响应面法优化中空介孔二氧化硅球包载吲哚美辛的工艺研究

采用硬模板法在室温下、中性水溶液中合成了中空介孔二氧化硅球,中空部分直径为250nm,外壳厚度25nm。利用氮气吸附-解吸附、透射电子显微镜、傅里叶变换红外光谱表征了微球的物理化学性质。该微球球形度良好,BET结果显示其比表面积为730.0m²/g,平均孔容1.084cm³/g ,平均孔道直径6.58nm。利用中空介孔二氧化硅球较好的载药性能负载吲哚美辛,并采用三因素的Box-Behnke实验设计对药物负载处方工艺进行优化研究。当IMC/HMSNs质量比为22:1,超声1.4h,震荡吸附23h时实验条件达到最佳,包封率理论值为85.2%。在此条件进行验证实验,吲哚美辛的包封率可达理论预测值的98.7%,说明将 Box-Behnken 实验设计法用于中空介孔二氧化硅球包载吲哚美辛的优化筛选是可行的,且得到的实验观察值与数学模型的预测值相符合。     

载姜黄素金纳米复合微粒的制备及体外释放研究

以氯金酸为原料,用水热法制备了金纳米复合微粒用作载体材料,再采用浸渍离心法负载姜黄素,得到负载姜黄素的金纳米复合微粒。采用粒度分析仪、XRD、红外、热重等方法,对金纳米复合微粒进行形貌结构表征。结果表明,所制备的材料为表面聚集微小孔隙、平均粒径为250nm左右的微小Au复合颗粒。当料液比为1∶1、姜黄素的质量浓度为3mg·m L-1、载药时间为6h时,金纳米复合微粒对姜黄素的包封率和载药量最大,分别为11.01%和35.48%。体外缓释实验结果表明,姜黄素原料在6h的释放率为64%,而金纳米复合微粒在6h的药物释放率仅为4.9%,可见用水热法制备的纳米金复合微粒具有较好的载药及缓释性能。     

木质素季铵盐-海藻酸钠聚合物负载阿维菌素粉体的制备及抗紫外光性能分析

以三甲基木质素季铵盐-海藻酸钠(QL-SA)为载体,用物理混合法制备了阿维菌素缓释聚合物(AVM-QL-SA),利用FT-IR对其结构进行了表征,探讨了交联剂用量、药物加入量、体系pH值等因素对载药量和包封率的影响,并对其缓释性能和抗紫外光降解进行了研究。结果表明:阿维菌素(AVM)均匀的混合在QL-SA载体中,主要以物理混合为主;最佳制备条件为:戊二醛为5%(以单体质量分数计)、药物加入量为1%(以单体质量分数计)、体系pH值为8.5,载药量和包封率分别达到1.36%和73.36%;阿维菌素缓释聚合物粒径符合正态分布,平均粒径为83.90 μm;阿维菌素缓释聚合物具有很好的缓释性能,在乙醇/水(体积比1:1)中释放30 h,累计释放率为88.97%;经8 h紫外光照射,阿维菌素原药中AVM残留量为6.24%,阿维菌素缓释聚合物中AVM残留量为37.75%,具有良好的抗紫外分解性能。     

氧化银-二氧化钛／膨润土复合光催化剂的制备及性能研究

为了提高光催化剂的实用性,以工业偏钛酸为原料,采用液相掺杂制备了氧化银-二氧化钛/膨润土复合光催化剂.以酸性橙Ⅱ为目标污染物,采用降解率来表征复合光催化剂的光催化活性.结果表明:当氧化银掺杂量为1.72%(质量分数)时,氧化银-二氧化钛/膨润土复合光催化剂在紫外光照射下和在太阳光照射下都有良好的光催化活性,其对应的降解率分别为96.25%和100%.对双氧水加入量和溶液pH的研究表明:当双氧水加入量为3 mmol/L或溶液pH为9的弱碱性条件下,催化剂光催化活性都有明显的提高.XRD分析表明,成功合成了氧化银-二氧化钛/膨润土复合物.     

蓝藻为载体的阿维菌素抗紫外缓释剂的制备及其性能

以滇池蓝藻为载体,利用其抗紫外特性,用卡波姆树脂包裹蓝藻-阿维菌素(Avermectin, Av)粉,制成阿维菌素抗紫外缓释剂,利用FT-IR, SEM和HPLC等对蓝藻和缓释剂进行表征,研究其吸附与释放行为. 结果表明,Av在异丙醇中的饱和吸附量为160.81 mg/g,包裹10%卡波姆树脂的抗紫外缓释剂具有很好的缓释功能,在乙醇/水(4:1, j)中释放20 d,累计释放率为51.8%,释放机制是Fick扩散和骨架溶蚀的双重机制. 经4 h紫外光照射,含蓝藻的制剂中Av残留量为61%,不含蓝藻的制剂中Av残留量为39%.     

