High-performance sono/nano-catalytic system: Fe3O4@Pd/CaCO3-DTT core/shell nanostructures,a suitable alternative for traditional reducing agents for antibodies

Herein, a novel heterogeneous nanoscale reducing agent for antibody cleavage, made of iron oxide nanoparticles, silica network, palladium on calcium carbonate (10%), and dithiothreitol (Fe₃O₄@Pd/CaCO₃-DTT), is presented as a substantial alternative for traditional homogeneous analogues. Conventionally, antibody fragmentation is accomplished using reducing agents and proteases that digest or cleave certain portions of the immunoglobulin protein structure to provide active thiol sites for drug tagging aims. Then, dialysis process is needed to separate excess chemical structures and purify the reduced antibody. In this work, we have made an effort to design a suitable heterogeneous tool for protein cleavage and skip the dialysis process for purification of the reduced antibody. In this regard, firstly, various preparation methods including microwave irradiation, reflux and ultrasonication have been precisely compared, and it has been proven that the best result is obtained through 10 min ultrasound (US) irradiation using an US bath with 50 KHz frequency and 200 W L⁻¹ power density. Then, all the necessary structural analyses have been done and thoroughly interpreted for the final product. Afterward, the catalytic performance of Fe₃O₄@Pd/CaCO₃-DTT nanoscale system in the presence of US waves (50 KHz, 200 W) has been monitored using some disulphide derivatives. The NPs could be conveniently separated from the mixture through their substantial paramagnetic property. Thus, dialysis process in which various types of membranes are used is practically jumped after the reduction process. In this work, this is clearly demonstrated that there is a constructive synergistic effect between US waves and prepared Fe₃O₄@Pd/CaCO₃-DTT nanoscale reducing agent. Ultimately, trastuzumab (anti HER-2) antibody has been used to test the performance of the prepared Fe₃O₄@Pd/CaCO₃-DTT NPs in a real protein reduction reaction.     

Preparation and photocatalytic properties of magnetically reusable Fe3O4@ZnO core/shell nanoparticles

Fe₃O₄@ZnO binary nanoparticles were synthesized by a simple two-step chemical method and characterized using various analytical instruments. TEM result proved the binary nanoparticles have core/shell structures and average particle size is 60 nm. Photocatalytic investigation of Fe₃O₄@ZnO core/shell nanoparticles was carried out using rhodamine B (RhB) solution under UV light. Fe₃O₄@ZnO core/shell nanoparticles showed enhanced photocatalytic performance in comparison with the as prepared ZnO nanoparticles. The enhanced photocatalytic activity for Fe₃O₄@ZnO might be resulting from the higher concentration of surface oxygen vacancies and the suppressing effect of the Fe³⁺ ions on the recombination of photoinduced electron–hole pairs. Magnetization saturation value (5.96 emu/g) of Fe₃O₄@ZnO core/shell nanoparticles is high enough to be magnetically removed by applying a magnetic field. The core/shell photocatalyst can be easily separated by using a commercial magnet and almost no decrease in photocatalytic efficiency was observed even after recycling six times.     

Mechanism study of Single-Step synthesis of Fe(core)@Pt(shell) nanoparticles by sonochemistry

