer concentration].     

溴代烷烃与活性氮的反应发光研究

在流动余辉装置上, 利用N₂空心阴极放电制备活性氮, 研究了活性氮与溴代烷烃(CHBr₃、CH₂Br₂、C₂H₅Br、C₄H₉Br) 反应的化学发光.上述所有反应中, 在550～750 nm波段均观察到了较强的NBr (b¹Σ+→X³Σ^-)跃迁发射谱. 同时在活性氮与CHBr₃和CH₂Br₂的反应中, 在流动管下游还观察到了CN (A²π, B²π→X²Σ⁺)的发射谱. 验证性的实验表明, 激发态NBr (b¹Σ⁺)是由二步过程形成: N(⁴S)与溴代烷烃反应生成NBr (X³Σ^-), 再通过N₂ (A ³Σ_u⁺)分子能量转移到激发态NBr (b¹Σ⁺); 而激发态的CN是通过N(⁴S) + CBr→CN(A, B) + Br过程形成的.     

SIFSIX-3-Ni膜的制备及氢气分离性质

利用(NH₄)₂SiF₆修饰大孔玻璃基底后, 在溶剂热条件下制备了SIFSIX-3-Ni膜, 并研究了温度和浓度对制备SIFSIX-3-Ni膜的影响. 能谱分析(XPS)结果表明大孔玻璃表面引入了氟元素. SIFSIX-3-Ni膜的粉末X射线衍射(PXRD)峰位置和模拟结果一致, 表明成功制备出SIFSIX-3-Ni膜. 从扫描电子显微镜(SEM)照片中观察到膜连续均匀, 厚度约为20 μm. 热重分析(TGA)结果表明, 活化前的膜没有客体分子. 单组分测试结果表明, 膜的H₂, CO₂和N₂渗透量分别为6.83×10 ^-6, 7.42×10 ^-7和8.89×10 ^-7 mol·m ^-2·s ^-1·Pa ^-1, H₂/CO₂和H₂/N₂的理想分离比分别为9.20和7.68. 在连续测试5 h后, H₂, CO₂和N₂渗透量基本保持不变, 表明SIFSIX-3-Ni膜具有很好的稳定性.     

OPTIMIZATION OF THE SYNTHESIS OF ACRYLAMIDE HYDROGEL BY γ-RAY IRRADIATION

Hydrogels have been synthesized from 10%, 20%, 30%, 40%, 50% and 60% aqueous solutions of acrylamide monomer by gamma radiation employing doses in the range of 0.2-30 kGy from a Co-60 source. The effect of solution concentration, γ-ray dose, pH and time was studied in order to observe the optimizing conditions in the characterization of hydrogels. Gel fraction increases with dose for all concentrations indicating hundred-percentage conversion of gel at doses ≥5 kGy for homogenous solutions in the range of 20%-50% concentration. On the other hand, 10% solution provides conversion less than 86% even at 30 kGy, whereas 60% monomer makes an inhomogeneous solution which stile gives about 100% gel fraction. Swelling of hydrogels under water with respect to time varies with both the doses and concentrations due to the change of crosslinking density in the gels. The maximum volume change of hydrogels during swelling and water desorption mainly occurs within 24 h. Swelling is also enhanced with the rise of pH due to change of ionic content of the solvent. Considering the amount of gel fraction and the properties of hydrogel, the samples prepared from 20% solution at 5kGy show better results. Moreover, the effect of bacteria on hydrogel was found to be nil, suggesting a prohibition of growth of microorganism in it.     

MgF2改性Alq3纳米复合材料的制备及其对OLED抗老化性能的提高

提高有机电致发光器件(OLED)的稳定性和寿命是其市场化应用中需要解决的关键问题.本文从提高发光材料自身的稳定性出发,以Mg(CF₃COO)_2-x(CH₃COO)_x溶胶为前驱体,将其与8-羟基喹啉铝(Alq₃)混合浓缩成糊状后, 300 ℃真空烧结,经过MgF₂的生成和Alq₃的相变后,形成了一系列Mg含量不同的具有超结构ε相的纳米复合材料Alq₃-MgF₂.研究结果表明,相比于纯Alq₃, Alq₃-MgF₂纳米复合材料制备的OLED可以很好地保持Alq₃的发光特性,同时,其抗老化性能得到显著提高.特别是, Mg(CH₃COO)₂投料量为Alq₃的5% (摩尔分数)时,所得Alq₃-MgF₂纳米复合材料制备的器件抗老化性能最优,在空气中老化72 h,最大发光亮度仍保持在起始值的93.5%;而Alq₃制备的OLED在空气中老化24 h后基本失活.     

Nitrite formation in the radiolysis of aerated aqueous solutions of ammonia

Gamma irradiation of aerated aqueous solutions of ammonia leads to the formation of nitrite as a radiolytic product. Its yield increases with increasing concentration of NH₃ as well as O₂. OH radicals react with NH₃ to give NH₂ radicals, which in the presence of O₂ form NH₂O₂ radicals. These radicals finally lead to the formation of nitrite. G(NO₂⁻) decreases with increasing radiation dose due to secondary reactions. Its initial yield, however, is more than 1/2G_OH, while hydrogen peroxide yield is less than the expected value viz. G(H₂O₂) + 1/2G(e_aq⁻), indicating its participation in reactions with radiation produced free radicals. G(H₂) is 0.35 in aerated aqueous solutions of 10⁻³ mol dm⁻³ NH₃ and 0.23 in the absence of oxygen. Implications of these results to the use of NH₃ in primary coolant water of pressurized water nuclear power reactors of the VVER type are discussed.     

