The potential of asymmetric flow field-flow fractionation hyphenated to multiple detectors for the quantification and size estimation of silica nanoparticles in a food matrix

This work represents a first systematic approach to the size-based elemental quantification and size estimation of metal(loid) oxide nanoparticles such as silica (SiO₂) in a real food matrix using asymmetric flow field-flow fractionation coupled online with inductively coupled plasma mass spectrometry (ICP-MS) and multi-angle light scattering (MALS) and offline with transmission electron microscopy (TEM) with energy-dispersive X-ray analysis (EDAX). Coffee creamer was selected as the model sample since it is known to contain silica as well as metal oxides such as titania at the milligramme per kilogramme levels. Optimisation of sample preparation conditions such as matrix-to-solvent ratio, defatting with organic solvents and sonication time that may affect nanoparticle size and size distribution in suspensions was investigated. Special attention was paid to the selection of conditions that minimise particle transformation during sample preparation and analysis. The coffee creamer matrix components were found to stabilise food grade SiO₂ particles in comparison with water suspensions whilst no significant effect of defatting using hexane was found. The use of sample preparation procedures that mimic food cooking in real life was also investigated regarding their effect on particle size and particle size distribution of silica nanoparticles in the investigated food matrix; no significant effect of the water temperature ranging from ambient temperature to 60 °C was observed. Field-flow fractionation coupled to inductively coupled plasma-mass spectrometry (FFF-ICP-MS) analysis of extracts of both unspiked coffee creamer and coffee creamer spiked with food grade silicon dioxide, using different approaches for size estimation, enabled determination of SiO₂ size-based speciation. Element-specific detection by ICP-MS and post-FFF calibration with elemental calibration standards was used to determine the elemental composition of size fractions separated online by FFF. Quantitative data on mass balance is provided for the size-based speciation of the investigated inorganic nano-objects in the complex matrix. The combination of FFF with offline fractionation by filtration and with detection by ICP-MS and TEM/EDAX has been proven essential to provide reliable information of nanoparticle size in the complex food matrix.

Cerium oxide-deposited mesoporous silica nanoparticles for the determination of carcinoembryonic antigen in serum using inductively coupled plasma-mass spectrometry

CeO₂-deposited mesoporous silica nanoparticles were synthesized as a probe to determine carcinoembryonic antigen (CEA) in serum by inductively coupled plasma-mass spectrometry (ICP-MS). The prepared mesoporous nanoparticles were modified and tagged to the target for sandwich-type immunoassay. Fe₃O₄ magnetic nanoparticles (MNPs) were also synthesized and immobilized with antibody to extract the target biomarker. The calibration curve of the synthesized CeO₂-deposited silica nanoparticles, which was plotted by the signal ratio of ¹⁴⁰Ce/⁵⁷Fe measured by ICP-MS vs. the concentration of CEA, showed excellent linearity and sensitivity owing to the signal amplification and low spectral interference. Under optimal conditions, the sandwich-type analytical method was applied to determine CEA in serum spiked in the range of 0.001–5 ng mL⁻¹ and showed a limit of detection of 0.36 ng mL⁻¹. Since the deposited CeO₂ in the mesoporous silica layer can be substituted by other metal compounds, various kinds of metal-deposited nanoparticles can be prepared as probe materials for multiplex detection in bioanalysis.     

Differential determination of chromium(VI) and total chromium in natural waters using flow injection on-line separation and preconcentration electrothermal atomic absorption spectrometry.

A rapid, sensitive and selective method for the differential determination of CrIII and CrVI in natural waters is described. Chromium(vi) can be determined directly by flow injection on-line sorbent extraction preconcentration coupled with electrothermal atomic absorption spectrometry using sodium diethyldithiocarbamate as the complexing agent and C18 bonded silica reversed-phase sorbent as the column material. Total Cr can be determined after oxidation of CrIII to CrVI by potassium peroxydisulfate. Chromium(III) can be calculated by difference. The optimum conditions for sorbent extraction of CrVI and oxidation of CrIII to CrVI are evaluated. A 12-fold enhancement in sensitivity compared with direct introduction of 40 microliters samples was achieved after preconcentration for 60 s, giving detection limits of 16 ng l-1 for CrVI and 18 ng l-1 for total Cr (based on 3 sigma). Results obtained for sea-water and river water reference materials were all within the certified range for total Cr with a precision of better than 10% relative standard deviation in the range 100-200 ng l-1. The selectivity of the determination of CrVI was evaluated by analysing spiked reference materials in the presence of CrIII, resulting in quantitative recovery of CrVI.     

