Preparation and adsorption properties of monodisperse chitosan-bound Fe3O4 magnetic nanoparticles for removal of Cu(II) ions

Monodisperse chitosan-bound Fe(3)O(4) nanoparticles were developed as a novel magnetic nano-adsorbent for the removal of heavy metal ions. Chitosan was first carboxymethylated and then covalently bound on the surface of Fe(3)O(4) nanoparticles via carbodiimide activation. Transmission electron microscopy micrographs showed that the chitosan-bound Fe(3)O(4) nanoparticles were monodisperse and had a mean diameter of 13.5 nm. X-ray diffraction patterns indicated that the magnetic nanoparticles were pure Fe(3)O(4) with a spinel structure, and the binding of chitosan did not result in a phase change. The binding of chitosan was also demonstrated by the measurement of zeta potential, and the weight percentage of chitosan bound to Fe(3)O(4) nanoparticles was estimated to be about 4.92 wt%. The chitosan-bound Fe(3)O(4) nanoparticles were shown to be quite efficient for the removal of Cu(II) ions at pH>2. In particular, the adsorption rate was so fast that the equilibrium was achieved within 1 min due to the absence of internal diffusion resistance. The adsorption data obeyed the Langmuir equation with a maximum adsorption capacity of 21.5 mg g(-1) and a Langmuir adsorption equilibrium constant of 0.0165 L mg(-1). The pH and temperature effects revealed that the adsorption capacity increased significantly with increasing pH at pH 2-5, and the adsorption process was exothermic in nature with an enthalpy change of -6.14 kJ mol(-1) at 300-330 K.     

乙二胺改性磁性壳聚糖纳米粒子对酸性染料的吸附特性

利用乙二胺改性磁性壳聚糖纳米粒子(EMCN)吸附酸性橙7 (AO7)和酸性橙10 (AO10). EMCN制备时先通过在由环已烷/正已醇、壳聚糖和铁盐组成的反相微乳体系中加NaOH溶液沉淀剂, 得到磁性壳聚糖纳米粒子, 再经乙二胺改性以增加氨基含量和提高吸附容量. 透射电镜表明, EMCN分散良好, 粒径15-40 nm. 吸附实验表明, AO7和AO10最佳吸附分别在pH 4.0和pH 3.0. EMCN具有粒径小和高表面活性, 因此吸附速率快. 吸附平衡符合Langmuir模型, AO7和AO10的最大吸附容量分别为3.47和2.25 mmol·g^-1. 热力学分析表明吸附过程放热, 且能自发进行. EMCN可用NH⁴OH/NH⁴Cl (pH 10.0)溶液再生并可重复使用.     

表面印迹纳米磁性壳聚糖的制备及对Cu(Ⅱ)的吸附研究

将壳聚糖与自制的纳米四氧化三铁反应,加入一定量的铜盐使其与壳聚糖络合,再用环氧氯丙烷交联,用酸洗脱铜离子,得到表面印迹的纳米磁性壳聚糖.考察了阴离子、交联剂浓度对铜印迹效果的影响.用振动磁力仪及透射电镜对样品的性质进行表征.研究了表面印迹的纳米磁性壳聚糖对Cu2 的吸附性能.研究结果显示,用硝酸铜印迹制备的表面印迹纳米磁性壳聚糖吸附剂平均粒径为25nm,饱和磁化强度为98.56emu/g,壳聚糖含量为18.7%.吸附剂吸附容量大,吸附速度快.在Cu2 初始浓度为3.91mmol/L,pH为5时,15min即达到吸附平衡,以壳聚糖计Cu2 的饱和吸附量为4.07mmol/g,比纯壳聚糖粉高2倍.在含Zn2 或Cd2 、Pb2 的二元体系溶液中,离子印迹吸附剂对Cu2 具有明显的选择吸附性,而未印迹的纯壳聚糖粉几乎没有选择性.吸附剂易回收,重复使用性好,重复使用4次后,吸附量约保留最初饱和吸附量的98%.     