Gas phase chemical equilibrium in dinitrogen trioxide and dinitrogen tetroxide

The ideal gas chemical thermodynamic properties for NO, NO₂, N₂O₃, and N₂O₄ for the temperature range 50 to 5000 K were evaluated by the statistical thermodynamic method using the most recent molecular parameters. In the calculations for NO and NO₂, the effects of anharmonicity and vibration—rotation interaction were included. The contributions due to centrifugal distortion were also included for NO₂. For evaluation of the thermodynamic properties for N₂O₃ and N₂O₄ molecules, the rigid-rotor and harmonic-oscillator model were adopted. A free internal rotation was assumed for N₂O₃ and an internal rotation barrier height (V₂) of 1.58 kcal mol⁻¹ was derived for N₂O₄. The thermodynamic properties due to hindered internal rotation were clculated using a partition function formed by summation of internal rotation energy levels. The thermodynamic properties for two equilibrium mixtures: NO₂---N₂O₄ and N₂O₃---NO---NO₂---N₂O₄ were also calculated. The effects of temperature and pressure on heat capacities and compositions of these two mixtures are illustrated graphically and the calculated heat capacities and equilibrim constants are in good agreement with available experimental values.     

Synthesis of Carboxymethyl Cellulose Based Drug Carrier Hydrogel Using Ionizing Radiation for Possible Use as Site Specific Delivery System

A unique natural polymer based colon specific drug carrier was prepared from carboxymethyl cellulose (CMC) and acrylic acid (AAc) in aqueous solution employing γ‐radiation induced copolymerization and crosslinking. The effect of preparation conditions such as the natural polymer content and irradiation dose on gelation process was investigated. The swelling behavior of the prepared hydrogels was characterized by investigating the time and pH dependent swelling of the (CMC/AAc) hydrogels of different CMC content. The effects of the hydrogel composition and pH of the swelling medium on the swelling indices were estimated. The results show that the increment in the CMC content in the feed solution enhances the gelation process. The results also show the dependence of the swelling indices on both hydrogel composition and pH value of the swelling medium. To evaluate the ability of the prepared hydrogel to be used as a colon‐specific drug carrier, the release profile of theophylline was studied as a function of time at pH 1 and pH 7.     

浓凝胶转换法制备纳米SAPO-34及其CH4/N2吸附分离性能研究

通过浓凝胶转换法合成了一种厚度约为50 nm, 大小约为200 nm的纳米片状SAPO-34分子筛, 经XRD, SEM, ICP和氮气(77 K)吸附-脱附等方法对其进行了表征, 结果显示, 相比于微米级立方体形的SAPO-34 (2 μm), 本文合成的纳米片状SAPO-34表现出更高的比表面积(818.68 m²/g)和孔容(0.57 cm³/g). 比表面和孔容积的增大使其气体吸附容量得到较大的提升, 其中CH₄的吸附容量达到25.74 cm³/g, 提升了60%, 高于绝大多数分子筛吸附剂, 同时CH₄/N₂的吸附选择性未出现明显下降(3.1), 且达到商用吸附剂水平(＞3.0). 通过CH₄/N₂(体积比1∶1, 298 K)混合气体穿透测试证明所合成的纳米SAPO-34是一种有效的CH₄/N₂分离吸附剂, 在煤层气富集脱氮工业中具有极大的应用潜力.     

k-型卡拉胶/聚乙烯吡咯烷酮共混水凝胶的辐射制备及性质研究

采用辐射技术制备了κ-型卡拉胶(KC)/聚乙烯基吡咯烷酮(PVP)共混水凝胶,研究了共混凝胶内KC含量、PVP的分子量和辐照剂量等对KC/PVP共混水凝胶性质的影响.实验发现,KC与高分子量的PVP(k-90)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含量的增加,凝胶强度及溶胀性能均显著提高.分析表明,KC与高分子量的PVP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.     

Pr掺杂对V2O5-MoO3/TiO2催化剂NH3-SCR反应活性的影响

采用溶胶-凝胶法制备了不同Pr掺杂量的Pr₆O₁₁-TiO₂载体, 并以浸渍法制备了V₂O₅-MoO₃/Pr₆O₁₁-TiO₂催化剂. 活性评价结果表明, 该催化剂在220~400 ℃范围内具有良好的脱硝效率和N₂选择性以及较强的抗SO₂和H₂O性能. 表征结果表明, 掺杂Pr可以提高V₂O₅-MoO₃/TiO₂催化剂的比表面积、 表面化学吸附氧物种浓度、 桥式硝酸盐物种和Brönsted酸位数量, 从而提高了催化剂上NO_x的选择性催化还原(NH₃-SCR)活性.