聚氨酯微球的接枝改性及温敏特性

以N-异丙基丙烯酰胺(NIPAAm)为单体, 二苯甲酮(BP)为光敏剂, 过硫酸胺(APS)为自由基引发剂, 采用溶液中光接枝方法制备了具有温度敏感特性的聚氨酯微球(PUS). 傅里叶变换红外光谱(FTIR)和扫描电子显微镜(SEM)结果表明, 在聚氨酯微球表面形成了聚异丙基丙烯酰胺(PNIPAAm)接枝聚合物层. 在接枝过程中, 延长反应时间与增加引发剂浓度均有利于提高接枝率. 常温下, 接枝率随反应时间延长呈线性增长, 当反应时间超过40 min后, 接枝率基本保持稳定; 而引发剂浓度对接枝率的影响存在最佳优化值, 即其浓度为单体质量分数的3%. 采用差示扫描量热法(DSC)对接枝改性前后聚氨酯微球的温敏特性进行分析表征, 证实改性后的微球在35 ℃左右出现低临界互溶温度(LCST), 在此温度附近表现出对温度敏感特性. 接触角测试与溶胀测试结果表明, 在低临界互熔温度以下, 接枝改性的聚氨酯微球具有良好的亲水性.     

聚氰基丙烯酸乙酯空心纳米纤维的制备

通过溶液聚合法制备了具有空心结构的聚氰基丙烯酸乙酯纳米纤维,纤维直径为50~100 nm.研究了3种溶液体系对形成聚氰基丙烯酸乙酯纳米纤维形貌与直径的影响,并探讨了其形成机理.通过调控溶液体系内外环境可得到不同形貌的聚合物纤维,且纤维表面表现出疏水性质.该方法适用于平整且具有粗糙结构的表面.所形成的聚氰基丙烯酸乙酯纳米纤维涂层可用于基底的疏水改性.     

Derivatization following hollow‐fiber microextraction with tetramethylammonium acetate as a dual‐function reagent for the determination of benzoic acid and sorbic acid by GC

Derivatization at the injection port following hollow‐fiber‐based liquid–liquid–liquid microextraction with tetramethylammonium acetate as a dual‐function reagent, i.e. an acceptor and derivatization reagent, for the determination of benzoic acid (BA) and sorbic acid (SA) in real samples by GC was developed. BA and SA were extracted from aqueous samples to an organic phase impregnated into the pores of the hollow fiber wall, and then back‐extracted to the acceptor solution located inside the lumen of the hollow fiber. Upon injection, the extracted analytes were quantitatively derivatized to their methyl esters with tetramethylammonium acetate in the GC injection port. Several parameters related to the derivatization and extraction efficiency were optimized. The linearity was satisfactory over a concentration range of 0.1–50 mg/L with r > 0.993 for both analytes. The LODs were 2.0 μg/L for SA and 20 μg/L for BA. The recoveries (83–116%) and precisions (RSDs of 1.2–11.4% (n = 3)) were examined by analyzing real spiked samples. The enrichment factors of BA and SA were 300 and 425. The results demonstrated that this is a simple, rapid, accurate, and sensitive method for the determination of BA and SA in various samples.     

氮掺杂石墨烯负载的硫化镉空心球纳米复合材料的光催化性能

通过无模板法一步合成了一种新型N掺杂石墨烯负载的CdS空心球复合材料. 采用X射线衍射、透射电镜、红外光谱、紫外-可见光谱、N₂吸附-脱附、荧光光谱和X射线光电子能谱等技术对该材料进行了表征, 并在可见光照射下测试了其在降解亚甲基蓝和水杨酸中的光催化性能. 结果表明, 相对于氧化石墨烯负载硫化镉空心球和单独的硫化镉空心球, 氮掺杂石墨烯负载的硫化镉空心球具有更高的光催化活性和稳定性. 这是由于氮掺杂的石墨烯能充当优异的电子受体和传输体, 从而抑制了载流子的复合. 另外发现, 羟基自由基是可见光下降解亚甲基蓝的主要活性物种.     

壬基酚表面印迹聚合物微球的合成及分子识别特性

采用表面分子印迹技术,在二氧化硅微粒表面通过乙烯基三甲氧基硅烷接枝,以壬基酚(NP)为模板、α-甲基丙烯酸为功能单体制备了壬基酚印迹聚合物。扫描电镜及比表面分析仪测试结果表明制备的印迹聚合物呈均匀分散的微球,具有较大的比表面积。采用红外光谱表征印迹聚合物微球制备过程中的化学结构变化情况,并用平衡吸附法研究了聚合物对NP的结合性能与分子识别特性。研究结果表明,聚合物对壬基酚具有良好的结合亲和性,最大结合量可达184.6 mg/g。印迹聚合物对NP的吸附量高于其结构类似物对特辛基酚和双酚A的吸附量,表现出较高的选择性识别能力。     

二氧化锆微球表面键合磺化交联聚苯乙烯固相萃取填料的制备及应用

以聚合诱导胶体凝聚法(PICA)制备二氧化锆微球,用钛酸酯偶联剂对其进行表面改性,使其接枝上碳碳双键基团。在溶液体系中,该双键与单体苯乙烯和二乙烯苯在自由基引发下交联聚合,形成的聚合物包覆在二氧化锆微球表面。再通过磺化方法将磺酸基离子连接到苯环上,得到阳离子交换固相萃取填料。通过红外光谱、扫描电镜/X射线能谱等手段对其进行了表征。将装填得到的固相萃取柱与高效液相色谱联用,测定了水中的甲基磺草酮、阿特拉津和乙草胺。3种化合物的色谱峰面积与质量浓度呈良好的线性关系,相关系数(r²)均大于0.99;甲基磺草酮、阿特拉津和乙草胺的检出限分别为5.41、6.72和13.4 μg/L。结果表明,制得的聚合物包覆二氧化锆微球的粒径为6~8 μm,用该填料制成的固相萃取小柱对3种目标物的吸附率高。     