Transition metal (TM) core-platinum (Pt) shell nanoparticles (TM@Pt NPs) are attracting a great deal of attention as highly active and durable oxygen reduction reaction (ORR) electrocatalysts of fuel cells and metal-air batteries. However, most of the reported synthesis methods of TM@Pt NPs are multistep in nature, a significant disadvantage for real applications. In this regard, our group has reported a single-step method to synthesize TM@Pt NPs for TM = Mn, Fe, Co, and Ni by using sonochemistry, namely the UPS (ultrasound-assisted polyol synthesis) method. Previously, we proposed the mechanism of the formation of these TM@Pt NPs by UPS method, but rather in a rough sense. Some details are missing and the optimal conditions have not been established. In the present work, we performed detailed studies on the formation mechanism of UPS reaction by using Fe@Pt NPs as the model system. Effects of synthesis parameters such as the nature of metal precursor, conditions of ultrasound, and temperature profile as a function of reaction time were assessed, along with the analyses of intermediates during the UPS reaction. As results, we verified our previously proposed mechanism that, under appropriate conditions, Fe core is formed through the cavitation and implosion of the solvent, induced by the ultrasound, and the Pt shell is formed by the chemical reaction between Fe core and Pt reagent, independent from the direct effect of ultrasound. In addition, we established the optimal conditions to obtain a high purity Fe@Pt NPs in a high yield (>90% based on Pt), which may enable the increase of synthesis scale of Fe@Pt NPs, a necessary step for the real application of TM@Pt NPs.     

Effect of gold nanoparticle size on acoustic cavitation using chemical dosimetry method

When a liquid is irradiated with high intensities of ultrasound irradiation, acoustic cavitation occurs. Acoustic cavitation generates free radicals from the breakdown of water and other molecules. Cavitation can be fatal to cells and is utilized to destroy cancer tumors. The existence of particles in liquid provides nucleation sites for cavitation bubbles and leads to decrease the ultrasonic intensity threshold needed for cavitation onset. In the present investigation, the effect of gold nanoparticles with appropriate amount and size on the acoustic cavitation activity has been shown by determining hydroxyl radicals in terephthalic acid solutions containing 15, 20, 28 and 35 nm gold nanoparticles sizes by using 1 MHz low level ultrasound. The effect of sonication intensity in hydroxyl radical production was considered.The recorded fluorescence signal in terephthalic acid solutions containing gold nanoparticles was considerably higher than the terephthalic acid solutions without gold nanoparticles at different intensities of ultrasound irradiation. Also, the results showed that the recorded fluorescence signal intensity in terephthalic acid solution containing finer size of gold nanoparticles was lower than the terephthalic acid solutions containing larger size of gold nanoparticles. Acoustic cavitation in the presence of gold nanoparticles can be used as a way for improving therapeutic effects on the tumors.     

Fe3O4@MIL-100(Fe) modified ZnS nanoparticles with enhanced sonocatalytic degradation of tetracycline antibiotic in water

Sonocatalysis has attracted excellent research attention to eradicate hazardous pollutants from the environment effectively. This work synthesised an organic/inorganic hybrid composite catalyst by coupling Fe₃O₄@MIL-100(Fe) (FM) with ZnS nanoparticles using the solvothermal evaporation method. Remarkably, the composite material delivered significantly enhanced sonocatalytic efficiency for removing tetracycline (TC) antibiotics in the presence of H₂O₂ compared to bare ZnS nanoparticles. By adjusting different parameters such as TC concentration, catalyst dosage and H₂O₂ amount, the optimized composite (20 %Fe₃O₄@MIL-100(Fe)/ZnS) removed 78.25% antibiotic in 20 min at the cost of 1 mL of H₂O₂. These much superior activities are attributed to the efficient interface contact, effective charge transfer, accelerated transport capabilities and strong redox potential for the superior acoustic catalytic performance of FM/ZnS composite systems. Based on various characterization, free radical capture experiments and energy band structures, we proposed a mechanism for the sonocatalytic degradation of tetracycline based on S-scheme heterojunctions and Fenton like reactions. This work will provide an important reference for developing ZnS-based nanomaterials to study sonodegradation of pollutants.     

