表面引发原子转移自由基聚合方法合成Fe3O4/PMMA复合纳米微粒

采用表面引发原子转移自由基聚合方法合成了核壳结构的磁性高分子纳米微粒. 作为聚合反应引发剂的3-氯丙酸, 首先与油酸修饰的Fe3O4纳米微粒表面的部分油酸置换, 然后在Fe3O4纳米微粒表面引发甲基丙烯酸甲酯聚合, 合成的纳米复合材料用TEM, FTIR, XRD和DSC表征. 磁性测试结果表明, 所制备的磁性高分子纳米微粒仍具有超顺磁性, 但由于聚合物的存在, 其饱和磁化强度降低.     

无溶剂Fe3O4纳米流体的制备及表征

采用共沉淀法合成Fe3O4纳米粒子, 将含有硅氧烷基的离子型改性剂二甲基十八烷基氯化铵与Fe3O4纳米粒子进行接枝反应, 再用脂肪醇聚氧乙烯醚磺酸盐的长链阴离子交换Cl-, 在Fe3O4纳米粒子表面生成具有阴、 阳离子双电层结构的表面处理层, 得到无溶剂Fe3O4纳米流体. 研究结果表明, 在Fe3O4纳米粒子表面成功接枝了有机物长链, 改性的Fe3O4纳米粒子呈单分散分布, 其损耗剪切模量G″明显大于储能剪切模量G', 具有明显的流体行为, 在室温下即可流动.     

Fe3O4纳米晶的粒径控制合成、表征及其吸波性能

采用十二烷基磺酸钠和聚乙二醇作为保护剂, 成功地制备出Fe3O4纳米晶. 通过改变实验条件, 可在10~200 nm范围内有效调控Fe3O4纳米晶的粒径. 采用X射线衍射仪、透射电子显微镜和扫描电子显微镜等对样品的微观结构、粒径和形貌进行了分析. 结果表明, 所得尖晶石型Fe3O4纳米晶粒径均匀, 形貌均为球形. 利用振动样品磁场计测量了不同粒径样品的磁性能. 结果显示, 粒径小时, 随着粒径的增加, Fe3O4的饱和磁化强度Ms逐渐增加, 但当粒径增加到80 nm时, Ms达到最大值; 随着粒径的减小, 矫顽力也随之减小. 利用矢量网络分析仪对不同粒径样品的电磁性能和吸波性能进行了研究, 结果表明, 当Fe3O4纳米晶的粒径小于100 nm时, 吸波性能良好, 其中, 粒径为20 nm的样品吸收峰的峰值在8 GHz附近达到了-32 dB.     

纳米Fe_3O_4及钴离子掺杂Fe_3O_4:有机碱共沉淀制备和磁性质

以有机碱四甲基氢氧化铵(TMAH)为沉淀剂合成了纳米Fe3O4和Co2+掺杂的纳米Fe3O4粒子。分别讨论了碱用量,铁盐溶液浓度,反应温度,有机碱及PEG-4000的分散性等因素对纳米Fe3O4的形貌影响。结果表明,所合成的纳米Fe3O4为30nm左右的反尖晶石型面心立方结构,有机碱除了起沉淀剂作用,还能够提高纳米Fe3O4的分散性。本文还讨论了不同Co2+掺入量的纳米Fe3O4粒子的磁性质,结果表明Co2+掺杂的纳米Fe3O4粒子的矫顽力在不同掺入量的下有较大的改变。当Co2+掺入量为10.0%时,纳米Fe3O4的矫顽力达到最大值,为1628Oe。     

磁性纳米金共价固定癌胚抗原单克隆抗体的电流型免疫传感器

合成了Fe3O4/Au磁性复合纳米粒子, 在粒子表面通过自组装硫脲分子使表面氨基化, 再用戊二醛共价交联固定癌胚抗原抗体(anti-CEA). 在外加磁场的作用下, 将anti-CEA复合磁性粒子吸附在固体石蜡碳糊电极表面, 制成了新型电流型免疫传感器. 免疫电极在含有癌胚抗原CEA和辣根过氧化物酶标记的癌胚抗原(HRP-CEA)的混合溶液中温育, CEA和HRP-CEA与固定在电极表面的anti-CEA发生竞争反应, 导致HRP对H2O2的催化降解作用的改变, 从而可间接测定CEA. 由于标记的HRP可催化降解H2O2, 导致媒介体间苯二酚浓度改变, 使测定的灵敏度大大提高. 响应电流与CEA质量浓度的对数在2~160 ng/mL的范围内呈线性关系, 检出限为0.57 ng/mL(3σ法). 该免疫传感器具有制作简单、价廉及表面易于更新等特点.     

