Hybrids consisting of silver nanoparticles (in varying fractions) and of TiOx/ZnO were prepared via top-down ion beam sputtering (IBS) deposition on silicon substrates. The deposited nanomaterials were characterized by scanning electron microscopy and X-ray photoelectron spectroscopy. It is shown that such composites represent a viable substrate for use in both surface enhanced Raman spectroscopy (SERS) and surface enhanced infrared absorption spectroscopy (SEIRAS), as exemplarily shown for crystal violet as the model analyte. The C-H bending mode at about 1181 cm?1 and the C-N vibration at 1361 cm?1 observed in the SERS and SEIRAS spectra, respectively, have been used as analytical signal. The substrate consisting of TiOx NPs with 33% fraction of silver provides the strongest enhancement in SERS (up to 10,000-fold), while TiOx/AgNPs with thickness of 2 and 1 nm in ion beam sputtering, respectively, provides the best sensitivity in SEIRAS. The substrates also display photocatalytic activity as shown by the degradation of adsorbed crystal violet under ultraviolet irradiation.
Graphical abstract Schematic of the preparation of hybrid substrates consisting of Ag and TiOx/ZnO nanoparticles via ion beam sputtering deposition. They were applied in both surface enhanced Raman and surface enhanced infrared absorption spectroscopies using crystal violet as model analyte, showing enhancements up to >10,000-fold in Raman.
Photonic encoding magnetized silica microspheres were synthesized from a polydisperse system containing silica and Fe3O4 nanoparticles by using a microfluidic self-assembly device. The optical and structural properties of the magnetized microspheres were characterized by scanning electron microscopy and reflection spectra. The concentration of Fe3O4 nanoparticles in polydisperse system was found to strongly affect the characteristics of magnetized microspheres. They possess a Janus face, are porous, and possess structural color (red). The magnetic characteristic of the synthesized microspheres is not lost after they are immersed in piranha solution for 12 h. The magnetized microspheres were applied to aptamer-based enrichment of the food toxin Ochratoxin A (OTA). Methods for immobilization of OTA aptamer on the microsphere surfaces were investigated. The modified microspheres can extract up to 80% of OTA if the surface of the microspheres is loaded with 275 ng·cm?2 of aptamer and the number of microspheres is 200. The work provides a new pathway for aptamer-based enrichment of small molecules from complex matrixes.
Graphical abstract Photonically encoded magnetized silica microspheres were synthesized by using microfluidic self-assembly device. The optical, magnetic and structural properties of the microspheres were investigated. The three-dimensional porous magnetized microspheres were applied to aptamer-based enrichment of the food toxin Ochratoxin A.
The authors describe the preparation of magnetic cobalt/nitrogen-doped carbon microspheres (Co-N/Cs) by combining a hydrothermal procedure with a carbonization process. The textures of the Co-N/Cs were investigated by powder X-ray diffraction, scanning electron microscopy, high-resolution transmission electron microscopy, nitrogen adsorption-desorption isotherms and vibration sample magnetometry. The Co-N/Cs possess a high surface area and strong magnetism. This results in good adsorption capability and enables magnetic separation. The Co-N/Cs are shown to be an effective magnetic solid-phase extraction adsorbent for the enrichment of various phthalate esters (diethyl phthalate, diallyl phthalate and diisobutyl phthalate) from sport beverages and milk samples prior to their determination by HPLC. The limits of detection (at an S/N ratio of 3) are between 0.1–0.2 and 0.08–0.3 ng mL?1 for sport beverages and milk samples, respectively. The recoveries when extracting all the spiked samples varied from 80.3% to 116.2%.
Graphical abstract Magnetic cobalt/nitrogen-doped carbon microspheres (Co-N/Cs) were prepared and used as an effective magnetic solid phase extraction adsorbent for the enrichment of phthalate esters from beverages and milk samples.