Surfactant-free coating of thiols on gold nanoparticles using sonochemistry: A study of competing processes

A method for the surfactant-free coating of gold nanoparticles with thiols using sonochemistry is presented. The gold nanoparticles were prepared by a modified Zsigmondy method, affording good control over the particle-size distribution, and the thiol coating was performed by the sonication of a biphasic system consisting of a nanoparticle suspension in water and thiols in toluene. The effects of two important reaction parameters on the particle morphology, viz. sonication time and thiol concentration, were investigated in detail using transmission electron microscopy. The effect of the thiol chain length was also studied. We show that the morphology of the coated particles is determined through a competition between two opposing effects: particle fusion, due to the sonication conditions, and digestive ripening, due to the action of the thiols. Additionally, we illustrate the utility of our technique for various applications, including surface-enhanced Raman scattering from bound molecules, and further functionalization using a thiol-exchange reaction. Our technique paves the way for an efficient synthesis of thiol-coated AuNPs of different shapes and sizes, suitable for a range of diverse applications.     

H2O2氧化法制备Fe3O4纳米颗粒及与共沉淀法制备该样品的比较

在近中性条件下,利用H2O2氧化Fe(OH)2胶体成功制备了Fe3O4纳米颗粒.分别利用透射电镜(TEM),x射线衍射仪(XRD),振动样品磁强计(VSM)和超导量子干涉仪(SQUID)对样品的形貌,结构,宏观磁性进行了表征和测量.TEM图像表明样品为球形颗粒,直径大小约18nm,且分布较均匀.XRD结果表明样品为立方尖晶石结构.穆斯堡尔谱测量表明样品室温下对应两套六线谱,样品的晶体结构存在缺陷,内磁场略小于块体Fe3O4的值.宏观磁测量表明样品的饱和磁化强度可达67×10-3A·m2/g,在20 K出现了Verwey转变.选择该法制备的Fe3O4纳米颗粒与共沉淀法得到的样品作了磁性比较.宏观磁测量表明共沉淀法制备的样品在外磁场为1T时仍未饱和,磁化强度仅为46×10-3A·m2/g,在178K出现了超顺磁转变温度,且在测量温度范围内没有发现Verwey转变.     

Electrostatic self-assembly of Fe3O4 nanoparticles on carbon nanotubes

Carbon nanotubes (CNTs)-based magnetic nanocomposites can find numerous applications in nanotechnology, integrated functional system, and in medicine owing to their great potentialities. Herein, densely distributed magnetic Fe₃O₄ nanoparticles were successfully attached onto the convex surfaces of carbon nanotubes (CNTs) by an in situ polyol-medium solvothermal method via non-covalent functionalization of CNTs with cationic surfactant, cetyltrimethylammonium bromide (CTAB), and anionic polyelectrolyte, poly(sodium 4-styrenesulfonate) (PSS), through the polymer-wrapping technique, in which the negatively charged PSS-grafted CNTs can be used as primer for efficiently adsorption of positively metal ions on the basis of electrostatic attraction. X-ray diffractometry (XRD), X-ray photoelectron spectroscopy (XPS) and transmission electron microscopy (TEM) analysis have been used to study the formation of Fe₃O₄/CNTs. The Fe₃O₄/CNTs nanocomposites were proved to be superparamagnetic with saturation magnetization of 43.5 emu g^?1. A mechanism scheme was proposed to illustrate the formation process of the magnetic nanocomposites.     

A facile one-pot ultrasound assisted for an efficient synthesis of benzo[g]chromenes using Fe3O4/polyethylene glycol (PEG) core/shell nanoparticles

In this research, a general synthetic method for the synthesis of benzo[g]chromenes has been developed using Fe₃O₄/polyethylene glycol (PEG) core/shell nanoparticle under ultrasonic irradiations. Compared to the conventional methods, ultrasound procedure showed several advantages including mild reaction conditions, high yield products, short reaction times, reusability of the catalyst and little catalyst loading.     