以Fe2O3为原料制备LiFePO4/C复合材料及其性能研究

以Fe2O3为铁源原料, 利用热还原法成功地制备了LiFePO4/C复合材料. 用XRD以及SEM对材料的晶体结构以及表面形貌进行了表征. 通过循环伏安和充放电测试研究了材料的电化学性能. 研究结果表明， 于700 ℃下制备的LiFePO4/C复合材料在0.1C的倍率下可以得到放电容量144.8 mA·h/g, 在循环160次后, 容量仍保持在141.4 mA·h/g. 这种以廉价的Fe2O3代替目前常用的二价铁盐原料方法, 具有减少LiFePO4合成成本的优点.     

新型有机-无机纳米复合粒子的制备及其固定化漆酶研究

制备了四氨基酞菁钴(CoTAPc)-Fe3O4纳米复合粒子, 用红外光谱(IR)、X射线衍射(XRD)、X射线能谱(EDS)、场发射扫描电镜(FEG-SEM)及振动样品磁强计等对其进行了表征. 结果表明, 形成了CoTAPc包覆在Fe3O4纳米粒子表面的纳米复合粒子. 粒子呈现不规则球形, 平均粒径为70 nm, 矫顽力为316.4 A/m, 接近超顺磁性. 以此纳米复合粒子作为载体, 通过交联法固定漆酶, 固定化酶最适反应温度为45 ℃, 最适pH为3; 固定化酶比游离酶具有更好的热稳定性、贮存稳定性及操作稳定性, 且易于分离.     

基于聚乙烯醇/Fe2O3纳米颗粒的纤维素酶固定化

以聚乙烯醇/Fe2O3磁性纳米颗粒为纤维素酶固定化载体, 通过反复冻融的方法成功地实现了纤维素酶固定化. 采用透射电镜、红外光谱仪、振动样品磁强度计对固定化酶复合体进行了表征, 结果显示, 固定化酶复合体为大小约1 μm的微凝胶团, 内含10 nm左右的Fe2O3纳米颗粒. 研究影响固定化因素后发现, 当pH为6, 固定化时间为11 h, 纤维素酶/PVA质量比为4, PVA/Fe质量比为50时, 固定化纤维素酶效果最好. 通过该方法固定后酶活回收率达42%, 酶水解效率显著提高, 经过5次反应后的固定化酶相对酶活力保留50%以上. 因此, 基于聚乙烯醇/Fe2O3纳米颗粒的纤维素酶固定有利于酶的循环使用并显著提高酶的使用效率, 是一种有效固定化纤维素酶的新方法.     

纳米Fe3O4/聚苯乙烯均匀分散体系的制备及结构

用化学共沉淀法制备了Fe3O4纳米颗粒,以油酸为表面活性剂,苯乙烯为载液,制备了稳定的纳米Fe3O4可聚合磁流体,将可聚合磁流体经自由基引发聚合制成纳米Fe3O4/聚苯乙烯均匀分散体系,用WAXRD研究了Fe3O4纳米粒子的结晶情况;用FTIR研究了油酸表面改性前后Fe3O4粒子表面官能团的变化;用TEM研究了Fe3O4颗粒的粒径大小及其在苯乙烯单体和聚苯乙烯中的分散情况;用DSC和TGA研究了纳米Fe3O4/聚苯乙烯均匀分散体系的玻璃化转变温度(Tg)和热稳定性,结果表明,合成的纳米Fe3O4为立方晶型,平均粒径在10nm左右,油酸分子在Fe3O4表面是化学吸附,经表面处理的Fe3O4超细颗粒在苯乙烯和聚苯乙烯基体中分散较均匀.界面粘结较好,含1.8％Fe3O4纳米颗粒的聚苯乙烯的最大热失重温度比聚苯乙烯提高了13K,Fe3O4/聚苯乙烯复合体系的饱和磁化强度σs为17.43emu/g.     