Magnetic microspheres (Fe3O4) were coated with polydopamine (PDA) and loaded with the metal ions Ti(IV) and Nb(V) to give a material of type Fe3O4@PDA-Ti/Nb. It is shown to be useful for affinity chromatography and for enrichment of phosphopeptides from both standard protein solutions and real samples. For comparison, such microspheres loaded with single metal ions only (Fe3O4@PDA-Ti and Fe3O4@PDA-Nb) and their physical mixtures were also investigated under identical conditions. The binary metal ion-loaded magnetic microspheres display better enrichment efficiency than the single metal ion-loaded microspheres and their physical mixture. Both multiphosphopeptides and monophosphopeptides can be extracted. The Fe3O4@PDA-Ti/Nb microspheres exhibit ultra-high sensitivity (the lowest detection amount being 2 fmol) and selectivity at a low mass ratio such as in case of β-casein/BSA (1:1000).
Graphical abstract Magnetic microspheres (Fe3O4) were coated with polydopamine (PDA) and loaded with the metal ions Ti(IV) and Nb(V) to give a material of type Fe3O4@PDA-Ti/Nb. Results showed its great potential as an affinity probe in phosphoproteome research due to rapid magnetic separation of phosphopeptides, ultrahigh sensitivity and selectivity, and remarkable reusability.
The authors describe an aptamer-based liquid crystal (LC) assay for kanamycin (KNM) that displays visible signal changes. The KNM aptamer was immobilized, along with the N,N-dimethyl-N-(3-(trimethoxysilyl)propyl)-1-octadecanaminiuchloride (DMOAP) on a glass slide, and this results in a homeotropic orientation of the LCs film. In the presence of KNM, its interaction with the aptamers will result in the formation of G-quadruplexes. These will destroy the orientated arrangement of the LCs on the surface to result in a color change from pink to green that can be visually observed by using crossed polarizers. The method possesses high specificity and the detection limit is as low as 1 nM. Unlike current laboratory-based KNM assays, this method does not require instrumental read-out which is highly beneficial in terms of on-site food analysis.
Graphical abstract Schematic presentation of an aptamer-based liquid crystal assay for detection of kanamycin. Kanamycin-binding aptamers form G-quadruplex structures. The binding event distorts the initial homeotropic orientation of the LCs, and this results in a color change of the polarized image of the liquid crystal films.
A zirconium(IV)-based metal organic framework (Zr-MOF) was deposited on polydopamine-coated silica microspheres to form microspheres of type SiO2@PDA@Zr-MOF. These were packed into capillary columns for enrichment of phosphopeptides. The column was off-line coupled to both matrix-assisted laser desorption/ionization time of flight mass spectrometry and LC-ESI-MS/MS. The method has a detection limit as low as 4 fmol of β-casein digest and a selectivity as high as 1:1000 (molar ratio of β-casein and BSA digest). It was applied to the analysis of human saliva. In total, 240 endogenous phosphopeptides were identified in only 25 μL human saliva.
Graphical abstract A zirconium-based metal organic framework (Zr-MOF) was modified outside of polydopamine-coated silica microspheres to form microspheres named SiO2@PDA@Zr-MOF. Then they were packed in capillary columns for selective enrichment of phosphopeptides via interaction between Zr-O clusters and phosphate groups. The pre-concentration resulted in a better detection of phosphopeptides by mass spectrometry. Tris: Tris(hydroxymethyl)aminomethane; DMF: Dimethyl Formamide; Zr-MOF: Zirconium(IV)-organic framework; MOAC: Metal oxide affinity chromatography.
An efficient approach is demonstrated for preparing particles consisting of a silver core and a shell of molecularly imprinted polymer (Ag@MIP). The MIP is prepared by using bisphenol A (BPA) as the template and 4-vinylpyridine as the functional monomer. The Ag@MIP fulfills a dual function in that the silver core acts as a SERS substrate, while the MIP allows for selective recognition of BPA. The Ag@MIP is characterized by scanning electron microscopy, transmission electron microscopy, X-ray powder diffraction, thermogravimetric analysis and Raman spectroscopy. The Raman intensity of Ag@MIP is higher than that of bare silver microspheres. The detection limit for BPA is as low as 10?9 mol·L?1.