酶消解-单颗粒电感耦合等离子质谱法测定农产品中纳米铂颗粒

铂纳米颗粒在汽车行业中被广泛用作汽车尾气催化剂。随着铂纳米颗粒在工业生产中的广泛应用,它在环境中广泛分布并可能从植物累积进入食物链中。因此,建立一种在农产品中的定量分析方法是至关重要的。以酶消解的前处理方法结合单颗粒-电感耦合等离子体质谱法(Single particle ICP-MS,SP-ICP-MS)测定农产品中纳米铂颗粒(PtNPs)粒径分布及颗粒数量浓度。通过优化前处理提取条件,当Macerozyme R-10酶为10 mg、柠檬酸缓冲溶液浓度为5 mmol/L、提取时间36 h时,农产品中PtNPs提取效果较高。PtNPs粒径检出限为20 nm,颗粒浓度检出限为5×10⁵ particle/L,铂颗粒浓度回收率在(81±3)%~(91±4)%,加标后平均粒径(41±3)~(47±2)nm,与50 nm PtNPs标准溶液粒径接近。方法操作简单、检出限低、准确度高,适用于农产品中PtNPs定量分析,为客观评价农产品铂纳米毒性效应提供可靠的分析技术。     

7-amino-4-azaheptyl grafted onto a silica gel as a sorbent for the on-line preconcentration and determination of iron(III) in water samples.

A new sorbent was synthesized by anchoring 7-amino-4-azaheptyltrimetoxisilane, freshly prepared, to silica gel, producing 7-amino-4-azaheptyl anchored silica gel (AAHSG). This material was characterized by infrared spectroscopy (IR), elemental analysis (CHN), and nitrogen adsorption-desorption isotherms. Isotherms of the adsorption of Fe3+, Fe2+ and Cu2+ on AAHSG were recorded, which indicated that Fe3+ presents a higher affinity by the sorbent. Therefore, AAHSG was successfully employed as a sorbent in a simple flow system for the preconcentration of Fe3+ in natural water samples, such as, river water, lagoonwater, springwater, stream water, well water and two water reference materials (NIST-SRM 1640, NIST-SRM 1643d). The obtained preconcentration factor was 82.2, and the detection limit achieved was 5.9 ng ml(-1). The recovery of spiked water samples ranged from 95.0 - 103.1%.     

Synthesis and characterization of pore size-tunable magnetic mesoporous silica nanoparticles

Magnetic mesoporous silica nanoparticles (M-MSNs) are emerging as one of the most appealing candidates for theranostic carriers. Herein, a simple synthesis method of M-MSNs with a single Fe(3)O(4) nanocrystal core and a mesoporous shell with radially aligned pores was elaborated using tetraethyl orthosilicate (TEOS) as silica source, cationic surfactant CTAB as template, and 1,3,5-triisopropylbenzene (TMB)/decane as pore swelling agents. Due to the special localization of TMB during the synthesis process, the pore size was increased with added TMB amount within a limited range, while further employment of TMB lead to severe particle coalescence and not well-developed pore structure. On the other hand, when a proper amount of decane was jointly incorporated with limited amounts of TMB, effective pore expansion of M-MSNs similar to that of analogous mesoporous silica nanoparticles was realized. The resultant M-MSN materials possessed smaller particle size (about 40-70 nm in diameter), tunable pore sizes (3.8-6.1 nm), high surface areas (700-1100 m(2)/g), and large pore volumes (0.44-1.54 cm(3)/g). We also demonstrate their high potential in conventional DNA loading. Maximum loading capacity of salmon sperm DNA (375 mg/g) was obtained by the use of the M-MSN sample with the largest pore size of 6.1 nm.     