烷基甜菜碱/果胶球的结肠定位给药释放行为

利用单因素法分别以氯化钙、氯化锌为交联剂,载荷吲哚美辛,复合十二烷基甜菜碱与果胶制备凝胶球。考察十二烷基甜菜碱、药物和交联剂质量分数对小球的形态、载药量、包封率和在模拟胃肠道中释药性能的影响,并比较钙锌体系的释放性能。结果表明:添加十二烷基甜菜碱可以提高凝胶球的载药量和包封率,减缓药物释放;吲哚美辛质量分数过高时会导致凝胶球的释药性能变差;交联剂质量分数的增加使凝胶球性能均呈现增长的趋势。2个体系的释药性能研究结果显示,添加十二烷基甜菜碱对果胶锌体系的释药性能影响较大。     

MIL-101(Fe)负载左旋咪唑制备缓控药物载体的研究

利用水热法制备金属有机骨架材料MIL-101(Fe),并用作模型药物左旋咪唑的药物递送载体。利用XRD、SEM、TEM、TGA、IR、Zeta电位和N₂吸附解吸等温线对材料进行表征,通过MTT法评价材料的细胞毒性。结果表明,合成的MIL-101(Fe)为八面体结构的晶体,粒径约为1μm。左旋咪唑质量浓度为5 mg/mL时MIL-101(Fe)载药量为22.20%。左旋咪唑释放研究在模拟肿瘤细胞酸性环境(pH=5.5)和模拟静脉内溶液(pH=7.4)2种不同pH的模拟体液中进行,体外释放72 h的结果表明,pH 5.5时释放率为57.31%,高于pH=7.4时的释放率;体外释放48 h后药物释放量趋于稳定,说明MIL-101(Fe)具有一定的缓释作用,MIL-101(Fe)对MCF-7细胞无毒。     

基于白藜芦醇还原特性的银基纳米载体制备及肿瘤细胞杀伤效应评价

以反式白藜芦醇(resveratrol,RES)为还原剂,硝酸银(AgNO_3)为前驱体,十六烷基三甲基溴化铵(cetyltrimethylammonium bromide,CTAB)为表面活性剂和相转移催化剂,采用原位液相还原工艺制备了负载RES的银基纳米载体(RES-AgNPs)。当AgNO_3、RES和CTAB摩尔比为1:1:0.5、40℃反应13 h时,制得平均粒径(45.5±2)nm、zeta电位-21 mV的RES-AgNPs。红外光谱和紫外吸收光谱分析结果表明,RES成功负载在纳米银表面,负载量达到0.0883 mg?mg~(-1)。体外释放实验表明,RES-AgNPs具有过氧化氢(H_2O_2)敏感响应的释放特性,当p H=5.4且CH_2O_2=25μmol?L~(-1)时RES释放率为89%。以人乳腺癌细胞MCF-7为肿瘤细胞模型,MTT实验结果显示,当样品剂量均为15μg?mL~(-1)时,与RES、AgNPs和RES+AgNPs联合给药相比,RES-AgNPs对细胞的生长抑制率分别提高了62.6%、68.2%和55.1%,体现了纳米载体中银纳米粒子与负载药物RES对肿瘤细胞的协同杀伤效应。     

β-环糊精/海藻酸钠水凝胶的制备及性能研究

将海藻酸钠(SA)和β-环糊精(β-CD)共混制备了复合水凝胶,并讨论了交联剂浓度、原料配比对水凝胶溶胀性能的影响。结果表明,当两者的共混比例为1∶2、w(交联剂)为6%、交联时间为1h时,水凝胶的溶胀性能较好。水凝胶在pH=1.2时的溶胀率仅为1.2,而在pH=7.4时的溶胀率达到14.2,具有良好的pH敏感性。以牛血清蛋白(BSA)为模型药物,研究了β-CD/SA水凝胶作为药物载体对BSA的负载及释放性能,结果表明:在模拟胃液中的累计释放量较小(21.5%),且释放速率较慢;在模拟肠液中的累计释放量为70.2%,具有良好的pH敏感控制释放性能。     