用于α-胰凝乳蛋白酶固定化的氨基超顺磁纳米凝胶的光化学合成与表征

通过霍夫曼降解光化学原位聚合制备的聚丙烯酰胺包覆的Fe3O4纳米粒子得到了氨基化磁性纳米凝胶, 用缩合剂1-乙基-3-(3-二甲胺)碳二亚胺成功地将α-胰凝乳蛋白酶固定到氨基化磁性纳米凝胶上, 并采用光子相关光谱、傅里叶变换红外光谱、透射电子显微镜、X射线粉末衍射和热重-示差扫描量热联用等多种手段对其进行了表征. 固定化了的α-胰凝乳蛋白酶平均粒径约为31 nm; 热重法测得每克凝胶上的载酶量为69 mg, BCA 法测得每克凝胶上的载酶量为61 mg; 酶的固定化和氙灯辐照并未改变Fe3O4的晶形结构; 固定化酶比活力为0.93 U/(mg·min), 为自由酶活力的59.3%; 磁含量高达88%, 具有优异的磁响应性能, 可应用于诸多生物医药领域的快速检测、分离及酶的再生利用.     

Dendrimer modified magnetite nanoparticles for protein immobilization

A cascading polyamidoamine (PAMAM) dendrimer was synthesized on the surface of magnetite nanoparticles to allow enhanced immobilization of bovine serum albumin (BSA). Characterization of the synthesis revealed exponential doubling of the surface amine from generations one through four starting with an amino silane initiator. Furthermore, transmission electron microscopy (TEM) revealed clear dispersion of the dendrimer-modified magnetite nanoparticles in methanol solution. The dendrimer-modified magnetite nanoparticles were used to carry out magnetic immobilization of BSA. BSA immobilizing efficiency increased with increasing generation from one to five and BSA binding amount of magnetite nanoparticles modified with G5 dendrimer was 7.7 times as much as that of magnetite nanoparticles modified with only aminosilane. There are two major factors that improve the BSA binding capacity of dendrimer-modified magnetite nanoparticles: one is that the increased surface amine can be conjugated to BSA by a chemical bond through glutaraldehyde; the other is that the available area has increased due to the repulsion of surface positive charge.     

Preparation of acid-resistant magnetic adsorbent for effective removal of p-nitrophenol

Bilayer-silane-coated Fe₃O₄ nanoparticles with inner layer of tetraethoxy silane（TEOS） and outer layer of vinyltriethoxysilane （VTEO） were generated to enhance their acid resistance.These nanoparticles were copolymerized with vinylbenzyl chloride（VBC） using suspension polymerization,and then post-crosslinked.The resulting hypercrosslinked magnetic resin M150 presented specific bimodal property with large specific surface area of 1109 m²/g.It exhibited more excellent adsorption capacity of p-nitrophenol compared to another two magnetic adsorbents Ql 50 and MIEX^.Moreover,the acid stable property of the magnetite in M150 extended its application at low pH value.     

Preparation and controlled self-assembly of Janus magnetic nanoparticles

Janus magnetic nanoparticles (~20 nm) were prepared by grafting either polystyrene sodium sulfonate (PSSNa) or polydimethylamino ethylmethacrylate (PDMAEMA) to the exposed surfaces of negatively charged poly(acrylic acid) (PAA)-coated magnetite nanoparticles adsorbed onto positively charged silica beads. Individually dispersed Janus nanoparticles were obtained by repulsion from the beads on reversal of the silica surface charge when the solution pH was increased. Controlled aggregation of the Janus nanoparticles was observed at low pH values, with the formation of stable clusters of approximately 2-4 times the initial size of the particles. Cluster formation was reversed, and individually dispersed nanoparticles recovered, by restoring the pH to high values. At intermediate pH values, PSSNa Janus nanoparticles showed moderate clustering, while PDMAEMA Janus nanoparticles aggregated uncontrollably due to dipolar interactions. The size of the stable clusters could be controlled by increasing the molecular weight of the grafted polymer, or by decreasing the magnetic nanoparticle surface availability for grafting, both of which yielded larger cluster sizes. The addition of small amounts of PAA-coated magnetic nanoparticles to the Janus nanoparticle suspension resulted in a further increase in the final cluster size. Monte Carlo simulation results compared favorably with experimental observations and showed the formation of small, elongated clusters similar in structure to those observed in cryo-TEM images.     