Fluorogenic Detection of Human Serum Albumin Using Curcumin-Capped Mesoporous Silica Nanoparticles

Mesoporous silica nanoparticles loaded with rhodamine B and capped with curcumin are used for the selective and sensitive fluorogenic detection of human serum albumin (HSA). The sensing mesoporous silica nanoparticles are loaded with rhodamine B, decorated with aminopropyl moieties and capped with curcumin. The nanoparticles selectively release the rhodamine B cargo in the presence of HSA. A limit of detection for HSA of 0.1 mg/mL in PBS (pH 7.4)-acetonitrile 95:5 v/v was found, and the sensing nanoparticles were used to detect HSA in spiked synthetic urine samples.     

Fabrication of Dendrimer－like PAMAM Based on Silica Nanoparticles

A G 4.0 dendrimer-like poly (amido amine) (PAMAM) based on silica nanoparticles was fabricated via a divergent approach.It was built from γ-aminopropyi silica nanoparfides (APSN) core via repetitive addition of acrylate (MA) and hexylenediamine (HDA). FT-IR and EA were used to monitor the progress of dendrimer during each step. The amino group content of the resulting product increased from 0.49 to 3.72 mmol/g after the 4th generation. In addition, the percentage of grafting increased with increasing generation and reached to 65.9% after 4th generation. It was found that the resulting silica nanoparticles could be dispersed in methanol with a mean hydrodynamic particle diameter of 152.7 nm although the silica nanoparticles had agglomerated during the storage period.     

Dye-doped silica nanoparticle labels/protein microarray for detection of protein biomarkers

We report a dye-encapsulated silica nanoparticle as a label, with the advantages of high fluorescence intensity, photostability, and biocompatibility, in conjunction with microarray technology for sensitive immunoassay of a biomarker, interleukin-6 (IL-6), on a microarray format. The tris(2,2'-bipyridyl)ruthenium(ii) chloride hexahydrate (Rubpy) dye was incorporated into silica nanoparticles using a simple one-step microemulsion synthesis. In this synthesis process, Igepal CA520 was used as the surfactant, therefore, no requirement of cosolvent during the synthesis and the particle size was reduced comparing to the commonly used Triton surfactant system. The nanoparticles are uniform in size with a diameter of 50 nm. The microarray fluorescent immunoassay approach based on dye-doped silica nanoparticle labels has high sensitivity for practical applications with a limit of detection for IL-6 down to 0.1 ng mL(-1). The calibration curve is linear over the range from 0.1 ng mL(-1) to 10 ng mL(-1). Furthermore, results illustrated that the assay is highly specific for IL-6 in the presence of range of cytokines or proteins. The RuDS dye-labeled nanoparticles in connection with protein microarrays show the promise for clinical diagnosis of biomarkers.     

Lab-on-a-bubble: synthesis, characterization, and evaluation of buoyant gold nanoparticle-coated silica spheres

This paper describes the development and preparation of a new class of materials for surface-enhanced Raman scattering (SERS) consisting of gold nanoparticles coated onto hollow, buoyant silica microspheres. These materials allow for a new type of molecular assay designated as a lab-on-a-bubble (LoB). LoB materials serve as a convenient platform for the detection of analytes in solution and offer several advantages over traditional colloidal gold and planar SERS substrates, such as the ability to localize and concentrate analytes for detection. An example assay is presented using the LoB method and cyanide detection. Cyanide binds to SERS-active, gold-coated LoBs and is detected directly from the corresponding SERS signal. The abilities of LoBs and a gold colloid to detect cyanide are compared, and in both cases, a detection limit of ~170 ppt was determined. Differences in measurement error using LoBs versus gold colloid are also described, as well as an assay for 5,5'-dithiobis(2-nitrobenzoic acid) that shows the benefit of using LoBs over SERS analyses in colloids, which are often plagued by particle aggregation.     