在线性或交联的聚氨酯粒子内原位还原制备纳米银粒子

纳米金属粒子有特异性质 ,可用作高效催化剂、非线性光学材料等 .为防止其聚集 ,不少研究者采用表面活性剂 [1]、配位体 [2 ]和高分子等以阻止纳米金属粒子的聚集 .近年来高分子金属复合纳米粒子引起人们广泛的兴趣 [3～ 9] .文献上大多采用线性或嵌段双亲高分子作纳米金属的分散稳定剂[6 ] 或在高分子粒子表面沉积纳米金属粒子[5] ,也有人采用多孔交联高分子微球的孔洞作为微反应器形成纳米金属粒子[7] .这些方法均不能有效地控制金属粒子的粒径 ,特别难以合成粒径小于 3 0 nm的银粒子 .本文首次报道了在常温处于粘弹态 ,线性或交联的高分…     

The Synthesis and Application of the Mesoporous Molecular Sieves MCM-41 — A Review

We report a “delayed neutralization” process for the preparation of highly-ordered aluminosilicate MCM-41 molecular sieves with high thermal and hydrothermal stability, and sharp pore size distribution. However, the structural order and pore size are dependent on the carbon chain length. In the mixture surfactant systems, the pore size of the MCM-41 materials could be fine-tuned. The pore size can be extended from 2.5 to 4.5 nm by adding a suitable amount of hydrocarbons. The tubular morphology of the MCM-41 material of 0.3 to 10 micrometers diameter, where the wall consists of coaxial cylindrical pores of nanometers MCM-41, can be obtained by careful control of the surfactant-water content and the rate of condensation of silica. An optimum condition for automatic synthesis of the hierarchical TWT structure has been accomplished. The addition of 1-alkanols as cosurfactant would not only improve the order of the MCM-41 hexagonal structure but also promote the formation of micrometer-sized hierarchical materials, for example: tubules-within-tubule and uniform-sized hollow spheres of diameter 5.0 ± 1.0 μm. However, the inside of the micron spheres has intricate structures possessing various topological genus ranks. The MCM-41 is a good supporter for Molybdenum oxide catalysts. The rate of deactivation in the catalytic reaction of ethyl-benzene dehydrogenation to styrene increases in the order: M_T < M_P < SiO₂. The physically mixed samples have higher catalytic activity than impregnated ones.     

水热反应条件对多孔球状Bi2WO6光催化剂结构及性能的影响

采用水热法制备了Bi₂WO₆光催化剂, 考察了水热反应温度、 水热反应时间及前驱体溶液pH值等条件对其对乙烯可见光催化活性的影响, 并通过X射线衍射(XRD)、 扫描电子显微镜(SEM)、 紫外-可见漫反射光谱(UV-Vis DRS)和比表面积分析等对催化剂的晶相组成、 微观形貌和光学性质等进行表征. 结果表明, 在水热反应温度为120 ℃、 水热反应时间为12 h、 前驱体溶液pH=0.5条件下, Bi₂WO₆光催化剂经过各向异性生长以及自组装奥斯特瓦尔德成熟(Ostwald ripening)过程, 形成由二维纳米薄片自组装的多孔微球状结构, 有效增大了与乙烯气体的接触面积, 禁带宽度降至2.86 eV, 可见光响应范围拓宽, 表现出优异的光催化性能, 在可见光下240 min内对乙烯的降解率达到13.69%.     

Fabrication linalool-functionalized hollow mesoporous silica spheres nanoparticles for efficiently enhance bactericidal activity

To develop a novel food preservation technology for efficiently enhance bactericidal activity in a long term, hollow mesoporous silica spheres (HMSS) with regular nanostructures were applied to encapsulate natural organic antimicrobial agents. The chemical structures, morphologies and thermal stabilities of linalool, HMSS and linalool-functionalized hollow mesoporous silica spheres (L-HMSS) nanoparticles were evaluated by polarimeter, field emission scanning electron microscope (FE-SEM), transmission electron microscope (TEM), fourier transform infrared (FT-IR), thermal gravimetric analyzer (TGA), nitrogen adsorption-desorption, zeta potential and small angle X-ray diffraction (SXRD). The results show that the linalool was successfully introduced into the cavities of HMSS, and the inorganic host exhibited a high loading capacity of about 1500 mg/g. In addition, after 48 h of incubation, the minimum bactericidal concentrations (MBC) of L-HMSS against Escherichia coli (E. coli), Salmonella enterica (S. enterica) and Staphylococcus aureus (S. aureus), Listeria monocytogenes (L. monocytogenes) were decreased to be 4 (< 5) mg/mL and 8 (< 10) mg/mL, respectively. These results revealed linalool-functionalized hollow mesoporous spheres could efficiently improve the bactericidal activities of the organic component. Furthermore, SEM images clearly showed that L-HMSS indeed had an extremely inhibitory effect against gram-negative (E. coli) and gram-positive (S. aureus) by breaking the structure of the cell membrane. This research is of great significance in the application of linalool in nano-delivery system as well as food industry.