Highly sensitive fluorescent detection of EDIL3 overexpressed exosomes for the diagnosis of triple-negative breast cancer.

EDIL3 is a strong and highly accurate diagnostic marker for breast cancer, meanwhile, EDIL3 overexpressed exosomes are novel biomarkers for the early diagnosis of triple-negative breast cancer (TNBC). Here, we proposed a fluorescent detection method for EDIL3 overexpressed exosomes, which is simple and sensitive. Basically, we utilized a magnetic nanospheres (MNS) based liquid sandwich immunoassay strategy. MNS were modified with CD63 aptamers, which can immunologically bound to the CD63 protein on the surface of exosomes. Alexa Fluor 647 labeled anti-EDIL3 antibodies (Anti-EDIL3/AF647) were used as the fluorescent probes to recognize the EDIL3 on exosomes derived from a TNBC cell line (MDA-MB-231). With the target TNBC exosomes present, sandwich structures containing MNS, exosomes and fluorescent probes were formed. After magnetic purification, optical super resolution imaging of the products was conducted to check the specificity of the assay. In addition, fluorescence signals of the products were detected to quantitatively analyze the EDIL3 overexpressed exosomes. The linear range was found to be 7.78 × 101to 7.78× 106particlesµl-1. The detection limit was approximately 10 particlesµl-1. The feasibility of the method for the detection of exosomes in complex biological samples was also demonstrated. Such a simple and sensitive detection method for EDIL3 overexpressed exosomes holds a great potential in clinical diagnosis of TNBC.

Photoelectrochemical detection of human epidermal growth factor receptor 2 (HER2) based on Co3O4-ascorbic acid oxidase as multiple signal amplifier.

A sensitive photoelectrochemical (PEC) sensor based on hexagonal carbon nitride tubes (HCNT) as photoactive material was prepared for the detection of human epidermal growth factor receptor 2 (HER2). Magnetic Fe3O4 nanospheres (MNs) modified with anti-HER2 antibodies were employed for highly efficient capture of HER2 from serum sample, and Co3O4 nanoparticles (Co3O4 NPs) modified with ascorbic acid oxidase (AAO) as well as HER2 aptamer were used for signal amplification. When the aptamer-Co3O4-AAO probe was captured onto the electrode surface through the specific binding of the aptamer with HER2, the photocurrent intensity decreased. This was because Co3O4 NPs competed with HCNT for consumption of the excitation energy. As a consequence AAO catalyzed the oxidation of the electron donor (AA), and the aptamer-Co3O4-AAO probe increased the steric hindrance at the electrode surface, leading to significant photocurrent intensity decrease, thus realizing multiple signal amplification. Based on this signal amplification strategy, at 0 V (vs Ag/AgCl), the PEC sensor shows a wide linear response ranging from 1 pg mL-1 to 1 ng mL-1 with a low detection limit of 0.026 pg mL-1 for HER2. Importantly, the prepared PEC sensor was applied for detection of HER2 in human serum samples with recoveries between 98.8 and 101%. Sensitive photoelectrochemical sensor based on Co3O4 nanoparticles modified with ascorbic acid oxidase for signal amplification is reported.

Structure of Rat Testicles after Intravenous Injection of Nanosized Magnetite Particles.

The structure of the testicles was studied in adult rats in 120 days after a single intravenous injection of chitosan-modified (magnetic nanospheres) and lipid-modified (magnetoliposomes) nanosized magnetite particles. Perls histochemical reaction detected in the testicular interstitial connective tissue the cells which absorbed and accumulated magnetite nanoparticles. The dynamics of spermatogenesis index and the count of Perls+ cells in the rat testicles were traced throughout the experiment. The studied modified nanosized magnetite particles did not penetrate through the blood-testicle barrier in rats.

Detection of SNPs of T2DM susceptibility genes by a ligase detection reaction-fluorescent nanosphere technique.