Synthesis of nanocomposites of iron oxide/gold (Fe3O4/Au) loaded on activated carbon and their application in water treatment by using sonochemistry: Optimization study

This paper focuses on the finding best operational conditions using response surface methodology (RSM) for Rhodamine123 (R123) and Disulfine blue (DSB) dyes removal by ultrasound assisted adsorption onto Au-Fe₃O₄ nanoparticles loaded on activated carbon (Au-Fe₃O₄ NPs-AC). The influences of variables such as initial R123 (X₁) and DSB concentration (X₂), pH (X₃), adsorbent mass (X₄) and sonication time (X₅) on their removal were investigated by small central composite design (CCD) under response surface methodology. The significant variables and the possible interactions among variables were investigated and estimated accordingly. The best conditions were set as: 4 min, 4.0, 0.025 g, 13.5 and 26.5 mg L⁻¹ for sonication time, pH, adsorbent weight, initial R123 and DSB concentration, respectively. At above conditions, the adsorption equilibrium and kinetic follow the Langmuir isotherm and pseudo-second-order kinetic model, respectively. The maximum monolayer capacity (Q_max) of 71.46 and 76.38 mg g⁻¹ for R123 and DSB show sufficiency of model for well presentation of experimental data.     

多孔SiO2包裹磁性纳米颗粒Fe3O4的制备与表征

采用加热分解油酸铁法制备了Fe₃O₄磁性纳米颗粒,并用有机模板和反相微乳液相结合的方法将磁性纳米颗粒包裹在多孔二氧化硅中.用红外光谱(FTIR)研究了不同的处理方式对油酸铁表面官能团的影响及油酸的反应浓度和加热分解油酸铁的过程中升温速率对Fe₃O₄纳米颗粒的影响.结果表明,用乙醇和丙酮处理后的固态蜡状油酸铁表面的油酸基团会受到损害,将不利于加热分解时形成单分散性的Fe₃O₄纳 关键词： 3O₄纳米颗粒')" href="#">Fe₃O₄纳米颗粒 2包裹')" href="#">多孔SiO₂包裹 反相微乳液法 油酸铁     

Effects of pressure on maghemite nanoparticles with a core/shell structure

The magnetic property and intraparticle structure of the γ phase of Fe₂O₃ (maghemite) nanoparticles with a diameter (D) of 5.1±0.5 nm were investigated through AC and DC magnetic measurements and powder X-ray diffraction (XRD) measurements at pressures (P) up to 27.7 kbar. Maghemite originally exhibits ferrimagnetic ordering below 918 K, and has an inverse-spinel structure with vacancies. Maghemite nanoparticles studied here consist of a core with structural periodicity and a disordered shell without the periodicity, and core shows superparamagnetism. The DC and AC susceptibilities reveal that the anisotropy energy barrier (ΔE/k_B) and the effective value of the core moment decrease against the initial pressure (P≤3.8 kbar), recovering at P≥3.8 kbar. The change of ΔE/k_B with P is qualitatively identical with that of the core moment, suggesting a down-and-up fluctuation of the number of Fe³⁺ ions constituting the core at the pressure threshold of about 4 kbar. This phenomenon was confirmed by the analysis of the XRD measurement using Scherrer’s formula. The core volume decreased for P≤2.5 kbar, whereas at higher pressure the core was restructured. For 2.5≤P≤10.7 kbar, the volume shrinkage of particle hardly occurs. There, ΔE/k_B is approximately proportional to the volume associated to the ordered fraction of the nanoparticles as seen from XRD, V_core. From this dependence it is possible to separate the core/shell contribution to ΔE/k_B and estimate core and surface anisotropy constants. As for the structural experiments, similar experimental data have been obtained for D=12.8±3.2 nm as well.     