微波辅助紫外光催化氧化降解吲哚的研究

采用微波辅助紫外光催化氧化工艺处理吲哚污染物,并探讨了溶液pH值、TiO2用量、曝气时间和吲哚初始浓度对吲哚降解效果的影响。研究结果表明,曝气/MW/UV/TiO2系统中,当pH值为7、吲哚初始质量浓度为50 mg/L、催化剂质量浓度为0.2 g/L、曝气时间为60 min时,吲哚的降解效果最好,降解率为81.8%。微波辅助紫外光催化氧化工艺大大提高了TiO2的光催化性能,对难降解有机物吲哚具有良好的处理效果,对于解决目前日益严重的环境污染问题,具有一定的研究和实用价值。     

Preparation and characterization of UV‐curable ZnO/polymer nanocomposite films

A series of novel nano‐ZnO/polymer composite films with different ZnO contents was prepared through incorporation of pre‐made colloidal ZnO particles into monomer mixtures of urethane‐methacrylate oligomer and 2‐hydroxyethyl methacrylate, followed by ultraviolet (UV) radiation‐initiated polymerization. The colloidal ZnO nanoparticles with a diameter of 3–5 nm were synthesized from zinc acetate and lithium hydroxide in ethanol via a wet chemical method. In order to stabilize and immobilize the ZnO particles into the polymer matrix, the ZnO nanoparticles were further capped using 3‐(trimethoxysilyl)propyl methacrylate. Thermogravimetric analyses show that the ZnO nanoparticles were successfully incorporated into the polymer matrix and these ZnO/polymer composites have a good thermal stability. Transmission electron microscopy studies indicate the ZnO nanoparticles were uniformly dispersed in the polymer and they remained at the original size (3–5 nm) before immobilization. All nanocomposite films with ZnO particle contents from 1 to 15 wt% show good transparency in the visible region and luminescent properties. In addition, composite films with high ZnO content (>7 wt%) are able to absorb UV irradiation below 350 nm, indicating that these composite films exhibit good UV screening effects. Copyright © 2006 Society of Chemical Industry     

Crystallization behavior and UV‐protection property of PET‐ZnO nanocomposites prepared by in situ polymerization

The aim of this study was to investigate the crystallization behavior and UV‐protection property of polyethylene terephthalate (PET)‐ZnO nanocomposits. PET‐ZnO nanocomposites containing 0.5–3.0 wt % of ZnO were successfully synthesized by in situ polymerization. The Fourier transformed infrared (FTIR) spectroscopy indicated the silane coupling agent was anchored onto the surface of ZnO. Scanning electron microscope (SEM) images showed ZnO particles were dispersed homogeneously in PET matrix with amount of 0.5–1.0 wt %. Differential scanning calorimetry (DSC) results exhibited that the incorporation of ZnO into PET resulted in increase of the melting transition temperature (T_m) and crystallization temperature (T_c) of PET‐ZnO nanocomposites. The crystallization behavior of PET and PET‐ZnO nanocomposites was strongly affected by cooling rate. ZnO nanoparticles can act as an efficient nucleating agent to facilitate PET crystallization. UV–vis spectrophotometry showed that UV‐ray transmittance of PET‐ZnO nanocomposites decreased remarkably and reached the minimum value of 14.3% with 1.5 wt % of ZnO, compared with pure PET whose UV‐ray transmittance was 84.5%. PET‐ZnO nanocomposites exhibited better UV‐protection property than pure PET, especially in the range of UVA. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Preparation and characterization of poly(styrene butylacrylate) latex/nano‐ZnO nanocomposites

Poly(styrene butylacrylate) latex/nano‐ZnO composites were prepared by blending poly(styrene butylacrylate) latex with a water slurry of nano‐ZnO particles, and the effects of certain parameters, such as particle size, dispersant type, dispersing time and others, on the dispersibility, mechanical properties, ultraviolet (UV) shielding and near infrared (NIR) shielding were investigated with transmission electron microscopy (TEM), an Instron testing machine, dynamic mechanical analysis and ultraviolet‐visible‐near infrared (UV‐VIS‐NIR) spectrophotometry. TEM observation showed that dispersants with long chains are better than those with short chains at enhancing the dispersibility of nano‐ZnO particles in a matrix; extending dispersing time also improves the dispersibility of nano‐ZnO particles in a matrix. Instron tests showed that the nanocomposite polymers embedded with nano‐ZnO particles had much higher tensile strength than the corresponding composite polymers with micro‐ZnO particles. As the nano‐ZnO content increased, the temperature of glass transition (T_g) of the nanocomposite polymer embedded with 60 nm ZnO particles first increased then decreased, but 100 nm ZnO and micro‐ZnO particles seemed to have no influence on the T_g of the composite polymers. The better dispersibility of nano‐ZnO particles resulted in higher T_g values. Increasing nano‐ZnO content or dispersibility could enhance the UV shielding properties of the nanocomposite polymers, and 60 nm ZnO particles could more effectively shield UV rays than 100 nm ZnO particles. Micro‐ZnO particles basically had no effect on the UV absorbance of the composite polymers. A blue‐shift phenomenon was observed at 365 nm when nano‐ZnO particles were present in the nanocomposite polymers. NIR analysis indicated that as nano‐ZnO content increased, the NIR shielding of the nanocomposite polymers increased, but the NIR shielding properties seemed to be more influenced by particle size than by the nano‐effect. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 1923–1931, 2003     