Metal-doped inorganic nanoparticles for multiplex detection of biomarkers by a sandwich-type ICP-MS immunoassay

Metal-doped inorganic nanoparticles were synthesized for the multiplex detection of biomarkers by a sandwich-type inductively coupled plasma mass spectrometry (ICP-MS) immunoassay. The synthesized Cs-doped multicore magnetic nanoparticles (MMNPs) were used not only for magnetic extraction of targets but also for ratiometric measurement in ICP-MS. In addition, three different metal/dye-doped silica nanoparticles (SNPs) were synthesized as probes for multiplex detection: Y/RhBITC (rhodamine B isothiocyanate)-doped SNPs for CRP (cardiovascular disease), Cd/RhBITC-doped SNPs for AFP (tumor), and Au/5(6)-XRITC (X-rhodamine-5-(and-6)-isothiocyanate)-doped SNPs for NSE (heart disease). For quantification, the doped metals of SNPs were measured by ICP-MS and then the signal ratio to Cs of MMNPs was plotted with respect to the concentration of targets by a ratiometry. Limits of detection (LOD) of 0.35 ng/mL to 77 ng mL⁻¹ and recoveries of 83%–125% were obtained for serum samples spiked with the biomarkers. Since no sample treatment was necessary prior to the extraction, the proposed method provided short analysis time and convenience for the multiplex determination of biomarkers, which will be valuable for clinical application.     

Influence of surfactant surface coverage and aging time on physical properties of silica nanoparticles

The experimental results on the influence of surfactant surface coverage and aging time on physical properties of silica nanoparticles were reported. The spherical silica nanoparticles have been synthesized using polyethylene glycol (PEG) as the surfactant and oil shale ash (OSA) as a new silica source. In order to identify the optimal condition for producing the best quality silica nanoparticles with the good dispersion and uniformity, the effects of surfactant surface coverage and aging time were investigated. It was found that the particle size and distribution of silica nanoparticles depend on the concentration of PEG in dispersion. At relatively low concentration, 0–2 wt.%, the existing PEG is not sufficient to prevent further growth of the initially formed silica nanoparticles, leading to large aggregates of silica particles. When the PEG concentration increases to 3 wt.%, self-assembled PEG layer on the surface stabilizes the initially formed silica nanoparticles and the silica particles with average diameter of 10 nm are uniformly distributed. With further increasing the concentration of PEG, the number of PEG aggregates increases and silica nanoparticles are mainly formed inside the entangled PEG chains, resulting in an observation of clusters of silica nanoparticles. Moreover, it was found that as the aging time increased, the shape of silica nanoparticles becomes regular and the particle size distribution becomes narrow.     

Controllable synthesis of silica nanoparticle size and packing efficiency onto PVP-functionalized PMMA via a sol–gel method

This study aimed to investigate synthesis and adsorption behavior of silica nanoparticles onto polyvinylpyrrolidone (PVP)-functionalized poly(methyl methacrylate) under various conditions such as methanol/water ratio, ammonium hydroxide concentration, polymer contents, tetraethylorthosilicate contents, and total volume of solvent via sol–gel method. First, the copolymerization of methyl acrylate as a comonomer and 1-dodecanethiol as a chain transfer agent increased the thermal stability of the product; however, the uniformity of the PMMA particles decreased because of the chain transfer reaction. Second, the adsorption behavior and size of silica nanoparticles could be controlled by adjusting the silica synthesis conditions. The adsorbed silica particle size was greatly influenced by the ammonium hydroxide concentration and the addition of water further enhanced the size increase. However, increasing the water content reduced the packing efficiency of the adsorbed silica particles. Increasing the PVP-functionalized PMMA content at a fixed TEOS content linearly decreased the silica particle size. But TEOS concentration did not significantly affect the silica particle size. © 2020 Wiley Periodicals, Inc. J. Polym. Sci. 2020 , 58, 662–672     

An investigation of calibration materials for the measurement of metals in ambient particulate matter on filters by LA-ICP-MS

Three different types of simple and low-cost calibration material for the measurement of the metals content of ambient particulate matter (PM) on filters using laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS) have been compared: cellulose ester filters spiked with multi-element calibration solutions, pellets of compressed ambient particulate matter certified reference material (CRM), and powdered ambient particulate matter CRM adhered to a surface. Elements determined were As, Cd, Cr, Cu, Fe, Mn, Ni, Pb, V and Zn, each at approximate levels of 1000?ng per filter. Blank filters spiked with multi-elemental standards were found to be significantly more reproducible and repeatable than materials based on powdered reference materials. However, a comparison of these spiked filters with real samples of ambient PM showed that the analytical sensitivities obtained per mass of analyte were significantly different. It is concluded that the spiked filters could act as very effective quality control standards correcting, to within 1%, drifts in LA-ICP-MS measurements of up to 10%, or as indirect calibration materials supported by additional measurements using traditional wet chemical techniques.     

