核壳型纳米粒子合成方法及其性能的研究进展

核壳纳米粒子作为复合纳米粒子一个重要的分支,由于其光、磁和催化等方面的优异性能,近年来引起了人们广泛的关注.本文主要介绍了核壳纳米粒子的制备方法及诸多性能,并对核壳纳米粒子的发展进行了展望.     

Surface Functional Imprinting of Bensulfuron-methyl at Surface of Silica Nanoparticles Linked by Silane Coupling Agent

This article presents work on designing surface-imprinted core-shell nanoparticles via non-covalent interactions using bensulfuron-methyl (BSM) as the template and methacrylic acid as the functional monomer. About 3-(Trimethoxysilyl) propylmethacrylate (KH-570) functionalized SiO₂ nanoparticles were produced by sonochemical reaction. The grafting copolymerization of methacrylic acid and ethylene glycol dimethacrylate at the surface of KH-570 functionalized SiO₂ nanoparticles and in the presence of BSM as the template led to the formation of surface-imprinted core-shell nanoparticles. The core-shell nanoparticles were characterized, and their capacity to rebind BSM was analyzed. Results showed that the surface-imprinted core-shell nanoparticles binded the original template BSM with an appreciable selectivity over structurally related compounds. Compared to traditional imprinted particles, the density of effective imprinted sites in the nanoshells has been increased by four folds.     

以核壳结构聚合物模板合成P(St-co-DEA)/SiO_2杂化粒子

本文采用聚(苯乙烯-co-甲基丙烯酸-N,N-二甲氨基乙酯)[P(St-co-DEA)]核壳纳米粒子为模板,在环境条件下以四甲基硅氧烷(TMOS)为前体,原位可控沉积纳米结构SiO2,合成了具有PSt核和PDEA-SiO2杂化的壳层纳米粒子,将杂化粒子进一步煅烧可得到空心的SiO2纳米微球。采用FT IR、TEM以及DLS对所合成的杂化纳米粒子进行了详细的表征。TEM观察证实了纳米结构SiO2在粒子壳层中的沉积,随着矿化反应的进行,体系形成了具有核壳结构的树莓状纳米粒子。研究表明:杂化粒子的表面粗糙程度及大小可以通过简单改变体系试验参数(如TMOS的用量和矿化时间等)而控制。     

Development of Core-Shell Nanoparticle Drug Delivery Systems Based on Biomimetic Mineralization

Among various drug-delivery systems, core-shell nanoparticles have many advantages. Inspired by nature, biomimetic synthesis has emerged as a new strategy for making core-shell nanoparticles in recent years. Biomimetic mineralization is the process by which living organisms produce minerals based on biomolecule templating that leads to the formation of hierarchically structured organic–inorganic materials. In this minireview, we mainly focus on the synthesis of core-shell nanoparticle drug-delivery systems by biomimetic mineralization. We review various biomimetic mineralization methods for fabricating core-shell nanoparticles including silica-based, calcium-based and other nanoparticles, and their applications in drug delivery. We also summarize strategies for drug loading in the biomolecule-mineralized core-shell NPs. Current challenges and future directions are also discussed.     

Controllable synthesis of SiC@Graphene core-shell nanoparticles via fluidized bed chemical vapor deposition

SiC@Graphene (SiC@G) core-shell nanoparticles were successfully prepared by a facile fluidized bed (FB) chemical vapor deposition (CVD) method. SiC@G core-shell nanoparticles with an average size of 10 nm and graphene from 1 to 5 layers with a controllable thickness were obtained by finely adjusting the experimental temperatures. The formation of SiC nanoparticles and graphene layers was confirmed by the results of X-ray diffraction (XRD) and Raman Spectroscopy. The graphene content in SiC@G core-shell nanoparticles prepared at different temperatures was measured from thermogravimetric analysis (TG), which varied from 5.89% to 11.88 mass%. From X-ray photoelectron spectroscopy (XPS) results, no absorption assigned to Si-O band was detected, indicating the effective protection of the SiC nanoparticles against oxidation by the graphene shell to resist oxidation of SiC nanoparticles. This novel method of preparation of SiC@G core-shell nanoparticles could be applied to large-scale production and find diverse applications in related fields.     