OBJECTIVE: To establish a high throughput, low cost, and simple nanotechnology-based method for the detection of single nucleotide polymorphism (SNP) loci in type 2 diabetes mellitus (T2DM). METHODS: Multiplex ligase detection reaction (LDR) amplification was performed using fluorescently labeled magnetic nanosphere-bound upstream LDR probes and downstream probes labeled with a unique fluorescent group for each SNP locus. The amplified LDR products were separated by magnetic nanospheres and then scanned by fluorescence spectroscopy. Four SNP loci associated with T2DM were detected, including the rs13866634 locus in SLC30A8, rs10811661in CDKN2A/2B, rs1111875 in the HHEX gene, and rs7903146 in the TCF7L2 gene. The SNP genotype was also determined by DNA sequencing as a control. RESULTS: The SNP genotypes of the four gene loci determined by the nanosphere-based multiplex LDR method were consistent with the DNA sequencing results. The accuracy rate was 100%. CONCLUSION: A method based on multiplex PCR and LDR was established for simultaneous detection of four SNP loci of T2DM susceptibility genes.

Microwave-assisted preparation of poly(ionic liquids)-modified polystyrene magnetic nanospheres for phthalate esters extraction from beverages.

The fabrication of novel poly(ionic liquids)-modified polystyrene (PSt) magnetic nanospheres (PILs-PMNPs) by a one-pot miniemulsion copolymerization reaction was achieved through an efficient microwave-assisted synthesis method. The morphology, structure, and magnetic behavior of the as-prepared magnetic materials were characterized by using transmission electron microscopy, vibrating sample magnetometry, etc. The magnetic materials were utilized as sorbents for the extraction of phthalate esters (PAEs) from beverage samples followed by high-performance ultrafast liquid chromatography analysis. Significant extraction parameters that could affect the extraction efficiencies were investigated particularly. Under optimum conditions, good linearity was obtained in the concentration range of 0.5-50 (dimethyl phthalate), 0.3-50 (diethyl phthalate), 0.2-50 (butyl benzyl phthalate), and 0.4-50 µg/L (di-n-butyl phthalate), with correlation coefficients R2  > 0.9989. Limits of detection were in the range 125-350 pg. The proposed method was successfully applied to determine PAEs from beverage samples with satisfactory recovery ranging from 77.8 to 102.1% and relative standard deviations ranging from 3.7 to 8.4%. Comparisons of extraction efficiency with PSt-modified MNPs as sorbents were performed. The results demonstrated that PILs-PMNPs possessed an excellent adsorption capability toward the trace PAE analytes.

Aptamer-functionalized magnetic and fluorescent nanospheres for one-step sensitive detection of thrombin.

A one-step sandwich method is described for detecting proteins with magnetic nanospheres (MNs) and fluorescent nanospheres (FNs). Thrombin is selected as a model analyte to validate the method. Two DNA aptamers (Apt 29 and Apt 15 targeting two different exosites of thrombin) are chosen as recognition elements to modify MNs and FNs. The superparamagnetic MN-Apt 29 conjugate is used to separate and concentrate thrombin. The FN-Apt 15 conjugate encapsulates hundreds of fluorescent quantum dots and is used as reporter to provide a stable signal. Magnetic capture and fluorescence identification are performed simultaneously to form a sandwich complex (MN-Apt 29-thrombin-FN-Apt 15) for fluorescence determination (at excitation/emission wavelengths of 380/622 nm). The method is convenient, time saving, and gives a strong signal (compared to the two-step method where capture and identification are performed in two steps). The one-step method presented here is completed within 30 min and has a 3.5 ng·mL-1 (97 pM) detection limit. The method is reproducible, has an intra-assay variability of 1.5%, and an inter-assay variability of 4.9%. Other serum proteins (HSA, CEA, PSA, and AFP) do not interfere. The method was also applied to analyze serum samples. Almost the same fluorescence intensity was measured when analyzing 1% serum samples (compared to buffer samples). Graphical abstract Magnetic nanospheres with excellent superparamagnetic property and fluorescent QD-based nanospheres were prepared and used in a one-step sensitive method for detecting thrombin. The method exhibits good reproducibility, high specificity, and good selectivity.

