Nafion covered core–shell structured Fe3O4@graphene nanospheres modified electrode for highly selective detection of dopamine

Nafion covered core–shell structured Fe₃O₄@graphene nanospheres (GNs) modified glassy carbon electrode (GCE) was successfully prepared and used for selective detection dopamine. Firstly, the characterizations of hydro-thermal synthesized Fe₃O₄@GNs were investigated by scanning electron microscopy (SEM), transmission electron microscopy (TEM) and Raman spectroscopy. Then Fe₃O₄@GNs/Nafion modified electrode exhibited excellent electrocatalytic activity toward the oxidations of dopamine (DA). The interference test showed that the coexisted ascorbic acid (AA) and uric acid (UA) had no electrochemical interference toward DA. Under the optimum conditions, the broad linear relationship was obtained in the experimental concentration from 0.020 μM to 130.0 μM with the detection limit (S/N = 3) of 0.007 μM. Furthermore, the core–shell structured Fe₃O₄@GNs/Nafion/GCE was applied to the determination of DA in real samples and satisfactory results were got, which could provide a promising platform to develop excellent biosensor for detecting DA.     

Hydrophilic Nb-immobilized magnetic core–shell microsphere – A novel immobilized metal ion affinity chromatography material for highly selective enrichment of phosphopeptides

Rapid and selective enrichment of phosphopeptides from complex biological samples is essential and challenging in phosphorylated proteomics. In this work, for the first time, niobium ions were directly immobilized on the surface of polydopamine-coated magnetic microspheres through a facile and effective synthetic route. The Fe₃O₄@polydopamine-Nb⁵⁺ (denoted as Fe₃O₄@PD-Nb⁵⁺) microspheres possess merits of high hydrophilicity and good biological compatibility, and demonstrated low limit of detection (2 fmol). The selectivity was also basically satisfactory (β-casein:BSA = 1:500) to capture phosphopeptides. They were also successfully applied for enrichment of phosphopeptides from real biological samples such as human serum and nonfat milk. Compared with Fe₃O₄@PD-Ti⁴⁺ microspheres, the Fe₃O₄@PD-Nb⁵⁺ microspheres exhibit superior selectivity to multi-phosphorylated peptides, and thus may be complementary to the conventional IMAC materials.     

Pt–Sn/Al2O3 catalyst for the selective hydrodeoxygenation of esters

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Aptamer-functionalized solid phase microextraction–liquid chromatography/tandem mass spectrometry for selective enrichment and determination of thrombin

In this publication, a novel solid phase microextraction (SPME) coating functionalized with a DNA aptamer for selective enrichment of a low abundance protein from diluted human plasma is described. This approach is based on the covalent immobilization of an aptamer ligand on electrospun microfibers made with the hydrophilic polymer poly(acrylonitrile-co-maleic acid) (PANCMA) on stainless steel rods. A plasma protein, human α-thrombin, was employed as a model protein for selective extraction by the developed Apt-SPME probe, and the detection was carried out with liquid chromatography/tandem mass spectrometry (LC–MS/MS). The SPME probe exhibited highly selective capture, good binding capacity, high stability and good repeatability for the extraction of thrombin. The protein selective probe was employed for direct extraction of thrombin from 20-fold diluted human plasma samples without any other purification. The Apt-SPME method coupled with LC–MS/MS provided a good linear dynamic range of 0.5–50 nM in diluted human plasma with a good correlation coefficient (R² = 0.9923), and the detection limit of the proposed method was found to be 0.30 nM. Finally, the Apt-SPME coupled with LC–MS/MS method was successfully utilized for the determination of thrombin in clinical human plasma samples. One shortcoming of the method is its reduced efficiency in undiluted human plasma compared to the standard solution. Nevertheless, this new aptamer affinity-based SPME probe opens up the possibility of selective enrichment of a given targeted protein from complex sample either in vivo or ex vivo.     

Bifunctional polydopamine@Fe3O4 core–shell nanoparticles for electrochemical determination of lead(II) and cadmium(II)

The present paper has focused on the potential application of the bifunctional polydopamine@Fe₃O₄ core–shell nanoparticles for development of a simple, stable and highly selective electrochemical method for metal ions monitoring in real samples. The electrochemical method is based on electrochemical preconcentration/reduction of metal ions onto a polydopamine@Fe₃O₄ modified magnetic glassy carbon electrode at −1.1 V (versus SCE) in 0.1 M pH 5.0 acetate solution containing Pb²⁺ and Cd²⁺ during 160 s, followed by subsequent anodic stripping. The proposed method has been demonstrated highly selective and sensitive detection of Pb²⁺ and Cd²⁺, with the calculated detection limits of 1.4 × 10⁻¹¹ M and 9.2 × 10⁻¹¹ M. Under the optimized conditions, the square wave anodic stripping voltammetry response of the modified electrode to Pb²⁺ (or Cd²⁺) shows a linear concentration range of 5.0–600 nM (or 20–590 nM) with a correlation coefficient of 0.997 (or 0.994). Further, the proposed method has been performed to successfully detect Pb²⁺ and Cd²⁺ in aqueous effluent.     