Plasmon enhanced upconversion luminescence of NaYF(4):Yb,Er@SiO(2)@Ag core-shell nanocomposites for cell imaging

NaYF(4):Yb,Er@SiO(2)@Ag core-shell nanocomposites were prepared to investigate metal-enhanced upconversion luminescence. Two sizes (15 and 30 nm) of Ag nanoparticles were used. The emission intensity of the upconversion nanocrystals was found to be strongly modulated by the presence of Ag nanoparticles (NPs) on the outer shell layer of the nanocomposites. The extent of modulation depended on the separation distance between Ag NPs and upconversion nanocrystals. The optimum upconversion luminescence enhancement was observed at a separation distance of 10 nm for Ag NPs with two different sizes (15 and 30 nm). A maximum upconversion luminescence enhancement of 14.4-fold was observed when 15 nm Ag nanoparticles were used and 10.8-fold was observed when 30 nm Ag NPs were used. The separation distance dependent emission intensity is ascribed to the competition between energy transfer and enhanced radiative decay rates. The biocompatibility of the nanocomposites was significantly improved by surface modification with DNA. The biological imaging capabilities of these nanocomposites were demonstrated using B16F0 cells.     

Carbon-encapsulated Fe nanoparticles from detonation-induced pyrolysis of ferrocene

Carbon-encapsulated Fe nanoparticles with size between 5 and 20 nm were synthesized via a picric acid-detonation-induced pyrolysis of ferrocene, which is characterized by a self-heating and extremely fast process. The nanoparticles exhibit well-constructed core-shell structures, with bcc-Fe cores and graphitic shells. The graphitic shells can protect effectively the cores against the attack of HNO₃ solution. The formation of the core-shell nanoparticles can be selectively controlled by adjusting the composition of the picric acid-ferrocene mixture, which determines C/Fe atomic ratio of the reaction system. The core-shell nanoparticles are preferably formed at low C/Fe atomic ratios, while tubular structures are formed at high C/Fe ratio. The possible pathway for the carbon-encapsulated Fe nanoparticles formation is discussed briefly.     

Temperature effect on mechanical strength and frictional properties of polytetrafluoroethylene-based core-shell nanocomposites

Polytetrafluoroethylene (PTFE) has shown an outstanding lubricity as a solid lubricant, but its application is limited due to its low-mechanical strength and high-wear rate. In this study, core-shell nanoparticles were synthesized using PTFE as the core and polymethylmethacrylate (PMMA) as the shell. The formed core-shell nanocomposites by leveraging the core-shell nanoparticles as basic structural units exhibit remarkable enhancement on uniformity, tensile strength, and wear resistance, compared to mechanically mixed composites with the same composition. Our experiments demonstrated the following results: (1) Owing to the excellent uniformity, the maximum tensile strength of core-shell nanocomposites was 62 MPa, three times higher than that of mechanically mixed composites. (2) The composite matrix formed by PMMA shell had better reinforcement and protection effect on inner PTFE phase, resulting in a reduced wear rate of 0.3 × 10⁻⁵ mm³/(N m), one order of magnitude lower than that of mechanically mixed composites. (3) The friction coefficient and interfacial mechanical properties of the core-shell nanocomposites at different temperatures have been systematically studied to get insights into lubrication mechanisms. It is proved that the temperature can decrease the modulus and increase the interfacial adhesion as well as the loss tangent of the core-shell nanocomposites, thus affecting the lubrication properties in multiple ways.     

Preparation and sedimentation behavior of conductive polymeric nanoparticles

A facile route to prepare Fe₃O₄/polypyrrole (PPY) core-shell magnetic nanoparticles was developed. Fe₃O₄ nanoparticles were first prepared by a chemical co-precipitation method, and then Fe₃O₄/PPY core-shell magnetic composite nanoparticles were prepared by in-situ polymerization of pyrrole in the presence of Fe₃O₄ nanoparticles. The obtained nanoparticles were characterized by scanning electronic microscopy (SEM), transmission electronic microscopy (TEM) and laser particle size analyzer. The images indicate that the size of Fe₃O₄ particles is about 10 nanometers, and the particles are completely covered by PPY. The Fe₃O₄/PPY core-shell magnetic composite nanoparticles are about 100 nanometers and there are several Fe₃O₄ particles in one composite nanoparticle. The yield of the composite nanoparticles was about 50%. The sedimentation behavior of Fe₃O₄/PPY core-shell magnetic nanoparticles in electrolyte and soluble polymer solutions was characterized. The experimental results indicate that the sedimentation of particles can be controlled by adjusting electrolyte concentration, solvable polymers and by applying a foreign field. This result is useful in preparing gradient materials and improving the stability of suspensions.     