Graphical abstract Schematic illustration of the preparation of silver microspheres coated with a molecularly imprinted polymer (Ag@MIPs) for detecting bisphenol A (BPA) by surface enhanced Raman scattering (SERS).
Monodisperse nonmagnetic macroporous poly(glycidyl methacrylate) (PGMA) microspheres were synthesized by multistep swelling polymerization of glycidyl methacrylate, ethylene dimethacrylate and 2-[(methoxycarbonyl)methoxy]ethyl methacrylate (MCMEMA). This was followed (a) by ammonolysis to modify the microspheres with amino groups, and (b) by incorporation of iron oxide (γ-Fe2O3) into the pores to render the particles magnetic. The resulting porous and magnetic microspheres were characterized by scanning and transmission electron microscopy (SEM and TEM), atomic absorption and Fourier transform infrared spectroscopy (AAS and FTIR), elemental analysis, vibrating magnetometry, mercury porosimetry and Brunauer-Emmett-Teller adsorption/desorption isotherms. The microspheres are meso- and macroporous, typically 5 μm in diameter, contain 0.9 mM · g?1 of amino groups and 14 wt.% of iron according to elemental analysis and AAS, respectively. The particles were conjugated to p46/Myo1C protein, a potential biomarker of autoimmune diseases, to isolate specific autoantibodies in the blood of patients suffering from multiple sclerosis (MS). The p46/Myo1C loaded microspheres are shown to enable the preconcentration of minute quantities of specific immunoglobulins prior to their quantification via SDS-PAGE. The immunoglobulin M (IgM) with affinity to Myo1C was detected in MS patients.
Graphical abstract Monodisperse magnetic poly(glycidyl methacrylate) microspheres were synthesized, conjugated with 46 kDa form of unconventional Myo1C protein (p46/Myo1C) via carbodiimide (DIC) chemistry, and specific autoantibodies isolated from blood of multiple sclerosis (MS) patients; immunoglobulin M (IgM) level increased in MS patients.
The authors describe an ethylene glycol assisted precipitation method for synthesis of Er(III)/Yb(III)-doped BiF3 nanoparticles (NPs) at room temperature. Under 980-nm light irradiation, the NPs emit upconversion (UC) emission of Er(III) ions as a result of a two-photon absorption process. The temperature-dependent green emissions (peaking at 525 and 545 nm) are used to establish an unambiguous relationship between the ratio of fluorescence intensities and temperature. The NPs have a maximum sensitivity of 6.5?×?10?3 K?1 at 619 K and can be applied over the 291–691 K temperature range. The results indicate that these NPs are a promising candidate for optical thermometry.
Graphical abstract Schematic of the room-temperature preparation of Er(III)/Yb(III)-doped BiF3 nanoparticles with strongly temperature-dependent upconversion emission.
The authors describe an amperometric sensor for dopamine (DA) by employing olive-like Fe2O3 microspheres (OFMs) as the electrocatalyst for DA oxidization. The OFMs were prepared by using a protein templated method. The structure and properties of the OFMs were characterized by scanning electron microscopy, X-ray powder diffraction, energy dispersive x-ray spectroscopy, cyclic voltammetry and electrochemical impedance spectroscopy. The OFMs possess excellent catalytic activity towards DA oxidization due to their unique morphology. The sensor responds to DA within less than 5 s. The sensor, best operated at a voltage of +0.2 V (vs. SCE) responds linearly in the 0.2 to 115 μM DA concentration range and has a 30 nM detection limit. The selectivity, reproducibility and long-term stability of the sensor are acceptable. It performs well when applied to spiked human urine samples.
Graphical abstract Olive-like Fe2O3 microspheres (OFMs), synthesized using egg white as template, display excellent catalytic activity towards dopamine (DA) oxidization due to their unique morphology. They were applied for DA detection using the amperometric technique. The electrochemical sensor exhibited a high sensitivity and a 30 nM detection limit. DAQ: dopaquinone.