Ultrastructure of Rat Kidneys after Intravenous Administration of Modified Magnetite Nanoparticles.

The ultrastructure of nephrocytes of the proximal and distal convoluted tubules, podocytes, mesangial cells, and macrophages of the interstitial connective tissue was studied after single intravenous administration of magnetite nanoparticles modified with chitosan (magnetic nanospheres) or lipids (magnetic liposomes). Transmission electron microscopy showed ultrastructural features of absorption of magnetite nanoparticles. The shape, size, and number of vesicles containing nanoparticles in nephrocytes of convoluted tubules and macrophages after administration of the suspensions of magnetic nanospheres and magnetic liposomes were described.

Selective oxidation of benzyl alcohols to benzoic acid catalyzed by eco-friendly cobalt thioporphyrazine catalyst supported on silica-coated magnetic nanospheres.

A novel magnetically recoverable thioporphyrazine catalyst (CoPz(S-Bu)8/SiO2@Fe3O4) was prepared by immobilization of the cobalt octkis(butylthio) porphyrazine complex (CoPz(S-Bu)8) on silica-coated magnetic nanospheres (SiO2@Fe3O4). The composite CoPz(S-Bu)8/SiO2@Fe3O4 appeared to be an active catalyst in the oxidation of benzyl alcohol in aqueous solution using hydrogen peroxide (H2O2) as oxidant under Xe-lamp irradiation, with 36.4% conversion of benzyl alcohol, about 99% selectivity for benzoic acid and turnover number (TON) of 61.7 at ambient temperature. The biomimetic catalyst CoPz(S-Bu)8 was supported on the magnetic carrier SiO2@Fe3O4 so as to suspend it in aqueous solution to react with substrates, utilizing its lipophilicity. Meanwhile the CoPz(S-Bu)8 can use its unique advantages to control the selectivity of photocatalytic oxidation without the substrate being subjected to deep oxidation. The influence of various reaction parameters on the conversion rate of benzyl alcohol and selectivity of benzoic acid was investigated in detail. Moreover, photocatalytic oxidation of substituted benzyl alcohols was obtained with high conversion and excellent selectivity, specifically conversion close to 70%, selectivity close to 100% and TON of 113.6 for para-position electron-donating groups. The selectivity and eco-friendliness of the biomimetic photocatalyst give it great potential for practical applications.

Rapid and Quantitative Detection of Avian Influenza A(H7N9) Virions in Complex Matrices Based on Combined Magnetic Capture and Quantum Dot Labeling.

Avian influenza A(H7N9) virus, which emerged in China in the spring of 2013, has infected hundreds of people and resulted in many deaths. Herein, a rapid and quantitative assay is proposed for the one-step detection of H7N9 virions. Immunomagnetic nanospheres (IMNs) and antibody-conjugated quantum dots (Ab-QDs) are simultaneously employed to capture and identify the target virus, leading to a high efficiency, good specificity, and strong anti-interference ability. Moreover, this reliable detection assay, which combines the efficient magnetic enrichment and the unique photophysical properties of QDs, can achieve a high sensitivity for a low detection limit. At the same time, this detection strategy shows great flexibility for employment in a variety of fluorescence detectors, including fluorescence spectrometry, microscope assays, and handheld UV lamp tests. Furthermore, our one-step detection strategy induces very little change in the integrity of the vulnerable virions, which enables additional genotyping testing following the fluorescence detection. The present study, thus, reports a rapid and quantitative approach for the detection of H7N9 virions based on simultaneous magnetic capture and QD labeling, thereby providing a higher probability for detection and therefore faster diagnosis of H7N9-infected patients.

Facile synthesis of poly(ionic liquid)-bonded magnetic nanospheres as a high-performance sorbent for the pretreatment and determination of phenolic compounds in water samples.