Synthesis of silver/SiO2/Eu:Lu2O3 core-shell nanoparticles and their polymer nanocomposites

We report a core-shell approach that combines silver nanoparticles as the metal core component with Eu:Lu₂O₃ as the phosphor shell component. The core-shell design contains an optically transparent SiO₂ intermediate layer that separates the metallic nanoparticle core and the phosphor shell. The thickness of the SiO₂ layer is in the nanometer range and can be tuned, so as to provide for different interactions between the core and shell. To demonstrate the versatility of the design, spherical silver nanoparticles or wavelength-tunable plasmonic silver nanoplates are used as the core component. In addition, a nanocomposite phosphor was fabricated by embedding the core-shell nanoparticles into a transparent polymeric matrix. The core-shell metal-phosphor design presented here serves as framework for the fabrication of inexpensive nanocomposite scintillator.     

Hyperthermia of Magnetically Soft-Soft Core-Shell Ferrite Nanoparticles

Magnetically soft-soft MnFe₂O₄-Fe₃O₄ core-shell nanoparticles were synthesized through a seed-mediated method using the organometallic decomposition of metal acetyl acetonates. Two sets of core-shell nanoparticles (S1 and S2) of similar core sizes of 5.0 nm and different shell thicknesses (4.1 nm for S1 and 5.7 nm for S2) were obtained by changing the number of nucleating sites. Magnetic measurements were conducted on the nanoparticles at low and room temperatures to study the shell thickness and temperature dependence of the magnetic properties. Interestingly, both core-shell nanoparticles showed similar saturation magnetization, revealing the ineffective role of the shell thickness. In addition, the coercivity in both samples displayed similar temperature dependencies and magnitudes. Signatures of spin glass (SG) like behavior were observed from the field-cooled temperature-dependent magnetization measurements. It was suggested to be due to interface spin freezing. We observed a slight and non-monotonic temperature-dependent exchange bias in both samples with slightly higher values for S2. The effective magnetic anisotropy constant was calculated to be slightly larger in S2 than that in S1. The magnetothermal efficiency of the chitosan-coated nanoparticles was determined by measuring the specific absorption rate (SAR) under an alternating magnetic field (AMF) at 200–350 G field strengths and frequencies (495.25–167.30 kHz). The S2 nanoparticles displayed larger SAR values than the S1 nanoparticles at all field parameters. A maximum SAR value of 356.5 W/g was obtained for S2 at 495.25 kHz and 350 G for the 1 mg/mL nanoparticle concentration of ferrogel. We attributed this behavior to the larger interface SG regions in S2, which mediated the interaction between the core and shell and thus provided indirect exchange coupling between the core and shell phases. The SAR values of the core-shell nanoparticles roughly agreed with the predictions of the linear response theory. The concentration of the nanoparticles was found to affect heat conversion to a great extent. The in vitro treatment of the MDA-MB-231 human breast cancer cell line and HT-29 human colorectal cancer cell was conducted at selected frequencies and field strengths to evaluate the efficiency of the nanoparticles in killing cancer cells. The cellular cytotoxicity was estimated using flow cytometry and an MTT assay at 0 and 24 h after treatment with the AMF. The cells subjected to a 45 min treatment of the AMF (384.50 kHz and 350 G) showed a remarkable decrease in cell viability. The enhanced SAR values of the core-shell nanoparticles compared to the seeds with the most enhancement in S2 is an indication of the potential for tailoring nanoparticle structures and hence their magnetic properties for effective heat generation.     

Emulsifier-free core-shell polyacrylate latex nanoparticles containing fluorine and silicon in shell

The emulsifier-free core-shell polyacrylate latex nanoparticles containing fluorine and silicon in shell were successfully synthesized by emulsifier-free seeded emulsion polymerization with water as the reaction medium. The silicon-containing fluorinated polymer could be fixed on the surface of polyacrylate nanoparticles due to the formation of the crosslinked network structure. Transmission electron microscopy (TEM) and dynamic light scattering (DLS) analysis indicated that the obtained emulsifier-free core-shell nanoparticles were uniform and possessed narrow size distributions. The core-shell structure and chemical components of the emulsifier-free core-shell nanoparticles were investigated by TEM and Fourier transform infrared (FTIR) spectrometry, respectively. X-ray photoelectron spectroscopy (XPS) analysis and contact angle measurement on the latex films proved the propensity of fluorine and silicon enrichment at film-air interface. In addition, the thermal stability of the latex films was improved with increasing the concentration of fluorine and silicon.     

