PMMA纳米球的制备及其银膜包覆技术

采用无皂乳液聚合法制备了单分散、直径为170 nm左右的聚甲基丙烯酸甲酯(PMMA)纳米球, 然后利用3-甲基丙烯酰氧基丙基三甲氧基硅烷(MATS)和3-巯丙基三甲氧基硅烷(MPTMS)对PMMA纳米球进行表面改性, 在其表面包覆一层均匀的巯基, 通过巯基与银离子之间的相互作用, 使银在PMMA纳米球表面成核长大, 从而合成PMMA/Ag纳米球壳粒子. 通过扫描电子显微镜、投射电子显微镜和紫外-可见吸收光谱测试技术对产物性能进行了表征, 研究结果表明, 制备的PMMA/Ag纳米球壳粒子的分散性好、包覆均匀.     

烷基化聚甲基倍半硅氧烷色谱填料的制备与其反相保留机理探究

以甲基三甲氧基硅烷(MTMS)和巯丙基三甲氧基硅烷(MpTMS)为原料利用二步酸碱催化水解缩聚法,制备得到了多孔单分散性巯丙基功能化聚甲基倍半硅氧烷微球(Mp-PMSQ)。然后通过"巯基-乙烯基"点击化学反应,成功将微球烷基化,制备得到了具有不同C_(12)浓度的烷基化(C_(12)-S-PMSQ)微球。结果表明,该类微球单分散性良好、粒径分布较窄(D90/D101.5);烷基化后随着C_(12)浓度的增加,对应微球的孔结构参数减小而碳含量增加。采用苯同系物对其进行反相色谱行为评价,发现随着C_(12)浓度的增加,苯同系物的保留因子下降,因此我们推测吸附机理为其主导反相保留机理。     

Yolk-shell结构磺化聚苯乙烯@介孔二氧化硅微球制备及其离子交换性能

采用乳液聚合法制备聚苯乙烯微球,并经硅酸四乙酯水解、双三甲氧基硅氧乙烷交联、三甲氧基苯基硅烷修饰以及溶剂刻蚀后制得一种苯基官能化且具有Yolk-shell结构的聚苯乙烯@介孔二氧化硅的微球(Ph-Pst@SiO_2);进一步采用氯磺酸对微球进行磺酸化改性,最终获得交换性能优良且具有Yolk-shell结构的微球,考察了其离氧基苯基硅烷用量、反应时间等因素对微球形貌的影响;利用红外光谱仪、元素分析仪对微球组成成分进行分析;利用酸碱滴定法测定了微球的离子交换容量。实验结果表明,未经三甲氧基苯基硅烷修饰的磺化聚苯乙烯@介孔二氧化硅微球S-Pst@SiO_2的比表面积为435.06m~2/g,离子交换容量为2.4mmol/g。与之相比,磺化的苯基官能化聚苯乙烯@介孔二氧化硅微球(S-Ph-Pst@SiO_2)的比表面积和离子交换容量分别提高了47%和54%,具体为640.41m~2/g和3.5mmol/g。说明本研究采用苯基硅烷修饰介孔二氧化硅提升Pst@SiO_2微球离子交换性能的方法简单有效。     

含酰胺结构的硅胶键载二乙烯三胺螯合微粒的合成及其吸附性能

硅胶与γ-氨丙基三甲氧基硅烷(AFFS)进行硅烷化反应,然后与丙烯酸甲酯(MA)进行迈克尔加成反应引入酯基,最后与二乙烯三胺(DETA)反应生成氨基结尾的酰胺基硅胶,其结构经红外光谱、元素分析,热重分析(TG)和X射线衍射仪(XRD)表征.元素分析表明,Ⅰ、Ⅱ、Ⅲ的氨基含量分别为1.992mmol/g、1.699mmol/g、3.416mmol/g.研究了该硅胶微粒对重金属离子Ag 、Hg2 、Cu2 的吸附容量、吸附动力学、等温吸附过程等静态吸附性能.结果表明,对3种离子的吸附量分别为0.71mmol/g、0.46mmol/g,0.35mmol/g.动力学吸附过程为液膜扩散控制,吸附过程符合Langmuir或Freundlich模型.     