Poly(ionic liquid)-bonded magnetic nanospheres were easily synthesized and applied to the pretreatment and determination of phenolic compounds in water samples, which have detrimental effects on water quality and the health of living beings. The high affinity of poly(ionic liquid)s toward the target compounds as well as the magnetic behavior of Fe3 O4 were combined in this material to provide an efficient and simple magnetic solid-phase extraction approach. The adsorption behavior of the poly(ionic liquid)-bonded magnetic nanospheres was examined to optimize the synthesis. Different parameters affecting the magnetic solid-phase extraction of phenolic compounds were assessed in terms of adsorption and recovery. Under the optimal conditions, the proposed method showed excellent detection sensitivity with limits of detection in the range of 0.3-0.8 ng/mL and precision in the range of 1.2-3.3%. This method was also applied successfully to the analysis of real water samples; good spiked recoveries over the range of 82.5-99.2% were obtained.

Solid-phase extraction based on chloromethylated polystyrene magnetic nanospheres followed by gas chromatography with mass spectrometry to determine phthalate esters in beverages.

An ultrasound-assisted magnetic solid-phase extraction procedure with chloromethylated polystyrene-coated Fe3 O4 nanospheres as magnetic adsorbents has been developed to determine eight phthalate esters (bis(4-methyl-2-pentyl) phthalate, dipentyl phthalate, dihexyl phthalate, benzyl butyl phthalate, bis(2-butoxyethyl) phthalate, dicyclohexyl phthalate, di-n-octyl phthalate, and dinonyl phthalate) simultaneously in beverage samples, in combination with gas chromatography coupled to tandem mass spectrometry for the first time. Several factors related to magnetic solid-phase extraction efficiencies, such as amount of adsorbent, extracting time, ionic strength, and desorption conditions were investigated. The enrichment factors of the method for the eight analytes were over 2482. A good linearity was observed in the range of 10-500 ng/L for bis(2-butoxyethyl) phthalate and 2-500 ng/L for the other phthalate esters with correlation coefficients ranging from 0.9980 to 0.9998. The limits of detection and quantification for the eight phthalate esters were in the range of 0.20-2.90 and 0.67-9.67 ng/L, respectively. The mean recoveries at three spiked levels were 75.8-117.7%, the coefficients of variations were <11.6%. The proposed method was demonstrated to be a simple and efficient technique for the trace analysis of the phthalate esters in beverage samples.

A miRNA-based gene therapy nanodrug synergistically enhances pro-inflammatory antitumor immunity against melanoma.

MicroRNA (miRNA)-based gene therapy is a robust approach to treating human cancers. However, the low target specificity and safety issues associated with viral vectors have limited the clinical use of miRNA therapeutics. In the present study, we aimed to develop a biocompatible nanocarrier to deliver the tumor suppressor miR-30a-5p for gene therapy of ocular melanoma. The quasi-mesoporous magnetic nanospheres (MMNs) were prepared by polyelectrolytes-mediated self-assembling Fe3O4 nanocrystals; the cationic polymer capped quasi-mesoporous inner tunnels of the MMNs facilitate high miRNA loading and protect from nuclease degradation. Then, the outer layer of the MMNs was modified with a disulfide bond bridged very low molecular weight polyethyleneimine (PEI) network to form redox-responsive nanospheres (rMMNs) that enhance the miRNA payload and enable miRNA release under glutathione-dominant tumor microenvironment. The miR-30a-5p loaded rMMNs nanodrug (miR-30a-5p@rMMNs) upregulated miR-30a-5p level and inhibited malignant phenotypes of ocular melanoma by targeting the transcription factor E2F7 both in vitro and in vivo. Additionally, rMMNs act as an enhancer to increase cancer cell apoptosis by modulating M1-like macrophage polarization and activating Fenton reaction. Thus, the rMMNs is a promising miRNA carrier for gene therapy and could enhance pro-inflammatory immunity in melanoma and other cancers. STATEMENT OF SIGNIFICANCE: • miR-30a-5p@rMMNs inhibited malignant phenotypes of ocular melanoma both in vitro and in vivo. • The rMMNs promoted M1 macrophage polarization thus synergistically enhancing pro-inflammatory anti-tumor immunity against melanoma. • The rMMNs showed no obvious toxicity under the injection dose.