Optical properties of hybrid plasmonic nanofluid based on core/shell nanoparticles

The plasmonic effect is used in nanofluid to help capture and absorb sunlight. The optical absorption is significantly enhanced as plasmonic effect excited. To obtain an enhanced absorption in a broad band, the hybrid plasmonic nanofluid is developed. It is composed of core/shell nanoparticles of different sizes. The overall absorption of hybrid nanofluid is examined. Compared to the nanofluid of single particle size, the hybrid nanofluid exhibits a broadband absorption. As particle size increases, the plasmon resonance peak is shifted to longer wavelength. The variation in the sizes of core/shell nanoparticles can broaden the absorption spectrum. In the near-infrared region, the proportion of different size particles has an obvious influence. With the increase of proportion of larger particles, the absorption band is broadened. Since the suspended nanoparticles have different sizes, the particle distribution in base fluid also has an effect on absorption of light. The large particle in upper has a broadband absorption, however, less energy can be transmitted to lower after the absorption of upper particles. The contribution from the particles in lower is relatively weak.     

Preparation of Fe3O4/polystyrene composite particles from monolayer oleic acid modified Fe3O4 nanoparticles via miniemulsion polymerization

Fe₃O₄/polystyrene composite particles were prepared from oleic acid (OA) modified Fe₃O₄ nanoparticles via miniemulsion polymerization. It was concluded that the surface properties of OA modified magnetite nanoparticles have a great effect on preparation of the composite particles. When Fe₃O₄ nanoparticles coated by multilayer of OA was employed, there were large amounts of free polystyrene particles in the product. Fe₃O₄/polystyrene composite particles with defined structure and different magnetite content can be readily prepared from monolayer OA modified Fe₃O₄ nanoparticles. It was concluded that surface of the monolayer OA modified Fe₃O₄ nanoparticles is more hydrophobic than that of the multilayer coated ones, thus improving the dispersibility of the Fe₃O₄ nanoparticles in styrene monomer and allowing preparation of the Fe₃O₄/polystyrene composite particles with defined structure and controllable magnetite content.     

Growth and characterization of Fe3O4 nanoparticles in silica matrix

Nano-magnetic Fe₃O₄ particles coated with silica are synthesized. The study of structural and magnetic properties was carried out using X-ray diffraction, scanning electron microscopy, transmission electron microscopy, and vibrating sample magnetometer (VSM) techniques. The VSM results show that these kinds of composite particles exhibit superparamagnetic behavior with zero coercivity and remanence. The magnetic spheroid alumina carriers containing these magnetic composite particles were prepared by an internal gelation process. The SiO₂ coatings prevent the reaction between Fe₃O₄ and Al₂O₃ during the sintering process and maintain the superparamagnetic behavior of the catalyst carriers.     

Sonochemical fabrication of Fe3O4 nanoparticles on reduced graphene oxide for biosensors

This study synthesized Fe₃O₄ nanoparticles of 30–40 nm by a sonochemical method, and these particles were uniformly dispersed on the reduced graphene oxide sheets (Fe₃O₄/RGO). The superparamagnetic property of Fe₃O₄/RGO was evidenced from a saturated magnetization of 30 emu/g tested by a sample-vibrating magnetometer. Based on the testing results, we proposed a mechanism of ultrasonic waves to explain the formation and dispersion of Fe₃O₄ nanoparticles on RGO. A biosensor was fabricated by modifying a glassy carbon electrode with the combination of Fe₃O₄/RGO and hemoglobin. The biosensor showed an excellent electrocatalytic reduction toward H₂O₂ at a wide, linear range from 4 × 10^?6 to 1 × 10^?3 M (R² = 0.994) as examined by amperometry, and with a detection limit of 2 × 10^?6 M. The high performance of H₂O₂ detection is attributed to the synergistic effect of the combination of Fe₃O₄ nanoparticles and RGO, promoting the electron transfer between the peroxide and electrode surface.     