Kinetics of the thermal dissociation of ZnO exposed to concentrated solar irradiation using a solar‐driven thermogravimeter in the 1800–2100 K range

The two‐step H₂O‐splitting thermochemical cycle based on the Zn/ZnO redox reactions is considered for solar H₂ production, comprising the endothermal dissociation of ZnO followed by the exothermal hydrolysis of Zn. A solar‐driven thermogravimeter, in which a packed‐bed of ZnO particles is directly exposed to concentrated solar radiation at a peak solar concentration ratio of 2400 suns while its weight loss is continuously monitored, was applied to measure the thermal dissociation rate in a set‐up closely approximating the heat and mass transfer characteristics of solar reactors. Isothermal thermogravimetric runs were performed in the range 1834–2109 K and fitted to a zero‐order Arrhenius rate law with apparent activation energy 361 ± 53 kJ mol^?1 K^?1 and frequency factor 14.03 × 10⁶ ± 2.73 × 10⁶ kg m^?2 s^?1. Application of L‘vov’s kinetic expression for solid decomposition along with a convective mass transport correlation yielded kinetic parameters in close agreement with those derived from experimental data. © 2009 American Institute of Chemical Engineers AIChE J, 2009     

Solution combustion synthesis of ZnO powders using CTAB as fuel

Zinc oxide (ZnO) powders have been prepared by solution combustion synthesis method using cetyltrimethylammonium bromide (CTAB) as fuel. The effects of fuel to oxidant ratios (? = 0.5, 0.75, 1 and 1.5) on the combustion behavior, phase evolution, microstructure, optical properties and photocatalytic performance were investigated by thermal analysis, X-ray diffractometry, electron microscopy, and diffuse reflectance spectrometry techniques. The slow decomposition rate of CTAB guaranteed the direct formation of single phase and well-crystalline ZnO powders regardless of fuel content. The specific surface area of the as-combusted ZnO powders with platelet particles increased from 21 ± 1 to 35 ± 2?m²/g with fuel content. The band gap energy also increased from 2.99 to 3.13?eV due to the decrease of particle size. The as-combusted ZnO powders at ? = 1.5 exhibited the highest photodegradation (~69%) of methylene blue under ultraviolet light irradiation, due to their good crystallinity and smaller particle size.     

Surface functionalization of aramid fibers via constructing different zinc oxide nanostructures for improved UV resistance

Aramid fibers (AFs) with high strength and modulus have a vital application in harsh outdoor bulletproof protection and ship ropes; however, solar radiation, especially ultraviolet (UV) radiation, is one of the main factors for affecting their service life. Herein, different zinc oxide (ZnO) nanostructures were constructed on the surface of AFs by the growth of ZnO nanowires (AF-ZnO NW) and coating of waterborne polyurethane/ZnO nanoparticles composite emulsion (AF/ZnO), respectively. The surface functionalized AFs exhibited enhanced mechanical properties retention after UV radiation. Nevertheless, the tensile strength of AF-ZnO NW before UV aging was already lower than the tensile strength of original AFs due to the surface structure damage from chemical grafting modification. The tensile strength and elongation retention rates of AF/ZnO-5% reached 74.4% and 84.4% after UV exposure for 168 h, respectively, which were much higher than the value of 48.3% and 60.5% of the neat AFs. These results provide an effective and low-cost strategy for improving the UV-resistance of advanced high-performance fibers.     