Magnetic Dendritic Polymer Nanospheres for High-Performance Separation of Histidine-Rich Proteins.

Magnetic nanospheres are becoming a promising platform for a wide range of applications in pharmacy, life science, and immunodiagnostics due to their high surface area, ease of synthesis and manipulation, fast separation, good biocompatibility, and recyclable performance. In this work, an innovative and efficient method is developed by in situ reducing and growing Ni(OH)2 for the preparation of dendritic mesoporous nanocomposites of silica@Fe3O4/tannic acid@nickel hydroxide (dSiO2@Fe3O4/TA@Ni(OH)2). The flower-like nanospheres have good magnetic response, large surface area, and high histidine-rich protein (His-protein) purification performance. The dSiO2@Fe3O4/TA@Ni(OH)2 nanospheres were synthesized on the basis of a φ(NaSal/CTAB) of 1/1 and a mass of ferrous chloride tetrahydrate of 0.3 g, resulting in a saturation magnetization value of 48.21 emu/g, which means it can be collected within ∼1 min using a magnetic stand. Also, the BET test showed that the surface area is 92.47 m2/g and the pore size is ∼3.9 nm for dSiO2@Fe3O4/TA@Ni(OH)2 nanocomposites. Notably, the nickel hydroxide with unique flower-like structural features enables the combination of a large number of Ni2+ ions and His-proteins for high performance. The isolation and purification experiments of the synthesized dSiO2@Fe3O4/TA@Ni(OH)2 were performed by separating His-proteins from a matrix composed of bovine hemoglobin (BHb), bovine serum albumin (BSA), and lysozyme (LYZ). The result showed that the nanospheres have a high combination capacity of ∼1880 mg/g in a rapid equilibrium time of 20 min, which was selective for the adsorption of BHb. In addition, the stability and recyclability of BHb are 80% after seven cycles. Furthermore, the nanospheres were also used to isolate His-proteins from fetal bovine serum, proving its utility. Therefore, the strategy of separating and purifying His-proteins using dSiO2@Fe3O4/TA@Ni(OH)2 nanospheres is promising for practical applications.

Vancomycin-Loaded Furriness Amino Magnetic Nanospheres for Rapid Detection of Gram-Positive Water Bacterial Contamination.

Bacterial pathogens pose high threat to public health worldwide. Different types of nanomaterials have been synthesized for the rapid detection and elimination of pathogens from environmental samples. However, the selectivity of these materials remains challenging, because target bacterial pathogens commonly exist in complex samples at ultralow concentrations. In this study, we fabricated novel furry amino magnetic poly-L-ornithine (PLO)/amine-poly(ethylene glycol) (PEG)-COOH/vancomycin (VCM) (AM-PPV) nanospheres with high-loading VCM for vehicle tracking and the highly efficient capture of pathogens. The magnetic core was coated with organosilica and functionalized with cilia. The core consisted of PEG/PLO loaded with VCM conjugated to Gram-positive bacterial cell membranes, forming hydrogen bonds with terminal peptides. The characterization of AM-PPV nanospheres revealed an average particle size of 56 nm. The field-emission scanning electron microscopy (FE-SEM) micrographs showed well-controlled spherical AM-PPV nanospheres with an average size of 56 nm. The nanospheres were relatively rough and contained an additional 12.4 nm hydrodynamic layer of PLO/PEG/VCM, which provided additional stability in the suspension. The furry AM-PPV nanospheres exhibited a significant capture efficiency (>90%) and a high selectivity for detecting Bacillus cereus (employed as a model for Gram-positive bacteria) within 15 min, even in the presence of other biocompatible pathogens. Moreover, AM-PPV nanospheres rapidly and accurately detected B. cereus at levels less than 10 CFU/mL. The furry nano-design can potentially satisfy the increasing demand for the rapid and sensitive detection of pathogens in clinical and environmental samples.