二异丁胺修饰的天然壳聚糖磁性微球与铼的吸附行为

以生物质废弃物螃蟹壳为原料,通过简单的化学处理制成磁性微球,再经二异丁胺(DIBA)修饰合成了生物质吸附剂FCS-DIBA[FCS:Fe3O4与壳聚糖(CS)复合微球]。 FCS-DIBA对Re(Ⅶ)具有很高的吸附选择性,最大吸附量可达185 mg/g,而且不受环境酸度的影响,在pH=2条件下可实现Re(Ⅶ)与Cu(Ⅱ)、Zn(Ⅱ)、Mn(Ⅶ)和Fe(Ⅲ)等常见共存金属离子的分离,该吸附等温线符合Langmuir方程。 此外,对FCS-DIBA吸附铼的机制和吸附稳定性能等进行了探讨。     

壳聚糖亲和磁性毫微粒的制备及其对蛋白质的吸附性能研究

以壳聚糖为包裹材料包埋自制的磁流体 ,制备了具有核 壳结构的磁性毫微粒 ,并偶联色素配基CibacronBlue 3GA(偶联量 1 4 .5μmol/mL)得到了一种新型亲和磁性毫微粒 .结果表明 ,所得亲和磁性微球具有较窄的粒径分布、形状规整 .以牛血清白蛋白 (BSA)和溶菌酶 (Lys)为目标蛋白 ,考察了该亲和磁性毫微粒的吸附性能 ,发现其对BSA和Lys的吸附量分别为 4和 2 8mg/g,吸附行为满足Langmuir吸附等温式 ,且对时间依赖性小而对溶液离子强度敏感 .     

Kinetics of adsorption of Saccharomyces cerevisiae mandelated dehydrogenase on magnetic Fe3O4–chitosan nanoparticles

The adsorption of Saccharomyces cerevisiae mandelated dehydrogenase (SCMD) protein on the surface-modified magnetic nanoparticles coated with chitosan was studied in a batch adsorption system. Functionalization of surface-modified magnetic particles was performed by the covalent binding of chitosan onto the surface of magnetic Fe₃O₄ nanoparticles. Characterization of these particles was carried out using FTIR spectra, transmission electron micrography (TEM), X-ray diffraction (XRD) and vibrating sample magnetometry (VSM). Magnetic measurement revealed that the magnetic Fe₃O₄–chitosan nanoparticles were superparamagnetic and the saturation magnetization was about 37.3 emu g⁻¹. The adsorption capacities and rates of SCMD protein onto the magnetic Fe₃O₄–chitosan nanoparticles were evaluated. The adsorption capacity was influenced by pH, and it reached a maximum value around pH 8.0. The adsorption capacity increased with the increase in temperature. The adsorption isothermal data could be well interpreted by the Freundlich isotherm model. The kinetic experimental data properly correlated with the first-order kinetic model, which indicated that the reaction is the adsorption control step. The apparent adsorption activation energy was 27.62 kJ mol⁻¹ and the first-order constant for SCMD protein was 0.01254 min⁻¹ at 293 K.     

Modifying the surface of Fe3O4/SiO2 magnetic nanoparticles with C18/NH2 mixed group to get an efficient sorbent for anionic organic pollutants

In this article, C(18)/NH(2) mixed group modified Fe(3)O(4)/SiO(2) magnetic nanoparticles (Fe(3)O(4)/SiO(2)/C(18)+NH(2) MNPs) were successfully synthesized and used for the extraction of perfluorinated compounds (PFCs) from large volume of water solution. The Fe(3)O(4)/SiO(2)/C(18)+NH(2) MNPs, about 25 nm in diameter, possess high extraction ability to the anionic organic pollutants due to the dual function of hydrophobic octadecyl group and cationic aminopropyl groups at low pH. More than 90% of the targets can be extracted from 500 mL of water solution with 0.1g of the MNP sorbent at pH 3. Twenty min is sufficient to reach adsorption equilibrium, and the targets can be desorbed from the sorbent readily with 12 mL of alkalized methanol after magnetic separation. Simplified extraction procedure could be achieved because of the superparamagnetism and high saturation magnetization of the sorbent (44 emu g(-1)). Therefore, preconcentration of trace level of PFCs from water solution can be performed by using this Fe(3)O(4)/SiO(2)/C(18)+NH(2) MNP sorbent which are stable for multiple reuses.     