Manipulating microparticles with single surface-immobilized nanoparticles

This experimental study explores the capture and manipulation of micrometer-scale particles by single surface-immobilized nanoparticles. The nanoparticles, approximately 10 nm in diameter, are cationic and therefore attract the micrometer-scale silica particles in an analyte suspension. The supporting surface on which the nanoparticles reside is negative (also silica) and repulsive toward approaching microparticles. In the limit where there are as few as 9 nanoparticles per square micrometer of collector, it becomes possible to capture and hold micrometer-scale silica particles with single nanoparticles. The strong nanoparticle-microparticle attractions, their nanometer-scale protrusion forward of the supporting surface, and their controlled density on the supporting surface facilitate microparticle-surface contact occurring through a single nanoelement. This behavior differs from most particle-particle, cell-cell, or particle (or cell)-surface interactions that involve multiple ligand-receptor bonds or much larger contact areas. Despite the limited contact of microparticles with surface-immobilized nanoparticles, microparticles resist shear forces of 9 pN or more but can be released through an increase in the ionic strength. The ability of nanoparticles to reversibly trap and hold much larger targets has implications in materials self-assembly, cell capture, and sorting applications, whereas the single point of contact affords precision in particle manipulation.     

Viscoelastic properties of nanosilica‐filled epoxy composites investigated by dynamic nanoindentation

The viscoelastic properties of the epoxy filled with silica nanoparicles have been investigated by dynamic nanoindentation and characterized by the storage modulus and loss tangent. The materials studied are neat epoxy and silica/epoxy composites with silica volume fraction of 1, 3, 6, 10, and 14 vol %, respectively. The silica nanoparticles with an average diameter of 25 nm are found to disperse homogeneously in the epoxy matrix. The effect of the particle content, force frequency, and penetration load on the viscoelastic behavior is studied and discussed. The comparison with traditional testing methods such as tension, bending, and DMTA is made. Besides, theoretical results by using micromechanics models are also obtained and compared with the experimental results. © 2009 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 47: 1030–1038, 2009     

Development and validation of single particle ICP-MS for sizing and quantitative determination of nano-silver in chicken meat

The application of nanomaterials is leading to innovative developments in industry, agriculture, consumer products, and food and related sectors. However, due to the special properties of these materials there are concerns about their safety, especially because of our limited knowledge of human health effects and the fact that constantly new nanomaterials and applications thereof are being produced. The development of analytical techniques is a key element to understand the benefits as well as the risks of the application of such materials. In this study, a method is developed and validated for sizing and quantifying nano-silver in chicken meat using single particle inductive coupled plasma mass spectrometry (ICP-MS). Samples are processed using an enzymatic digestion followed by dilution of the digest and instrumental analysis of the diluted digest using single particle ICP-MS. Validation of the method in the concentration of 5–25 mg/kg 60-nm silver nanoparticles showed good performance with respect to trueness (98–99 % for size, 91–101 % for concentration), repeatability (<2 % for size, <11 % for concentration), and reproducibility (<6 % for size, <16 % for concentration). The response of the method is linear, and a detection limit as low as 0.1 mg/kg can be obtained. Additional experiments showed that the method is robust and that digests are stable for 3 weeks at 4 °C. Once diluted for single particle ICP-MS analysis, the stability is limited. Finally, it was shown that nano-silver in chicken meat is not stable. Silver nanoparticles dissolved and were transformed into silver sulfide. While this has implications for the form in which nano-silver will be present in real-life meat samples, the developed method will be able to determine the presence and quantity of nanoparticle silver in such samples.     