Epsilon-polylysine based magnetic nanospheres as an efficient and recyclable antibacterial agent for Alicyclobacillus acidoterrestris.

In this work, polyacrylic acid modified ferroferric oxide (Fe3O4-PAA) was synthesized via a one-step hydrothermal method. The magnetic nanospheres modified with carboxyl groups were combined with epsilon-polylysine (EPL) via an EDC/NHS coupling reaction to obtain Fe3O4-PAA-EPL nanospheres. Fe3O4-PAA-EPL was employed as an antibacterial agent against Alicyclobacillus acidoterrestris and characterized by XRD, FTIR, XPS, VSM, SEM and TEM techniques. Experimental results showed the minimum inhibition concentration (MIC) of Fe3O4-PAA-EPL against A. acidoterrestris was 1.25 mg mL-1. Furthermore, A. acidoterrestris treated with Fe3O4-PAA-EPL nanospheres obviously lysed. Morphological analysis of bacteria supported by SEM indicated that the cell membrane of A. acidoterrestris was damaged, revealing that Fe3O4-PAA-EPL is an effective antibacterial agent. Additionally, the nanospheres with excellent magnetism can be simply separated from a reaction system via an external magnet. The construction of magnetic nanospheres with satisfactory antibacterial activity provides an effective and new method to control A. acidoterrestris.

Heteroporous 3D covalent organic framework-based magnetic nanospheres for sensitive detection of bisphenol A.

Covalent organic frameworks (COFs) showed great promise in effective adsorption of target molecule via size selectivity. Although various magnetic 2D COFs composites have been studied and exhibited the intensive applications, the incorporation of 3D COFs and magnetic nanoparticles to form a new class of magnetic adsorbents with enhanced function still has no reports. Herein, a novel Fe3O4@3D COF with heteroporous structure matching to the sizes of bisphenol A (BPA) was firstly synthesized for better adsorption of BPA than common magnetic 2D-COFs. Three Fe3O4@3D COFs nanospheres were synthesized under the solvothermal conditions in autoclave, and the optimum Fe3O4@3D-COF denoted as Fe3O4@COF-TpTAM (Tp, 1,3,5-triformylphloroglucinol; TAM, tetra(p-aminophenyl)-methane) was selected and employed. Detailed characteristics of Fe3O4@COF-TpTAM were evaluated via various techniques including TEM, FTIR, TGA, XRD and BET. Excellent chemical and thermal stability, high surface area (294.6 m2 g-1) and pore volume (0.2 m3 g-1) with multiple pore sizes comparable with the simulated three-dimensional sizes of BPA were exhibited. A high adsorption capacity of BPA up to 209.9 mg/g that was better than common 2D-COFs was achieved, and the sensitive MSPE-LC-MS method with wide linear range (10-5000 pg/mL), low detection limit (4 pg/mL, S/N = 3) was built. Satisfactory recoveries of BPA as 93.8 ± 1.4%-101.4 ± 5.1% (n = 3) and 100.4 ± 1.9% ~ 107.3 ± 1.2% (n = 3) were obtained in milk and river water samples, respectively. This work demonstrates the promising application of Fe3O4@3D COF as efficient adsorbents of trace BPA, and opens up a new access for the efficient MSPE in sample pretreatment for food or environmental safety analysis.

Photoelectrochemical detection of circulating tumor cells based on aptamer conjugated Cu2O as signal probe.