Ce0.67Zr0.33O2对CH4燃烧催化剂Fe2O3/Al2O3的改性作用

固定n(Ce)/n(Zr)比为0.67/0.33, 用共沉淀法制得一系列CeO2-ZrO2-Al2O3固溶体. 采用这些固溶体作载体, 以Fe2O3为活性组分, 用浸渍法制备了一系列催化剂. BET结果显示, 将适量Ce0.67Zr0.33O2引入到Al2O3载体中有助于催化剂保持较高的比表面积. TPR结果显示, 载体中引入适量的Ce0.67Zr0.33O2可以改善催化剂的氧化还原性能. XRD结果表明, Fe2O3在CeO2-ZrO2-Al2O3载体上呈现出良好的分散状况, 老化前后催化剂的晶相结构基本无明显变化. 特别是当载体中m(Ce0.67Zr0.33O2)∶m(Al2O3)的值为1∶2时, Fe2O3/CeO2-ZrO2-Al2O3催化剂在甲烷催化燃烧中显示出最佳的催化性能和抗高温老化性能.     

Ce0.67Zr0.33O2对CH4燃烧催化剂Fe2O3/Al2O3的改性作用

固定n(Ce)/n(Zr)比为0.67/0.33,用共沉淀法制得一系列CeO2-ZrO2-Al2O3固溶体.采用这些固溶体作载体,以Fe2O3为活性组分,用浸渍法制备了一系列催化剂.BET结果显示,将适量Ce0.67Zr0.33O2引入到Al2O3载体中有助于催化剂保持较高的比表面积.TPR结果显示,载体中引入适量的Ce0.67Zr0.33O2可以改善催化剂的氧化还原性能.XRD结果表明,Fe2O3在CeO2-ZrO2-Al2O3载体上呈现出良好的分散状况,老化前后催化剂的晶相结构基本无明显变化.特别是当载体中m(Ce0.67Zr0.33O2)∶m(Al2O3)的值为1∶2时,Fe2O3/CeO2-ZrO2-Al2O3催化剂在甲烷催化燃烧中显示出最佳的催化性能和抗高温老化性能.     

Fe2O3/Al2O3氧载体制备方法的研究

采用溶胶-凝胶法、共沉淀法、水热合成法、低热固相合成法、机械混合法、燃烧合成法和冷冻成粒法制备铁基氧载体Fe₂O₃/Al₂O₃,并通过物理和化学表征手段来筛选和优化制备方法和制备工艺。对煅烧后的氧载体进行硬度测试,结果表明,溶胶-凝胶法、共沉淀法、机械混合法、燃烧合成法和冷冻成粒法制备的氧载体硬度较高;载体的X射线衍射(XRD)谱图表明,各种制备方法均能制得物相组成为Fe₂O₃/Al₂O₃的氧载体,且随着煅烧温度的提高、煅烧时间的延长,氧载体的结晶度、晶体粒径逐渐增大,煅烧温度1 200℃的氧载体的机械性能、晶体结构、晶相组成更稳定。借助化学吸附仪的程序升温还原(TPR)实验表征氧载体的反应活性,并计算氧载体活性度。综合物理和化学表征实验结果表明,最优制备方法为溶胶-凝胶法和冷冻成粒法。     

Comparison of liquid chromatography-microchip/mass spectrometry to conventional liquid chromatography–mass spectrometry for the analysis of steroids

The feasibility of a microfluidic-based liquid chromatography-electrospray ionization/mass spectrometric system (HPLC-Chip/ESI/MS) was studied and compared to a conventional narrow-bore liquid chromatography-electrospray ionization/mass spectrometric (LC-ESI/MS) system for the analysis of steroids. The limits of detection (LODs) for oxime derivatized steroids, expressed as concentrations, were slightly higher with the HPLC-Chip/MS system (50–300 pM) using an injection volume of 0.5 μL than with the conventional LC-ESI/MS (10–150 pM) using an injection volume of 40 μL. However, when the LODs are expressed as injected amounts, the sensitivity of the HPLC-Chip/MS system was about 50 times higher than with the conventional LC-ESI/MS system. The results indicate that the use of HPLC-Chip/MS system is clearly advantageous only in the analysis of low-volume samples. Both methods showed good linearity and good quantitative and chromatographic repeatability. In addition to the instrument comparisons with oxime derivatized steroids, the feasibility of the HPLC-Chip/MS system in the analysis of non-derivatized and oxime derivatized steroids was compared. The HPLC-Chip/MS method developed for non-derivatized steroids was also applied to the quantitative analysis of 15 mouse plasma samples.     