Synthesis and Characterization of ZnO Nanorods and Nanodisks from Zinc Chloride Aqueous Solution

ZnO nanorods and nanodisks were synthesized by solution process using zinc chloride as starting material. The morphology of ZnO crystal changed greatly depending on the concentrations of Zn²⁺ ion and ethylene glycohol (EG) additive in the solution. The effect of thermal treatment on the morphology was investigated. Photocatalytic activities of plate-like Zn₅(OH)₈Cl₂ · H₂O and rod-like ZnO were characterized. About 18% of 1 ppm NO could be continuously removed by ZnO particles under UV light irradiation.     

Modeling of photooxidation of acetamide herbicides in natural waters by UV radiation and the combinations UV/H2O2 and UV/O3

The photooxidation of several herbicides belonging to the acetamides group (specifically propachlor, metolachlor and butachlor) by means of a monochromatic UV irradiation in ultrapure water was studied. In the case of propachlor, the quantum yield for its photolysis was evaluated directly, and a value 0.127 ± 0.01 mol Eins^?1 was obtained independent of the pH. The quantum yields for the photolysis of metolachlor and butachlor were determined by using a competition kinetic model which used propachlor as reference compound, and values of 0.56 ± 0.05 and 0.78 ± 0.04 mol Eins^?1 were deduced respectively for metolachlor and butachlor. In a second step, the elimination of the selected herbicides in some natural and mineral waters was studied by means of several oxidation systems: UV radiation alone, and UV radiation combined with hydrogen peroxide and ozone. The influence of the operating variables in these processes (acetamide type, presence or absence of tert‐butyl alcohol and types of waters) are discussed as a consequence of the amounts of herbicides removed. Two different kinetic studies were carried out for the oxidation of the herbicides: the first one for UV radiation alone and UV radiation combined with H₂O₂; the second one for the combination UV radiation plus ozone. In these studies, the specific rate constants were evaluated in every process. Finally, kinetic models for the prediction of the elimination of these herbicides in the natural waters selected by the different oxidation systems are proposed. The values of concentrations predicted by these models agree well with the experimental results obtained. Copyright © 2004 Society of Chemical Industry     

CO2 reduction with Zn particles in a packed‐bed reactor

A two‐step solar thermochemical cycle for splitting CO₂ with Zn/ZnO redox reactions is considered, consisting of: (1) the endothermic dissociation of ZnO with concentrated solar radiation as the heat source and (2) the non‐solar, exothermic, reduction of CO₂ to CO by oxidizing Zn to ZnO; the latter is recycled to the first step. The second step of the cycle is investigated using a packed‐bed reactor where micron‐sized Zn particles were immobilized in mixtures with submicron‐sized ZnO particles. Experimental runs were performed for Zn mass fractions in the range 67–100 wt % and CO₂ concentration in the range 25–100%, yielding Zn‐to‐ZnO conversions up to 71% because of sintering prevention, as corroborated by SEM analysis. © 2010 American Institute of Chemical Engineers AIChE J, 2011     

Versatile poly(maltose) micro/nanoparticles with tunable surface functionality as a biomaterial

Maltose, a natural disaccharide, was crosslinked with divinyl sulfone to prepare poly(maltose) (p(MAL)) micro/nanoparticles via one step microemulsion system with ≥90% ± 5% yield in a size rage of 0.5–100 μm for the first time. P(MAL) was modified (m-p(MAL)) with ethylenediamine (EDA), polyethyleneimine (PEI), and taurine (TA) to render additional functionalities, that is, amine and sulfate groups. The isoelectronic point of bare p(MAL) particles were calculated at pH 2.2 ± 0.5 and was changed to 1.3 ± 0.5, 4.3 ± 1.0, and 8.1 ± 0.7 for TA (p(MAL)/TA), EDA (p(MAL)/EDA), and PEI (p(MAL)/PEI) modification, respectively. Bare p(MAL) particles were found to be biocompatible up to 2 mg/ml with hemolysis and blood clotting tests, whereas the modified p(MAL) particles were found to be biocompatible at 1 mg/ml concentration. Additionally, it was found that TA- and PEI-modified p(MAL) particles induced blood clotting mechanisms. Sodium diclofenac as model drug was released at proportions of 8.7% ± 1.3%, 3.9% ± 0.2%, 8.8% ± 0.9%, and 31.6% ± 0.4% of the loaded drug in phosphate buffered saline solution from p(MAL), p(MAL)/TA, p(MAL)/EDA, and p(MAL)/PEI, respectively. The inhibition of antimicrobial activity of p(MAL)/PEI particles at 20 mg/ml concentration for Escherichia coli and Staphylococcus aureus strain was determined as 99.86% ± 0.3% and 99.79% ± 0.25%, respectively.