Synthesis and drug-loading properties of folic acid-modified superparamagnetic Fe3O4 hollow microsphere core/mesoporous SiO2 shell composite particles

Magnetic nanoparticles with immobilized metal ligands were prepared for the separation of antibody fragments. First, iron oxide nanoparticles were produced in a solvothermal synthesis using triethylene glycol as solvent and iron(III) acetylacetonate as organic precursor. Via functionalization of the particles with priorly reacted 3-glycidoxypropyltrimethoxysilane and N α,N α-bis(carboxymethyl)-l-lysine (NTA), and charging with Ni²⁺, magnetic affinity adsorbents were obtained. The particles were applied to separate a His-tagged antibody fragment from a heterogeneous protein mixture of a microbial cultivation supernatant. Binding properties and specificity for purification of the target product ABF D1.3 scFv were optimized regarding the GNTA concentration and were found superior as compared to commercially available systems. A molar ratio of 1:2 Fe₂O₃:GNTA was most beneficial for the specific purification of the antibody fragment.     

Removal of heavy metals from aqueous solutions using Fe3O4, ZnO, and CuO nanoparticles

This study investigated the removal of Cd²⁺, Cu²⁺, Ni²⁺, and Pb²⁺ from aqueous solutions with novel nanoparticle sorbents (Fe₃O₄, ZnO, and CuO) using a range of experimental approaches, including, pH, competing ions, sorbent masses, contact time, scanning electron microscopy, transmission electron microscopy, and X-ray diffraction. The images showed that Fe₃O₄, ZnO, and CuO particles had mean diameters of about 50?nm (spheroid), 25?nm (rod shape), and 75?nm (spheroid), respectively. Tests were performed under batch conditions to determine the adsorption rate and uptake at equilibrium from single and multiple component solutions. The maximum uptake values (sum of four metals) in multiple component solutions were 360.6, 114.5, and 73.0?mg?g^?1, for ZnO, CuO, and Fe₃O₄, respectively. Based on the average metal removal by the three nanoparticles, the following order was determined for single component solutions: Cd²⁺?>?Pb²⁺?>?Cu²⁺?>?Ni²⁺, while the following order was determined in multiple component solutions: Pb²⁺?>?Cu²⁺?>?Cd²⁺?>?Ni²⁺. Sorption equilibrium isotherms could be described using the Freundlich model in some cases, whereas other isotherms did not follow this model. Furthermore, a pseudo-second order kinetic model was found to correctly describe the experimental data for all nanoparticles. Scanning electron microscopy, energy dispersive X-ray before and after metal sorption, and soil solution saturation indices showed that the main mechanism of sorption for Cd²⁺ and Pb²⁺ was adsorption, whereas both Cu²⁺ and Ni²⁺ sorption were due to adsorption and precipitation. These nanoparticles have potential for use as efficient sorbents for the removal of heavy metals from aqueous solutions and ZnO nanoparticles were identified as the most promising sorbent due to their high metal uptake.     

Effect of a SiO2 coating on the magnetic properties of Fe3O4 nanoparticles

In this work the effect of a SiO2 coating on the magnetic properties of Fe3O4 nanoparticles obtained by the sol-gel method is analyzed. Two sets of samples were prepared: Fe3O4 nanoparticles and Fe3O4@SiO2 core-shell composites. The samples display the characteristic spinel structure associated with the magnetite Fe3O4 phase, with the majority of grain sizes around 5-10 nm. At room temperature the nanoparticles show the characteristic superparamagnetic behavior with mean blocking temperatures around 160 and 120 K for Fe3O4 and Fe3O4@SiO2, respectively. The main effect of the SiO2 coating is reflected in the temperature dependence of the high field magnetization (μ(0)H = 6 T), i.e. deviations from the Bloch law at low temperatures (T < 20 K). Such deviations, enhanced by the introduction of the SiO2 coating, are associated with the occurrence of surface spin disordered effects. The induction heating effects (magnetic hyperthermia) are analyzed under the application of an AC magnetic field. Maximum specific absorption rate (SAR) values around 1.5 W g(-1) were achieved for the Fe3O4 nanoparticles. A significant decrease (around 26%) is found in the SAR values of the SiO2 coated nanocomposite. The different heating response is analyzed in terms of the decrease of the effective nanoparticle magnetization in the Fe3O4@SiO2 core-shell composites at room temperature.