Enhanced antibacterial activity of bimetallic gold-silver core-shell nanoparticles at low silver concentration

Herein we report the development of bimetallic Au@Ag core-shell nanoparticles (NPs) where gold nanoparticles (Au NPs) served as the seeds for continuous deposition of silver atoms on its surface. The core-shell structure and morphology were examined by UV-Vis spectroscopy, transmission electron microscopy (TEM), energy dispersive X-ray (EDX) analysis and X-ray diffraction (XRD). The core-shell NPs showed antibacterial activity against both gram negative (Escherichia coli and Pseudomonas aeruginosa) and gram positive (Enterococcus faecalis and Pediococcus acidilactici) bacteria at low concentration of silver present in the shell, with more efficacy against gram negative bacteria. TEM and flow cytometric studies showed that the core-shell NPs attached to the bacterial surface and caused membrane damage leading to cell death. The enhanced antibacterial properties of Au@Ag core-shell NPs was possibly due to the more active silver atoms in the shell surrounding gold core due to high surface free energy of the surface Ag atoms owing to shell thinness in the bimetallic NP structure.     

Effect of shell phase composition on the dielectric property and energy density of core-shell structured BaTiO3 particles modified poly(vinylidene fluoride) nanocomposites

Dielectric nanocomposites have attracted much attention due to their wide applications in electronics and electrical industry. Recently, incorporating core-shell nanoparticles into polymer matrix to improve the dielectric properties of nanocomposites has been widely reported. Tailoring the interfacial region between the polymer and the nanoparticles plays a crucial role in achieving the desired dielectric and energy storage properties of nanocomposites. However, the effect of shell structure in the interface region on the dielectric and energy storage properties is rarely studied. Based on this, core-shell BaTiO₃ nanoparticles with two different shell polymers, a “hard-soft” copolymer of methyl methacrylate and butyl acrylate (P[MMA-BA]) and a “hard” homopolymer of methyl methacrylate (PMMA), were prepared in this paper. The effect of core-shell BaTiO₃ nanoparticles with different shell structures on the dielectric and energy storage properties of poly(vinylidene fluoride) (PVDF) was investigated in depth. Due to the formation of a tight interfacial region between P(MMA-BA)@BT and PVDF matrix, P(MMA-BA)@BT/PVDF nanocomposites not only have low dielectric loss but also higher energy efficiency than PMMA@BT/PVDF nanocomposites. This study suggests a potential strategy that fabricating a “hard-soft” copolymer shell on BaTiO₃ surface can obtain desirable energy storage efficiency than the single “hard” shell structure in dielectric nanocomposites.     

Au/Pd core-shell nanoparticles with varied hollow Au cores for enhanced formic acid oxidation

A facile method has been developed to synthesize Au/Pd core-shell nanoparticles via galvanic replacement of Cu by Pd on hollow Au nanospheres. The unique nanoparticles were characterized by X-ray diffraction, X-ray photoelectron spectroscopy, transmission electron microscopy, ultraviolet–visible spectroscopy, and electrochemical measurements. When the concentration of the Au solution was decreased, grain size of the polycrystalline hollow Au nanospheres was reduced, and the structures became highly porous. After the Pd shell formed on these Au nanospheres, the morphology and structure of the Au/Pd nanoparticles varied and hence significantly affected the catalytic properties. The Au/Pd nanoparticles synthesized with reduced Au concentrations showed higher formic acid oxidation activity (0.93 mA cm^-2 at 0.3 V) than the commercial Pd black (0.85 mA cm^-2 at 0.3 V), suggesting a promising candidate as fuel cell catalysts. In addition, the Au/Pd nanoparticles displayed lower CO-stripping potential, improved stability, and higher durability compared to the Pd black due to their unique core-shell structures tuned by Au core morphologies.     