细乳液法制备聚硅氧烷-Ag纳米复合微球及其抗菌性

首先以苯乙烯(St)及3-甲基丙烯酰氧基三甲氧基硅烷(MPS)为反应单体,通过细乳液聚合制备表面功能化聚硅氧烷微球,然后利用该微球表面的硅羟基及硅氧烷基团对Ag+的吸附及还原作用原位制备聚硅氧烷-Ag纳米复合微球。采用透射电镜(TEM)、紫外(UV-Vis)、热重分析(TG)及X射线衍射(XRD)等对聚硅氧烷-Ag纳米复合微球的形貌和组成进行了表征。研究表明:改变MPS和硝酸银的用量可调控聚硅氧烷-Ag纳米复合微球的形貌及表面银含量;抗菌实验结果表明,聚硅氧烷-Ag纳米复合微球具有较好的抑菌性。     

巯基功能化磁性微球的构建及其对蛋白质的亲和分离

通过水热法一步合成了纳米Fe3O4微球,并在甲苯中用巯基丙基三甲氧基硅烷(MPS)对其进行表面修饰得到了Fe3O4-SH微球,通过DTNB法测得微球表面巯基含量为333.54μg/mg.该纳米微球可以吸附溶液中的Ni2+,从而形成Fe3O4-SH-Ni2+复合材料.以此复合材料为载体,可以将以组氨酸为标签的(His-tagged)融合蛋白直接从细胞裂解液中进行提纯,并在外加磁场的作用下实现对目标蛋白的快速分离,其对His-tagged TRX蛋白的分离能力为20.6μg/mg,特别适合于对以组氨酸为标签蛋白的分离纯化.     

改性果胶磁性微球的制备及吸附性能研究

为了提高果胶磁性微球的分散性及成球性,采用油酸对磁性微球进行表面改性后,制备改性果胶磁性微球。通过红外光谱、扫描电镜、XRD和磁性分析等对样品进行表征。油酸和果胶在纳米四氧化三铁表面形成了良好的修饰层,且油酸的加入提高了果胶磁性微球的分散性及成球性。研究了改性果胶磁性微球用量和溶液pH值等对其吸附Cu(Ⅱ)性能的影响,考察了其吸附动力学和吸附等温线。25℃时,改性果胶磁性微球对Cu(Ⅱ)的吸附达平衡需要2 h,饱合吸附容量为52.36 mg/g,Freundlich模型和Langmuir模型可以较好的拟合实验结果,最大吸附量为119.05 mg·g~(-1)。     

“一锅法”制备氨基官能化介孔二氧化硅用于吸附As(V)EI北大核心CSCD

采用3-[2-(2-氨基乙基氨基)乙基氨基]丙基-三甲氧基硅烷(AAAPTS)为单体,通过“一锅法”制备了一种氨基官能化介孔二氧化硅吸附材料用于吸附As(V)。通过傅立叶红外光谱(FT-IR)、扫描电镜(SEM)和氮气吸附-脱附分析对材料进行表征,并对吸附条件进行优化。结果表明,氨基官能化介孔二氧化硅在吸附环境为pH 3,温度25℃,吸附时间30 min时达到最佳吸附效果,其饱和吸附量为93.74 mg/g。动力学吸附、等温吸附实验结果表明,合成的材料符合伪二阶动力学模型且属于单层吸附的化学结合过程。本研究为去除环境水样品中的As(V)提供了潜在吸附材料。     

微流控法制备的多孔微球对Cr(Ⅵ)的吸附性能

利用玻璃毛细管搭建单级微流控装置制备单分散水包油(O/W)乳液,以乳液为模板,紫外光照射乳液引发自由基聚合,成功制备了单分散聚(甲基丙烯酸甲酯/甲基丙烯酸二甲氨基乙酯)[P (MMA/DMAEMA)]多孔微球。微球粒径偏差系数(CV)值小于5%,单分散性良好。研究P (MMA/DMAEMA)多孔微球对Cr(Ⅵ)的吸附性能、再生吸附性能、吸附机理。结果表明,p H对微球吸附Cr(Ⅵ)有较大影响,当pH=3时,微球对Cr(Ⅵ)的吸附率达到52. 9%,循环4次后其吸附性能基本不变;微球的吸附符合准二级动力学模型,属于化学吸附;微球等温吸附符合Langmuir模型,属于单分子层吸附。     