两亲性高度枝化聚酯纳米微粒的合成与表征

用最简单的缩聚反应制备了一系列新的两亲性高度枝化聚酯纳米微粒（ＨＢＰＮ），用激光光散射技术对其在二甲基甲酰胺（ＤＭＦ）和缓冲溶液（ｐＨ＝１２）中的溶液性质进行了研究。结果表明。ＨＢＰＮ粒径大小原则上可以由聚合时间来控制；在ＤＭＦ中呈单分子分散，不溶于水，溶于碱性溶液，表面带负电荷；在ｐＨ＝１２的缓冲液中稳定，但会有极少量的缔合。     

Heterostructured magnetic nanotubes

Heterostructured magnetic tubes with submicrometer dimensions were assembled by the layer-by-layer deposition of polyelectrolytes and nanoparticles in the pores of track-etched polycarbonate membranes. Multilayers composed of poly(allylamine hydrochloride) and poly(styrene sulfonate) assembled at high pH (pH > 9.0) were first assembled into the pores of track-etched polycarbonate membranes, and then multilayers of magnetite (Fe3O4) nanoparticles and PAH were deposited. Transmission electron microscopy (TEM) confirmed the formation of multilayer nanotubes with an inner shell of magnetite nanoparticles. These tubes exhibited superparamagnetic characteristics at room temperature (300 K) as determined by a SQUID magnetometer. The surface of the magnetic nanotubes could be further functionalized by adsorbing poly(ethylene oxide)-b-poly(methacrylic acid) block copolymers. The separation and release behavior of low molecular weight anionic molecules (i.e., ibuprofen, rose bengal, and acid red 8) by/from the multilayer nanotubes were studied because these tubes could potentially be used as separation or targeted delivery vehicles. The magnetic tubes could be successfully used to separate (or remove) a high concentration of dye molecules (i.e., rose bengal) from solution by activating the nanotubes in acidic solution. The release of the anionic molecules in physiologically relevant buffer solution showed that whereas bulky molecules (e.g., rose bengal) release slowly, small molecules (i.e., ibuprofen) release rapidly from the multilayers. The combination of the template method and layer-by-layer deposition of polyelectrolytes and nanoparticles provides a versatile means to create functional nanotubes with heterostructures that can be used for separation as well as targeted delivery.     

Effect of surface interaction of silica nanoparticles modified by silane coupling agents on viscosity of methylethylketone suspension

In order to control the viscosity of a dense silica methylethylketone (MEK) suspension, the surfaces of silica nanoparticles were modified by 3-glycidoxypropyltrimethoxysilane (GPS) or hexyltrimethoxysilane (C6S) in MEK with the addition of a small amount of pH-controlled water. First, the effect of water addition on the amount of chemisorbed coupling agent was investigated. pH-controlled water enhanced the reactivity of the coupling agent in MEK. The amount of chemisorbed coupling agent increased slightly with the addition of pH 3 water and increased remarkably with the addition of pH 12 water. Next, the effect of the organic functional groups of the coupling agent, pH of the additive water, and additive amount of coupling agent on surface interaction were determined by colloid probe AFM. The steric repulsive force between the silica nanoparticles increased due to water addition, particularly when the pH was maintained at 3. The viscosity of the silica MEK suspension reduced effectively when this repulsive force appeared; however, the optimum condition for reducing the suspension viscosity was dependent on the coupling agent species. The viscosity of the dense silica MEK suspension can be controlled by the addition of small amounts of pH-controlled water and the functional groups of the coupling agent.     