Adsorption of anionic dye by anionic surfactant modified chitosan beads: Influence of hydrophobic tail and ionic head-group

In this paper, how chitosan hydrogel beads were modified by anionic surfactants (SDS, SDOS, SDBS, AOT, and DTM-12) and then used for the adsorption and removal of an anionic dye (congo red) from aqueous solutions were described. The effect of surfactant concentration, surfactant ionic head-group, and surfactant hydrophobic tail were investigated in detail. The result revealed the modified CS beads all had the obviously higher adsorption capacity than CS beads. Compared to the ionic head-group, the hydrophobic tail of the surfactant plays more important role in the adsorption, and a high adsorption capacity was observed for CS/AOT beads and CS/DTM-12 beads (both with two hydrophobic tails). The Sips isotherm model showed a good fit with the equilibrium experimental data, and the values of the heterogeneity factor (n) indicated heterogeneous adsorption. The adsorption kinetics analysis indicated that the pseudo-second-order rate model could better describe the adsorption process than the pseudo-first-order rate model.     

Electrochemical antioxidant detection technique based on guanine-bonded graphene and magnetic nanoparticles composite materials

An antioxidant (AO) amperometric technique based on guanine attached to graphene and Fe(3)O(4) nanoparticles (NPs) magnetic materials was developed. Guanine molecules acted as an antioxidant competitor were bonded with graphene nanosheets, onto which magnetic Fe(3)O(4) NPs were attached and the as-prepared magnetic composite can be attracted to the electrode surface by an external magnetic field. When applied with negative potentials, the dissolved oxygen was reduced to H(2)O(2) at the electrode surface, and then reacted with the EDTA-Fe(ii) complex via a Fenton-like reaction to produce OH radicals. After oxidation damage by OH radicals, the electrochemical oxidation of guanine gave a decreased current. In the presence of AOs, the reactive oxygen species (ROS, e.g. OH radicals and H(2)O(2)) were scavenged by AOs and fewer guanine probe molecules were oxidized, thus inducing a higher electrochemical oxidation current of guanine. So AOs competed with the guanine probe molecules toward oxidation by ROS. The current signals of the guanine probe molecules were proportional to the concentrations of AOs. A kinetic model was proposed to quantify the ROS scavenging capacities of the AOs. Using guanine as an oxidizable probe and OH radicals and H(2)O(2) as endogenous ROS, this kind of AO detection technique mimicks the antioxidant protection mechanism by small AO molecules in the human body.     

羧甲基壳聚糖对铅离子的吸附性能研究

本文研究羧甲基壳聚糖对Pb^2 的吸附作用,探讨反应时间,离子强度,溶液的PH值、羧甲基取代度,温度等因素对吸附性能的影响,结果表明羧基是吸附Pb^2 的主要活性基团,羧甲基壳聚糖对Pb^2 的饱和吸附量为3．1083mmol/g,吸附Pb^2 的能力比壳聚糖,水溶性低聚壳聚糖强。     

Preparation of magnetic chitosan and graphene oxide-functional guanidinium ionic liquid composite for the solid-phase extraction of protein