Aptamer-conjugated bio-bar-code Au–Fe3O4 nanoparticles as amplification station for electrochemiluminescence detection of tumor cells

An electrochemiluminescence (ECL) assay has been developed for highly sensitive and selective detection of tumor cells based on cell-SELEX aptamer-target cell interactions through a cascaded amplification process by using bio-bar-code Au–Fe₃O₄ as amplification station. Firstly, bio-bar-code toehold-aptamer/DNA primer/Au–Fe₃O₄ (TA/DP/Au–Fe₃O₄) nanoconjugates are fabricated with a ratio of 1:10 to efficiently avoid cross-linking reaction and recognize target cells, which are immobilized on the substrate by hybridizing aptamer to capture probe with 18-mer. Through strand displacement reaction (SDR), the TA/DP/Au–Fe₃O₄ composites further act as the amplification station to initiate rolling circle amplification (RCA). As a result, on the surface of TA/DP/Au–Fe₃O₄, a large number of Ru(bpy)₂(dcbpy)NHS-labeled probes hybridize to RCA products, which are easily trapped by magnetic electrode to perform the magnetic particle-based ECL platform. Under isothermal conditions, this powerful amplification strategy permits detection of Ramos cells as low as 16 cells with an excellent selectivity. Moreover, analysis of Ramos cells in complex samples and whole blood samples further show the great potential of this ultrasensitive approach in clinical application involving cancer cells-related biological processes.     

Deuterium exchange reaction of ethylbenzene over an Fe2O3?K2CO3?Cr2O3 catalyst

Isotope exchange reaction of ethylbenzene with water or hydrogen has been examined over Fe₂O₃–K₂CO₃–Cr₂O₃ catalyst. The participation of the hydrogen attached to -carbon or phenyl group was observed. The exchange rate of the -hydrogen was compared for different alkylbenzenes and found that toluene was the most active, whereas cumene was inactive. This order suggested that the -hydrogen dissociated as a proton. -Adsorbed state was supposed as an intermediate of dehydrogenation, which dissociates the -hydrogen reversibly as a proton on a basic site. Including the results of exchange reaction of styrene, the overall route of dehydrogenation is discussed.     

Synthesis and crystal structure of [Fe4O2(H2O)10(C5H5NCOO)4](NO3)8 · 2H2O

Crystals of the tetranuclear complex [Fe₄O₂(H₂O)₁₀(C₅H₅NCOO)₄](NO₃)₈ · 2H₂O are obtained by the slow evaporation of an aqueous solution of iron(III) nitrate and isonicotinic acid. According to the X-ray diffraction data, four metal atoms lie in the same plane and together with two μ₃-O oxygen atoms form the fragment [Fe₄(μ₃-O)₂]¹⁰⁺. The [Fe₄O₂(H₂O)₁₀(C₅H₅NCOO)₄]⁸⁺ cation has been obtained and structurally characterized for the first time.     

Growth of High Magnetic α-Fe2O3 and Fe3O4 Nanowires via an Oxide Assisted Vapor-Solid Process

We describes a controllable synthesis procedure for growing α-Fe₂O₃ and Fe₃O₄ nanowires. High magnetic hematite α-Fe₂O₃ nanowires are successfully grown on Fe_0.5Ni_0.5 alloy sub-strates via an oxide assisted vapor-solid process. Experimental results also indicate that previous immersion of the substrates in a solution of oxalic acid causes the grown nanowires to convert gradually into magnetite (Fe₃O₄) nanowires. Additionally, the saturated state of Fe₃O₄ nanowires is achieved as the oxalic acid concentration reaches 0.75 mol/L. The aver-age diameter and length of nanowires expands with an increasing operation temperature and the growth density of nanowires accumulates with an increasing gas flux in the vapor-solid process. The growth mechanism of α-Fe₂O₃ and Fe₃O₄ nanowires is also discussed. The results demonstrate that the entire synthesis of nanowires can be completed within 2 h.     