Synthesis of Composite Polystyrene/Silica Nanoparticles via Precipitation and Emulsion Polymerization Methods

Polystyrene/silica composite nanoparticles were synthesized via precipitation and emulsion polymerization methods, in the presence of a basic co‐monomer (e.g., 4‐VP and 1‐VID), and a colloidal aqueous silica solution. The effects of key process parameters, that is, solvent type, monomer/co‐monomer volume ratio and total monomers concentration for precipitation polymerization, and reaction temperature, pH value, initial silica‐sol concentration and initial monomer/co‐monomer molar ratio for emulsifier‐free emulsion polymerization on the particle morphology, silica content, and particle size distribution of the composite nanoparticles were experimentally investigated. Stable, spherical, and uniform in size composite nanoparticles were synthesized by both techniques. The average particle diameter varied from 108 to 182 nm for the emulsifier‐free emulsion polymerization and from 400 to 800 nm for the precipitation polymerization, while the silica content was as high as 38.3 wt.‐% for the former method and up to 15.5 wt.‐% for the later. The synthesized composite polymer/silica particles were then electrolytically co‐deposited with zinc on steel plates to improve the corrosion resistance of the metal's surface.

     

High-throughput determination of seven trace elements in food samples by inductively coupled plasma-mass spectrometry

A method was developed for high-throughput determinations of 7 elements in food samples, namely antimony (Sb), arsenic (As), cadmium (Cd), chromium (Cr), lead (Pb), mercury (Hg), and tin (Sn). The samples were digested by closed-vessel microwave-assisted digestion using concentrated nitric acid (HNO3) as the medium, followed by microwave- assisted evaporation to concentrate the sample solutions before dilution to the desired volume. The microwave-assisted evaporation procedure effectively reduced the final acid concentration to around 8% before analysis by inductively coupled plasma-mass spectrometry (ICP-MS). This reduction allows determination by ICP-MS to proceed without further sample dilution, which would affect the detection limit. The method was validated, and method recoveries for As, Cd, Cr, Pb, and Hg were within the certified ranges of the chosen certified reference materials. Recoveries of the 7 elements from spiked samples ranged from 93.1 to 103.6%. The standard uncertainties of precision for the 7 elements were between 3.1 and 4.3%. Interlaboratory comparison studies for As, Cd, and Pb gave z-scores ranging from -0.2 to 0.3.     

Dissolution and nanoparticle generation behavior of Be-associated materials in synthetic lung fluid using inductively coupled plasma mass spectroscopy and flow field-flow fractionation

Various Be-containing micro-particle suspensions were equilibrated with simulated lung fluid (SLF) to examine their dissolution behavior as well as the potential generation of nanoparticles. The motivation for this study was to explore the relationship between dissolution/particle generation behaviors of Be-containing materials relevant to Be-ore processing, and their epidemiologically indicated inhalation toxicities. Limited data suggest that BeO is associated with higher rates of beryllium sensitization (BS) and chronic beryllium disease (CBD) relative to the other five relevant materials studied: bertrandite-containing ore, beryl-containing ore, frit (a processing intermediate), Be(OH)₂ (a processing intermediate), and silica (control). These materials were equilibrated with SLF at two pH values (4.5 and 7.2) to reflect inter- and intra-cellular environments in lung tissue. Concentrations of Be, Al, and Si in SLF increased linearly during the first 20 days of equilibration, and then rose slowly, or in some cases reached a maximum, and subsequently decreased. Relative to the other materials, BeO produced relatively low Be concentration in solution at pH 7.2; and relatively high Be concentration in solution at pH 4.5 during the first 20 days of equilibration. For both pH values, however, the Be concentration in SLF normalized to Be content of the material was lowest for BeO, demonstrating that BeO was distinct among the four other Be-containing materials in terms of its persistence as a source of Be to the SLF solution. Following 149 days of equilibration, the SLF solutions were fractionated using flow-field flow fractionation (FlFFF) with detection via ICP-MS. For all materials, nanoparticles (which were formed during equilibration) were dominantly distributed in the 10–100 nm size range. Notably, BeO produced the least nanoparticle-associated Be mass (other than silica) at both pH values. Furthermore, BeO produced the highest Be concentrations in the size range corresponding to < 3 kDa (determined via centrifugal ultrafiltration), indicating that in addition to persistence, the BeO produced the highest concentrations of truly dissolved (potentially ionic) Be relative to the other materials. Mass balance analysis showed reasonable sample recoveries during FFF fractionation (50–100%), whereas recoveries during ICP-MS (relative to acidified standards) were much lower (5–10%), likely due to inefficiencies in nebulizing and ionizing the nanoparticles.