A series of novel cationic functional hexaalkylguanidinium ionic liquids and anionic functional tetraalkylguanidinium ionic liquids have been synthesized, and then magnetic chitosan graphene oxide (MCGO) composite has been prepared and coated with these functional guanidinium ionic liquids to extract protein by magnetic solid-phase extraction. MCGO-functional guanidinium ionic liquid has been characterized by vibrating sample magnetometer, field emission scanning electron microscopy, X-ray diffraction spectrometer and Fourier transform infrared spectrometer. After extraction, the concentrations of protein were determined by measuring the absorbance at 278 nm using an ultra violet visible spectrophotometer. The advantages of MCGO-functional guanidinium ionic liquid in protein extraction were compared with magnetic chitosan, graphene oxide, MCGO and MCGO-ordinary imidazolium ionic liquid. The proposed method has been applied to extract trypsin, lysozyme, ovalbumin and bovine serum albumin. A comprehensive study of the adsorption conditions such as the concentration of protein, the amount of MCGO-functional guanidinium ionic liquid, the pH, the temperature and the extraction time were also presented. Moreover, the MCGO-functional guanidinium ionic liquid can be easily regenerated, and the extraction capacity was about 94% of the initial one after being used three times.     

The influence of oxidative degradation on the preparation of chitosan nanoparticles

Chitosan nanoparticles were obtained via ionic crosslinking by using the sulfate ion. Chitosan molecular weight was varied by oxidative degradation of the chitosan β-glycoside bond, the molecular weight being indirectly monitored as the chitosan solution reduced viscosity at a fixed polymer concentration. The dependence between some physical properties of the resultant dispersions (turbidity, viscosity, zeta potential, and sedimentation column profile) and reduced viscosity was established. Atomic force microscopy images have shown the resultant particles formed to be clusters of chitosan nanoparticles with a diameter of ca. 70 nm, the interaction between these particles being characterized by FTIR spectroscopy as the result of sulfate bridging. At the end of the paper, the potential of these dispersions for the incorporation of anionic drugs via adsorption was evaluated using a model compound. The resultant dispersions were capable of adsorbing more than 25% of mass of chitosan, being the partition coefficient higher than 3,500.     

羧甲基化壳聚糖- Fe3O4纳米粒子的制备及对Zn2+的吸附行为

以共沉淀法制备纳米Fe3O4, 通过在颗粒表面接枝羧甲基化壳聚糖(CMC), 制备一种新型磁性纳米吸附剂, 用透射电镜(TEM)、X射线衍射分析(XRD)等对其进行了表征, 并考察了吸附剂对Zn2+的吸附性能. 结果表明, 制备的磁性纳米吸附剂平均粒径18 nm, 粒子中CMC的含量约5%. 该吸附剂对Zn2+吸附速率很快, 在2 min内基本达到平衡, 能有效去除Zn2+. 等温吸附数据符合Langmuir模型, 饱和吸附容量为20.4 mg•g−1, 吸附常数为0.0314 L•mg−1. 热力学计算表明吸附为放热过程, 焓变为−5.68 kJ•mol−1.     

磁性纳米材料的制备及其吸附重铬酸根离子的性能

采用沉降法合成的Fe3O4,通过二氧化硅的包裹和3-氯丙基三甲基硅烷处理后键合聚乙烯亚胺(PEI)、季铵盐化等步骤合成功能化的磁性纳米材料。 二氧化硅的包裹增加了Fe3O4纳米颗粒的分散性和稳定性。 使用FT-IR、SEM、TG和振动样品磁强计对其进行了表征,结果表明,成功的改性了磁性纳米材料。 采用静态法研究了磁性纳米材料对重铬酸根的吸附性能及各种因素对吸附性能的影响。 分离富集环境中重铬酸根的适宜条件为：酸性介质,温度25 ℃,重铬酸钾的浓度0.8 g/L,吸附量120 mg/g,接枝量越大,吸附量增加。     

Sonochemical formation of iron oxide nanoparticles in ionic liquids for magnetic liquid marble