微流控法制备的多孔微球对Cr(Ⅵ)的吸附性能

利用玻璃毛细管搭建单级微流控装置制备单分散水包油（O/W）乳液,以乳液为模板,紫外光照射乳液引发自由基聚合,成功制备了单分散甲基丙烯酸甲酯/甲基丙烯酸二甲基氨基乙酯（MMA/DMAEMA）多孔微球。微球粒径偏差系数（CV）值小于5%,单分散性良好。研究了MMA/DMAEMA多孔微球对Cr(Ⅵ)的吸附性能、再生吸附性能、吸附机理。结果表明：pH对微球吸附Cr(Ⅵ)的量有较大影响,当pH=3时,微球对Cr(Ⅵ)吸附率达到52.9%;循环4次后微球吸附率基本不降低,循环性能好;微球吸附符合准二级动力学模型,属于化学吸附;微球等温吸附符合Langmuir模型,属于单分子层吸附。     

一步法制备PNIPAAm-g-PAN/PSt载银复合微球及其抗菌性能研究

以AgNO3为金属源,通过乙醇将与聚N-异丙基丙烯酰胺接枝聚丙烯腈/聚苯乙烯（PNIPAAm-g-PAN/PSt）聚合物微球表面酰胺基团配位的银离子（Ag+）还原,一步法制备了PNIPAAm-g-PAN/PSt载银复合微球。通过傅立叶变换红外（FTIR）和紫外-可见光光谱表征发现,由Ag+还原所得的Ag纳米颗粒被成功地固载在PNIPAAm-g-PAN/PSt 微球上;用透射电子显微镜（TEM）对载银微球的大小和形态进行了表征;热重分析（TGA）结果表明,固载在微球表面的银纳米颗粒的含量（质量分数）为12%;抗菌实验结果表明,所制备的载银微球具有抗革兰氏阴性菌的活性。     

聚苯胺-木质素纳米复合物的制备及对银离子的吸附还原性能

以酶解木质素为分散剂、苯胺为单体,采用原位聚合法制备聚苯胺-酶解木质素(PANI-Lignin)纳米复合物.采用红外光谱、紫外-可见光谱、场发射扫描电子显微镜、透射电子显微镜、热重分析和宽角X射线衍射研究了PANI-Lignin纳米复合物的结构和性能.同时,采用静态吸附法研究了PANI-Lignin纳米复合物对银离子的吸附性能.研究结果表明,酶解木质素的添加量对PANI-Lignin纳米复合物的结构和性能有很大影响.酶解木质素添加量为10 wt%时,PANI-Lignin复合物为粒径约为70 nm的纳米粒子.随着酶解木质素添加量由0增加到30 wt%,PANI-Lignin纳米复合物对银离子的吸附容量和吸附率是先增加后减少.当酶解木质素添加量为10 wt%时,PANI-Lignin纳米复合物的银离子吸附容量达到最大值,为565.4 mg/g.对吸附后产物的分析可知,吸附后有长达1 cm,宽为0.220～4.38μm,厚为219～311 nm的纳米带状单质银生成,说明该PANI-Lignin复合物具有较强的反应性银离子吸附能力.     