In this work, a sensitive and reliable photoelectrochemical (PEC) biosensor was proposed based on hexagonal carbon nitride tubes (HCNT) as photoactive material for detection of circulating tumor cells (CTCs). Magnetic Fe3O4 nanospheres (MNs) and Cu2O nanoparticles (Cu2O NPs) were utilized for highly efficient magnetic capture of CTCs and for signal amplification, respectively. First, anti-epithelial cell adhesion molecule (EpCAM) antibody was linked onto MNs for capture and enrichment of CTCs. With the captured MCF-7 coated onto the electrode, the photocurrent intensity of HCNT was decreased due to the steric hindrance derived from MCF-7. Then, when the Cu2O-aptamer probe was bound onto the CTC surface, the photocurrent intensity was further decreased because Cu2O NPs competed with HCNT for absorption of exciting light and the aptamer molecules increased the steric hindrance, which leads to significantly decreased photocurrent response, thus realizing dual signal amplification. Using the breast cancer cell MCF-7 as a model, the proposed PEC biosensor displays good performances with a linear range from 3 to 3000 cell mL-1 and limit of detection down to 1 cell mL-1. The HCNT-based PEC biosensor shows good performance for detection of CTCs, which may have potential applications in cancer diagnostics and therapeutics.

Magnetic nanospheres for convenient and efficient capture and release of hepatitis B virus DNA.

Nucleic acid isolation and purification are essential steps in molecular biology. Currently-used isolation methods focus on the extraction of all the nucleic acids from crude samples, yet ignore the specific nucleic acids of interest, which may induce the loss of the specific nucleic acids and hinder their analyses. Herein, a magnetic nanospheres (MNs)-based strategy for efficient capture and release of specific nucleic acids is developed. The DNA sequence of hepatitis B virus (HBV) is taken as a model to validate this method. The MNs are modified with the complementary strand of HBV DNA for specific capture based on hybridization reaction. Then, by melting at high temperature, the captured DNAs are detached from the MNs to achieve release. The capture and release process are performed conveniently with magnetic separation. High capture efficiency (over 80%) and nearly 100% release efficiency for HBV DNA are achieved respectively via 40 min and 5 min interaction. While non-target DNAs are hardly captured, indicative of good selectivity. Moreover, after releasing DNAs, the MNs are directly regenerated and can be reused without degrading performance, which greatly reduces the operation costs. Finally, this method is applied to serum samples without any pretreatment, which exhibits similar capture and release capacity with those in the ideal samples, indicating its great application potential in practice.

Synthesis of poly(acrylic acid) coated magnetic nanospheres via a multiple polymerization route.

Magnetic nanospheres are versatile candidates for both fundamental and practical applications. Before they are applied in more complicated fields, their surface must be modified by several functionalities. However, the surface modification can be affected by the magnetic nanoparticles (MNP) embedded in the polymer matrix. Herein, the synthesis of poly(acrylic acid) coated magnetic nanospheres via a multiple polymerization route is described. During the synthesis process, seed emulsion polymerization was applied to redistribute the MNP in the polymer matrix, and the relationship between the structure of magnetic nanospheres and the thickness of the grafted poly(acrylic acid) layer was investigated. The development of size, morphology and magnetic properties of the nanospheres were characterized by transmission electron microscopy, dynamic light scattering, thermogravimetric analysis, X-ray diffraction and vibrating sample magnetometry. This work would pave the way to design and preparation of new structure of functional magnetic nanospheres with precise surface modification.

Fabrication of Core-Shell Magnetic Molecularly Imprinted Nanospheres towards Hypericin via Click Polymerization.

The core-shell structure molecularly imprinted magnetic nanospheres towards hypericin (Fe3O4@MIPs) were prepared by mercapto-alkyne click polymerization. The shape and size of nanospheres were characterized by dynamic light scattering (DLS) and transmission electron microscope (TEM). The nanospheres were analyzed by FTIR spectroscopy to verify the thiol-yne click reaction in the presence or absence of hypericin. The Brunauer⁻Emmet⁻Teller (BET) method was used for measuring the average pore size, pore volume and surface area. The Fe3O4@MIPs synthesized displayed a good adsorption capacity (Q = 6.80 µmol·g-1). In addition, so-prepared Fe3O4@MIPs showed fast mass transfer rates and good reusability. The method established for fabrication of Fe3O4@MIPs showed excellent reproducibility and has broad potential for the fabrication of other core-shell molecularly imprinted polymers (MIPs).