Ionic liquids (ILs)-stabilized iron oxide (Fe(2)O(3)) nanoparticles were synthesized by the ultrasonic decomposition of iron carbonyl precursors in [EMIm][BF(4)] without any stabilizing or capping agents. The Fe(2)O(3) nanoparticles were isolated and characterized by X-ray powder diffraction, transmission electron microscopy and susceptibility measurements. The physicochemical properties of ILs containing magnetic Fe(2)O(3) nanoparticles (denoted as Fe(2)O(3)@[EMIm][BF(4)]), including surface properties, density, viscosity and stability, were investigated in detail and compared with that of [EMIm][BF(4)]. The Fe(2)O(3)@[EMIm][BF(4)] can be directly used as magnetic ionic liquid marble by coating with hydrophobic and unreactive polytetrafluoroethylene (PTFE), for which the effective surface tension was determined by the puddle height method. The resulting magnetic ionic liquid marble can be transported under external magnetic actuation, without detachment of magnetic particles from the marble surface that is usually observed in water marble.     

Fe_3O_4/CdTe/聚氨酯纳米复合物的制备及其性能研究

由共沉淀法和Stober法制备了伯胺基功能化SiO2稳定的Fe3O4磁性纳米粒子Fe3O4@SiO2-NH2;Fe3O4@SiO2-NH2与二异氰酸酯及咪唑阳离子二醇、聚乙二醇的反应使其表面形成阳离子型聚氨酯稳定层;通过阳离子型聚氨酯与CdTe量子点表面修饰的巯基乙酸间的电荷相互作用,制备得到了Fe3O4/CdTe/聚氨酯纳米复合物.用X射线衍射(XRD)、红外吸收光谱(FTIR)、热重分析(TGA)、透射电子显微镜(TEM)、磁强计(VSM)、紫外吸收光谱(UV)、荧光发射光谱(PL)表征了该纳米复合物的结构与性能.结果表明,CdTe量子点均匀地分散在Fe3O4@SiO2磁性纳米粒子周围,所得纳米复合物在溶剂中分散均匀,不团聚,且具有超顺磁性,并保持了CdTe量子点的荧光性能.     

β-Cyclodextrin assisted one-pot synthesis of mesoporous magnetic Fe3O4@C and their excellent performance for the removal of Cr Ⅵ from aqueous solutions

Mesoporous magnetic Fe3O4@C nanoparticles have been synthesized by a one-pot approach and used as adsorbents for removal of Cr (Ⅳ) from aqueous solution. Magnetic iron oxide nanostructured materials encapsulated by carbon were characterized by scanning electron microscope (SEM), nitrogen adsorption and desorption, X-ray diffraction (XRD) and Fourier transform infrared (FTIR) spectroscopy. The adsorption performance of the nanomaterial adsorbents is tested with the removal of Cr (Ⅳ) from aqueous solution. The results reveal that the mesoporous magnetic Fe3O4@C nanospheres exhibit excellent adsorption efficiency and be easily isolated by an external magnetic field. In comparison with magnetic Fe3O4 nanospheres, the mesoporous magnetic Fe3O4@C exhibited 1.8 times higher removal rate of Cr Ⅵ. Themesoporous structure and an abundance of hydroxy groups on the carbon surfacemay be responsible for high absorbent capability.     

磁性Fe3O4@SiO2@CS镉离子印迹聚合物的制备及吸附性能

以SiO2包覆的纳米Fe3O4为载体, 壳聚糖(Chitosan, CS)为功能配体, γ-缩水甘油醚氧丙基三甲氧基硅烷为交联剂, 制备了磁性Fe3O4@SiO2@CS镉离子印迹聚合物(Magnetic ion-imprinted polymer, M-IIP). 采用扫描电镜和红外光谱对该磁性印迹聚合物进行了表征. 结果表明, 壳聚糖在环氧基硅烷交联作用下, 实现了印迹壳层在磁性Fe3O4表面的接枝, 该印迹材料是边长为60~120 nm的立方体. 吸附性能实验表明, M-IIP对Cd(Ⅱ)的吸附符合一级动力学吸附模型; M-IIP对Cd(Ⅱ)/Cu(Ⅱ), Cd(Ⅱ)/Zn(Ⅱ), Cd(Ⅱ)/Pb(Ⅱ)和Cd(Ⅱ)/Hg(Ⅱ)的相对选择系数分别为2.92, 3.43, 8.97和9.20. 原子吸收光谱检测结果表明, 该磁性Fe3O4@SiO2@CS离子印迹聚合物可用于水溶液中Cd(Ⅱ)的分离, Cd(Ⅱ)回收率在98%以上.     