Fabrication of a magmolecule using nanoparticle and evaluation of its adsorption capacity for selenium ions from nuclear wastewater

The purpose of present study is to fabrication of a magmolecule (amino-functionalized magnetite nanoparticles) and evaluation of its adsorption capacity for selenite (SeO₃ ^2?) ions from nuclear wastewater. To accomplish this, synthesized magnetite nanoparticles is coated with a layer of SiO₂ in order to be chemically stable and then functionalized with 3-aminopropyl triethoxysilane (APTES) to be more effective. Adsorption of SeO₃ ^2? ions was investigated in batch technique. The effect of parameters such as solution pH, presence of competing anions using sulfuric acid and nitric acid (NO₃ ^?, HSO₄ ^? and SO₄ ^2?) and temperature were studied. Maximum adsorption occurred at pH 2.4 for magnetite (naked nanoparticle) and 1.7 for functionalized nanoparticles, while the dose of adsorbent was 1 g/L and selenite ion concentration was 50 mg/L. sulfuric acid was selected as the better acidic agent for controlling pH of solution. Thermodynamic parameters were also calculated and it has been found that the adsorption was endothermic. The obtained result showed that the naked particles had more adsorption capacity but it has been suggested usage of functionalized particles in the magmolecule process duo to stability and reusable capability.     

Interaction between blood plasma proteins and magnetite nanoparticles

Spin label EPR spectroscopy and dynamic and Rayleigh light scattering are employed to study the interaction between magnetite nanoparticles with a diameter of 17 nm and plasma proteins (fibrinogen and albumin). Protein molecules are shown to be adsorbed on nanoparticle surface with the formation of multilayer shells. When a buffer solution (pH 8.5) contains 0.01 vol % nanoparticles, 90–100 fibrinogen molecules are adsorbed per one particle and the thickness of an adsorbed layer is 30–40 nm. For albumin, the layer thickness is 10–15 nm. In a constant magnetic field, large linear microsized aggregates oriented parallel to field lines are formed in dispersions of nanoparticles covered with adsorbed protein molecules. The study of fibrin gel formation resulting from the action of thrombin enzyme on fibrinogen suggests that, in the presence of nanoparticles, the rate of gelation decreases by a factor of approximately two, while the ratio between the average mass and average length of fibrin polymer fibers rises.     

Retention of ionisable compounds on high-performance liquid chromatography XVII. Estimation of the pH variation of aqueous buffers with the change of the methanol fraction of the mobile phase

The use of methanol-aqueous buffer mobile phases in HPLC is a common election when performing chromatographic separations of ionisable analytes. The addition of methanol to the aqueous buffer to prepare such a mobile phase changes the buffer capacity and the pH of the solution. In the present work, the variation of these buffer properties is studied for acetic acid-acetate, phosphoric acid-dihydrogenphosphate-hydrogenphosphate, citric acid-dihydrogencitrate-hydrogencitrate-citrate, and ammonium-ammonia buffers. It is well established that the pH change of the buffers depends on the initial concentration and aqueous pH of the buffer, on the percentage of methanol added, and on the particular buffer used. The proposed equations allow the pH estimation of methanol-water buffered mobile phases up to 80% in volume of organic modifier from initial aqueous buffer pH and buffer concentration (before adding methanol) between 0.001 and 0.01 mol L(-1). From both the estimated pH values of the mobile phase and the estimated pKa of the ionisable analytes, it is possible to predict the degree of ionisation of the analytes and therefore, the interpretation of acid-base analytes behaviour in a particular methanol-water buffered mobile phase.     

Modification of the wettability of a polymeric substrate by pH effect. Determination of the surface acid dissociation constant by contact angle measurements

The wetting properties of a substrate can be changed by chemical reaction. Here, we studied simple materials with acid-base properties, by preparing poly(vinyl chloride) films containing lauric acid. These substrates constitute simple polymeric surfaces the wettability of which can be easily controlled by the acid-base equilibrium. The roughness of the material was then varied by adding Aerosil (hydrophobic fumed silica). We then studied the wettability of these materials toward aqueous buffer solutions between pH 2 and 12 from contact angle measurements. The variation of the contact angle of a droplet of buffer solution with the pH of the solution was described by a simple thermodynamic model requiring only two parameters. Thus, we could characterize the acid polymer by an effective surface acid dissociation constant the value of which was consistent with those obtained with a similar surface. We showed that the behavior of any substrate could be described even if the surface geometry was not well-known.