The unexpected structures of "core-shell" and "alloy" LnF3 nanoparticles as examined by variable energy X-ray photo-electron spectroscopy

Lanthanide fluoride nanoparticles were synthesized in aqueous media using procedures intended for a core-shell structure of Ln((1))F(3)-Ln((2))F(3), its reverse architecture, and an alloy structure. Their structures were examined by variable photon energy photo-electron spectroscopy using synchrotron radiation, along with X-ray powder diffractometry, transmission electron microscopy, energy dispersive X-ray spectroscopy, and luminescence spectroscopy. The results show that the nanoparticles intended for a core-shell structure do not have a core-shell structure, and that nanoparticles intended for an alloy structure do not always have an alloy structure. A possible explanation for this is cation exchange, a phenomenon that occurs when LnF(3) nanoparticles are exposed to another Ln(3+) ion in aqueous media, resulting in Ln(3+) ions in nanoparticles being quickly replaced by Ln(3+) ions in solution. This cation exchange effectively competes with the precipitation of LnF(3), which leads to a concentration gradient in the case of the combination of LaF(3) and GdF(3), and to nearly an alloy structure (isotropic mixture of all the ions) in the case of the combination of LaF(3) and NdF(3), regardless of the procedure used. Finally, the intended "core-shell" nanoparticles were doped with Eu(3+) to show that a non-core-shell structure can also give rise to the improvement of optical properties as compared with the corresponding core nanoparticles. These results suggest that conclusions in the literature that a core-shell structure was obtained as inferred by TEM or enhanced luminescence may not be correct.     

Tunable synthesis of metal-graphene complex nanostructures and their catalytic ability for solvent-free cyclohexene oxidation in air

A one-step method was developed for the controllable construction of metal-graphene core-shell structures, hollow graphene nanospheres, and a high density of metal nanoparticles supported on graphene. The metal-graphene core-shell nanostructures as nanocatalysts show excellent catalytic ability for the selective oxidation of cyclohexene.     

Photocatalytic Preparation of Encapsulated Gold Nanoparticles by Jingle-bell-shaped Cadmium Sulfide–silica Nanoparticles

Gold (Au) nanoparticles were deposited inside silica: (SiO₂) shells containing cadmium sulfide (CdS) nanoparticles through photocatalytic reduction of potassium dicyanogold(I) by CdS. Photocatalytic Au deposition occurred only when core-shell nanoparticles having a void space between the core and shell, i.e., a jingle-bell-shaped structure, were used. These core-shell nanoparticles were prepared by size-selective photoetching of SiO₂ -covered CdS nanoparticles. The size of Au nanoparticles could be controlled by adjustment of the void space in SiO₂-covered CdS. Dissolution of CdS by acid treatment from the Au-deposited jingle-bell nanoparticles did not have any effect on the surface-plasmon absorption by Au. These facts indicate that Au nanoparticles of adjustable size can be prepared in an SiO₂ shell that prevents mutual coalescence of Au nanoparticles but allows permeation of molecules and ions.     

Influence of anionic and non-ionic surfactants on the synthesis of core-shell Fe3O4@TiO2 nanocomposite synthesized by hydrothermal method

Magnetite spinel nanoparticles (Fe₃O₄) coated titanium dioxide has been prepared by the solvo-hydrothermal method for application in dye degradation and wastewater remediation. The core-shell Fe3O4@TiO2 nanoparticles have been synthesized using titanium butoxide (TBT) and ferric chloride as precursors. In this method, firstly, magnetite nanoparticles have been prepared through a solvothermal process using ethylene glycol as a solvent. Then, titanium butoxide was used as a precursor to synthesize Fe₃O₄@TiO₂ core-shell nanoparticles using the hydrothermal method. The surfactants that were added, in separate synthetic processes, were anionic oleic acid and Sodium Dodecyl sulfonate, and non-ionic Polyvinylpyrrolidone and Polyethylene glycol. The effects of the various surfactants on the fabrication of core-shell magnetic nanoparticles were studied. Various characterization methods have been established to examine the morphology and magnetization features of the nanostructured particles, such as XRD, FTIR, TEM, FESEM, UV-spectroscopy, and VSM, etc., which validated the formation of Titania coated magnetite nanoparticles. The TiO₂ shell formation drastically reduces the saturation magnetization of the magnetic nanoparticles. The Oleic acid as a surfactant produces the smallest nanoparticles. The PVP coating is best amongst these surfactants for the retention of saturation magnetization upon coating.     

CdSe@ZnSe@SiO2核壳壳型纳米粒子的制备与表征

通过TOP-TOPO-HDA路线制备了CdSe纳米晶体,并在此基础上通过一步法制备出CdSe@ZnSe核壳纳米粒子。利用环己烷-壬基酚聚（5）氧乙烯醚（NP-5）-水的微乳体系为模板,通过硅烷偶联剂的作用制备出CdSe@ZnSe@SiO2复合纳米粒子,并通过TEM、EDX和UV-Vis等手段对所得纳米粒子进行了表征。