Cobalt and magnesium ferrite nanoparticles: preparation using liquid foams as templates and their magnetic characteristics

An easy and convenient method for the synthesis of cobalt and magnesium ferrite nanoparticles is demonstrated using liquid foams as templates. The foam is formed from an aqueous mixture of an anionic surfactant and the desired metal ions, where the metal ions are electrostatically entrapped by the surfactant at the thin borders between the foam bubbles and their junctions. The hydrolysis is carried out using alkali resulting in the formation of desired nanoparticles, with the foam playing the role of a template. However, in the formation of ferrites with the formula MFe(2)O(4), where the metal ion and iron possess oxidation states of +2 and +3, respectively, forming a foam from a 1:2 mixture of the desired ionic solutions would lead to a foam composition at variance with the original solution mixture because of greater electrostatic binding of ions possessing a greater charge with the surfactant. In our procedure, we circumvent this problem by preparing the foam from a 1:2 mixture of M(2+) and Fe(2+) ions and then utilizing the in situ conversion of Fe(2+) to Fe(3+) under basic conditions inside the foam matrix to get the desired composition of the metal ions with the required oxidation states. The fact that we could prepare both CoFe(2)O(4) and MgFe(2)O(4) particles shows the vast scope of this method for making even multicomponent oxides. The magnetic nanoparticles thus obtained exhibit a good crystalline nature and are characterized by superparamagnetic properties. The magnetic features observed for CoFe(2)O(4) and MgFe(2)O(4) nanoparticles are well in accordance with the expected behaviors, with CoFe(2)O(4) particles showing higher blocking temperatures and larger coercivities. These features can easily be explained by the contribution of Co(2+) sites to the magnetocrystalline anisotropy and the absence of the same from the Mg(2+) ions.     

Preparation of surface plasmon resonance biosensor based on magnetic core/shell Fe3O4/SiO2 and Fe3O4/Ag/SiO2 nanoparticles

In this paper, surface plasmon resonance biosensors based on magnetic core/shell Fe(3)O(4)/SiO(2) and Fe(3)O(4)/Ag/SiO(2) nanoparticles were developed for immunoassay. With Fe(3)O(4) and Fe(3)O(4)/Ag nanoparticles being used as seeding materials, Fe(3)O(4)/SiO(2) and Fe(3)O(4)/Ag/SiO(2) nanoparticles were formed by hydrolysis of tetraethyl orthosilicate. The aldehyde group functionalized magnetic nanoparticles provide organic functionality for bioconjugation. The products were characterized by scanning electronic microscopy (SEM), transmission electronic microscopy (TEM), FTIR and UV-vis absorption spectrometry. The magnetic nanoparticles possess the unique superparamagnetism property, exceptional optical properties and good compatibilities, and could be used as immobilization matrix for goat anti-rabbit IgG. The magnetic nanoparticles can be easily immobilized on the surface of SPR biosensor chip by a magnetic pillar. The effects of Fe(3)O(4)/SiO(2) and Fe(3)O(4)/Ag/SiO(2) nanoparticles on the sensitivity of SPR biosensors were also investigated. As a result, the SPR biosensors based on Fe(3)O(4)/SiO(2) nanoparticles and Fe(3)O(4)/Ag/SiO(2) nanoparticles exhibit a response for rabbit IgG in the concentration range of 1.25-20.00 μg ml(-1) and 0.30-20.00 μg ml(-1), respectively.