Magnetic IDA-modified hydrophilic methacrylate-based polymer microspheres for IMAC protein separation

Preparation of a new type of magnetic non-porous poly(2-hydroxyethyl methacrylate-co-glycidyl methacrylate) microspheres with hydrophilic properties containing coupled iminodiacetic acid (IDA) is described. The prepared microspheres were used for the immobilization of Ni(II) or Fe(III) ions to show their application in protein binding studies. Human IgG was bound to magnetic Ni(II)-IDA-modified microspheres and conditions of its adsorption and elution were optimized. Non-specific binding of the protein to magnetic microspheres in the absence of Ni(II) ions was low. Fe(III) ions immobilized on magnetic IDA-modified microspheres were used for the specific binding of porcine pepsin, as a model phosphoprotein. The ability of phosphate buffer to release the adsorbed enzyme from the microspheres and a low adsorption of the dephosphorylated protein indicate the participation of phosphate groups in the pepsin interaction. The elaborated method represents a rapid technique that can be used not only for the separation of proteins but also for analytical purposes.     

A rational approach in the design of selective mesoporous adsorbents

Two MCM-41 derived adsorbents have been tailor-made for the separation of silver and copper ions using the hard-soft, acid-base (HSAB) principle as the design guideline. NH2-MCM-41 containing "hard" Lewis base adsorption sites (i.e., RNH2) was prepared for the adsorption of the "hard" Lewis acid, Cu2+, and SH-MCM-41 with a grafted "soft" thiolpropyl base was prepared for the selective removal of Ag+, a "soft" Lewis acid. Single- and binary-component adsorption studies were conducted at different metal concentrations, solution compositions, and pH values. The experimental results showed that SH-MCM-41 has excellent affinity and capacity for silver adsorption and adsorbed only the silver ions with copper remaining in the solution. The selectivity was not affected by the metal concentration and composition, anion, and pH. Under similar experimental conditions, NH2-MCM-41 selectively adsorbed copper from the binary solution. The selectivity of NH2-MCM-41 remained for the copper at different pH values, although the adsorption capacity diminished at lower pH values. The type of anions used affected copper adsorption on NH2-MCM-41 with an increased copper uptake in the presence of the sulfate ions. A simple Freundlich adsorption model was sufficient to describe metal adsorption on SH-MCM-41 and NH2-MCM-41, and the LeVan and Vermeulen model was successfully used to predict the adsorption capacity and selectivity for binary-component adsorptions.     

Preparation, Properties and Mechanism of Inhomogeneous Calcium Alginate Ion Cross-linking Gel Microspheres

Inhomogeneous calcium alginate ion cross-linking gel microspheres,a novel ion absorbent,were prepared by dropping a sodium alginate solution to a calcium chloride solutioin via an electronic droplet generator.Calcium alginate microspheres have uniform particle sizes.a smooth surface and a microporous structure.The electrode probe reveals the inhomogeneous distribution of calcium ions with the highest concentration on the surface,and the lowest concentration in the cores of the spheres.As a novel ion adsorbent,calcium alginate gel microspheres have a lower limiting adsorption mass concentration,a higher enrichment capacity and a higher adsorption capacity for Pb^2 than usual ion exchange resins.The highest percentage of the adsorption is 99.79%.The limiting adsorption mass concentration is 0.0426mg/L.The adsorption capacity for Pb^2 is 644mg/g,Calcium alginate gel microspheres have a much faster ion exchange velocity than D418 chelating resin and D113 polyacrylate resin.The moving boundary model was employed to interpret the ion exchange kinetics process,which indicates that the ion exchange process is controlled by intraparticle diffusion of adsorbable ions.So the formation of inhomogeneous gel microspheres reduces the diffusion distance of adsorbable ions within the spheres and enhances the ion exchange velocity.Alginate has a higher selectivity for pb^2 than for Ca^2 and the selectivity coefficient KCa^Pb is 316. As an ion cross-linking gel,calcium alginate inhomogeneous microspheres can effectively adsorb heavy metal Pb^2 at a higher selectivity and a higher adsorption velocity.It is a novel and good ion adsorbent.     