碳纳米管负载纳米Fe2O3的研究

本文研究了用液相化学沉积法制备的碳纳米管负载Fe₂O₃。首先用浓HCl、浓HNO₃和浓HNO₃ / H₂SO₄(混酸)三种酸对碳纳米管进行改性处理，对样品进行了TEM形貌观察和FTIR光谱分析，FTIR分析表明浓HCl处理后不能在碳纳米管表面引入官能团，而浓HNO₃能在碳纳米管表面引入-OH和-C=O，浓HNOO₃ / H₂SO₄能在碳纳米管表面引入大量的-OH、-C=O、COOH。制备了以上三种碳纳米管分别负载Fe₂O₃。TEM分析表明，负载效果：混酸>浓HNO₃>浓HCl。经混酸处理后的碳纳米管所负载的Fe₂O₃的XRD分析，表明所负载的是α-Fe₂O₃。机理分析表明碳纳米管上的含氧基团能增强其在水溶液中的分散性，同时能增强其对Fe³⁺吸附和离子交换能力，使吸附在碳纳米管表面的Fe³⁺成为结晶成核中心，调节溶液pH值后，使Fe₂O₃沉积在碳纳米管表面。     

碳纳米管负载的Fe2O3催化剂制备

Carbon nanotubes were modified by FeSO₄-H₂O₂ system, iron hydroxides were adsorbed on the wall of carbon nanotubes simultaneously. These precursors were treated at 723K for 2 h under hydrogen, nitrogen and air atmosphere to prepare carbon nanotubes supported γ-Fe₂O₃catalyst, γ-Fe₂O₃and α-Fe₂O₃compound catalyst and amorphous Fe₂O₃catalyst, respectively. This is green method to prepare high Fe₂O₃loading (≥50 %) catalyst without adding other cation. The different structures Fe₂O₃catalysts can be synthesized by controlling the condition of thermal treatment to content active phase requirements for different catalytic reactions. The paper presents a new method to prepare carbon nanotubes supported catalysts.     

Ammoxidation of 3- and 4-picolines over V2O5?SnO2/γ?Al2O3 catalyst

The ammoxidation of 3- and 4-picolines has been studied over V₂O₅–SnO₂/–Al₂O₃ catalysts prepared by surface impregnation technique. Best results were obtained for the generation of cyanopyridines in the temperature range 400–450°C and sub-stoichiometric value with respect to O₂. Catalysts that were calcined above 700°C showed no activity.

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3- 4- V₂O₅–SnO₂/–Al₂O₃, . 400–450°C O₂. , 700 K, .

     

柠檬酸盐改性Fe3O4水溶液分散性研究

四氧化三铁(Fe3O4)的水溶液分散性是影响其在生物医学中使用效果的关键因素。以FeSO4和乙二醇为原料,通过柠檬酸根离子改性,采用水热法合成了水溶液分散性良好的Fe3O4粒子。采用X-射线衍射(XRD)、扫描电镜(SEM)和红外光谱(FT-IR)分析等测试手段对制备的Fe3O4的物相、形貌、尺寸、表面吸附官能团进行了表征。研究了柠檬酸盐对样品形貌、尺寸、结晶性和水溶液分散性的影响。与未改性的Fe3O4相比,柠檬酸盐改性后的Fe3O4粒子表现出优异的水溶液分散性。     

Dehydrogenation of Isobutane Over V2O5/γ-Al2O3 Catalyst

The effect of the type of the support and the amount of V₂O₅ loading on the activity of V₂O₅/γ-Al₂O₃ catalyst for the dehydrogenation of isobutane have been investigated. Based on the experimental results of TPR, XRD and ESR spectroscopy, it is suggested that there are strong interactions between vanadia and carrier and that the V⁴⁺ species on the surface is the active site of V₂O₅/γ-Al₂O₃ for this reaction. This revised version was published online in June 2006 with corrections to the Cover Date.     

Rapid Legionella pneumophila determination based on a disposable core–shell Fe3O4@poly(dopamine) magnetic nanoparticles immunoplatform

A novel amperometric magnetoimmunoassay, based on the use of core–shell magnetic nanoparticles and screen-printed carbon electrodes, was developed for the selective determination of Legionella pneumophila SG1. A specific capture antibody (Ab) was linked to the poly(dopamine)–modified magnetic nanoparticles (MNPs@pDA-Ab) and incubated with bacteria. The captured bacteria were sandwiched using the antibody labeled with horseradish peroxidase (Ab-HRP), and the resulting MNPs@pDA-Ab-Legionella neumophila-Ab-HRP were captured by a magnetic field on the electrode surface. The amperometric response measured at −0.15 V vs. Ag pseudo-reference electrode of the SPCE after the addition of H₂O₂ in the presence of hydroquinone (HQ) was used as transduction signal. The achieved limit of detection, without pre-concentration or pre-enrichment steps, was 10⁴ Colony Forming Units (CFUs) mL⁻¹. The method showed a good selectivity and the MNPs@pDA-Ab exhibited a good stability during 30 days. The possibility of detecting L. pneumophila at 10 CFU mL⁻¹ level in less than 3 h, after performing a membrane-based preconcentration step, was also demonstrated.