Preparation of Fluorescent Thiol Group‐Functionalized Silica Microspheres for the Detection and Removal of Silver Ions in Aqueous Solutions

We demonstrate that silica microspheres can act as a sensitive fluorescent sensor and adsorbent of Ag⁺ in aqueous media. These thiol‐functionalized silica microspheres are doped with quantum dots (QDs) using organosilane chemistry in a one‐step preparation. Ligand exchange takes place between the thiolated organosilane and acid‐capped QDs, making the doping easy. Ag⁺ adsorption by the silica microspheres causes the decrease of fluorescence intensity of the QDs. The detection limit for Ag⁺ is found to be 10 μmol/L. The abundance of thiol groups on the surface of the microspheres could effectively remove Ag⁺ through strong interaction. When microspheres with a diameter of 1.1 μm are used as the adsorbents, the adsorption capacity for Ag⁺ reached 102 mg/g. This excellent adsorption ability is due to the abundance of thiol groups that act as the active sites, facilitating the adsorption of the massive metal ions on the surface of the microspheres. Furthermore, the adsorption isotherm data follows the Freundlich model. The structure and content of the silica microspheres were investigated by scanning and high‐resolution transmission electron microscopy, energy dispersive X‐ray spectroscopy, and Raman analysis, and the fluorescence properties were characterized by fluorescence microscopy.     

Feasibility of static secondary ion mass spectrometry to study physicochemical interactions between organic components and silver in thermographic systems

Chemical engineering of high-technology products requires elucidation of intermolecular interactions in complex materials. As part of an extensive study on thermographic systems, static secondary ion mass spectrometry (S-SIMS) was used to probe the physicochemical behaviour of active compounds, such as different tone modifiers and stabilisers, on silver. In particular, the feasibility of detecting adsorption and/or binding of individual additives and mixtures to silver was examined. Substrates prepared by sputter coating silver on silicon wafers were exposed to solutions of the studied compounds in 2-butanone. The signal intensities measured with S-SIMS for the ad-layers showed reproducibility to within 10%. Radical ions containing silver such as [M-H+Ag]+ * were used as evidence for the formation of bonds in the solid. Also the [M-H+2Ag]+ ions could be assigned to chemisorbed species while [M+Ag]+ ions could be formed by adduct ionisation of molecules with co-ejected Ag+ ions. The signal intensities of [M-H+Ag]+ * and [M-H+2Ag]+ ions were used to monitor the adsorption quantitatively as a function of time.     

均苯四甲酸酐修饰壳聚糖微球对Pb2+和Cd2+的吸附

用交联的壳聚糖微球 (CTS) 与均苯四甲酸酐在无水条件下反应,合成均苯四甲酸酐修饰壳聚糖微球,并用FT-IR和XPS表征产物的结构。研究它对水溶液中Pb2+和Cd2+的吸附行为。考察溶液的pH,吸附时间及Pb2+和Cd2+的初始浓度对吸附金属离子的影响。吸附等温线可以用Langmuir 方程较好的描述,当pH 5.0时,该吸附剂对Pb2+和Cd2+的最大吸附量分别为296.7mg g-1和149.9mg g-1。动力学过程用二级吸附动力学模拟具有很好的线性相关性,从而确定了吸附过程为化学吸附。采用0.2mol L-1的EDTA为解析剂,Pb2+和Cd2+分别获得92.4%和85.3%的解析率。表明该吸附剂有再生性能。应用于电镀废水中铅的处理,结果满意。     

活性碳纤维ZnO—SACF的制备及其对Ag^＋的氧化还原吸附

制备了含有ＺｎＯ的活性碳纤维ＺｎＯ－ＳＡＣＦ，借助ＡＡＳ，ＷＡＸＤ和ＳＥＭ探讨了ＺｎＯ－ＳＡＣＦ对Ａｇ＾＋的氧化还原吸附特性，并考察了ＺｎＯ在氧化还原中的作用。结果表明，ＺｎＯ－ＳＡＣＦ比ＳＡＣＦ具有对Ａｇ＾＋更高的氧化还原吸附量。外加ＺｎＯ的实验发现，ＺｎＯ本身并不吸附Ａｇ＾＋，但却参与氧化还原反应，中和氧化还原体系所释放出的Ｈ＾＋，提高了体系的ＰＨ值，可以认为，ＰＨ值的提高有利于ＳＡＣＦ电极电