This paper describes a rapid method for fabrication of a paper substrate coated with gold nanoparticles (GNPs) that results in the formation of a large number of hot spots on the surface and allows an adequate control of the active area. The resulting substrate is shown to be a viable material for use in quantitative surface-enhanced Raman spectroscopy (SERS) analysis. The influence of the amount of GNPs on the SERS signals (using crystal violet as a sample analyte) was correlated with field-emission scanning electron microscopy, UV-visible and theoretical studies. The use of this substrates results in larger enhancement of Raman signals and in comparably repeatability when compared to commercially available substrates. The substrate was applied to SERS-based determination of nicotine and uric acid in aqueous solution, and the respective limits of detection are 20 and 30 μg L?1. The results indicate that the SERS substrates may be applied to the quantification of a wide variety of molecules.
Graphical abstract A novel and rapid procedure for preparation of sensitive and reproducible paper-based SERS substrates has been successfully developed and applied to quantitative detection of nicotine and uric acid.
Colloidal gold, quantum dots and polystyrene microspheres were used as labels in three kinds of lateral flow immunochromatographic assays (ICAs) for the detection of zearalenone (ZEN) in cereal samples. The assays allow ZEN to be quantified within 20 min. The LODs are 10 μg·L?1 of ZEN for the colloidal gold-based ICA, and 1 μg·L?1 for both the quantum dot and polystyrene microsphere based ICAs. The respective data are 60 μg·kg?1, 6 μg·kg?1 and 6 μg·kg?1, respectively, for spiked samples and cereals. Only minor cross-sensitivity occurred between ZEN and fusarium toxins, and no cross-sensitivity if found for aflatoxin B1, T-2 mycotoxin, ochratoxin A, deoxynivalenol, and fumonisin B1. LODs of the three assays are lower than the maximum limits of ZEN set by most standardization agencies.
Graphical abstract Schematic presentation of three lateral flow immunochromatographic assays (ICAs) based on the use of (a) colloidal gold (CG), (b) fluorescent quantum dots (QD), and (c) polystyrene microspheres (PMs) as signalling labels for the rapid and sensitive determination of zearalenone (ZEN) in cereal samples.
This review (with 144 refs.) focuses on the recent advances in the preparation and application of magnetic micro/nanoparticles. Specifically, it covers (a) methods for preparation (such as by coprecipitation, pyrolysis, hydrothermal, solvothermal, sol-gel, micro-emulsion, sonochemical, medium dispersing or emulsion polymerization methods), and (b) applications such as magnetic resonance imaging, magnetic separation of biomolecules (nucleic acids; proteins; cells), separation of metal ions and organic analytes, immobilization of enzymes, biological detection, magnetic catalysis and water treatment. Finally, the existing challenges and possible trends in the field are addressed.
Graphical abstract This review focuses on the recent advances in the preparation and application of magnetic micro/nano particles. Finally, the existed problems and possible trends in the field were discussed. a: Fe3O4@SiO2-PVAm: polyvinyl amine-coated Fe3O4@SiO2 b: CTS/MMT-Fe3O4 microsphere: chitosan/montmorillonite-Fe3O4 microsphere c: MTAMs: magnetic targeted antibiotic microspheres d: SM: the code of iron oxide-silica composite microspheres e: PSt: poly styrene f: gamma-PGA- PLA: poly(gamma-glutamic acid) and poly(lactide) g: poly(-MMA–DVB–GMA) microspheres: poly(methylmethacrylate–divinylbenzene–glycidylmethacrylate) microspheres h: AEAPS: N-(2-aminoethyl)-3-aminopropyltrimethoxysilane
CdSe:Eu nanocrystals were successfully synthesized and characterized by transmission electron microscopy, X-ray powder diffraction, and X-ray photoelectric spectroscopy. The CdSe:Eu nanocrystals showed enhanced green electrochemiluminescence (ECL) intensity when compared to pure CdSe nanocrystals. Further, the nanocrystals were used to design an ECL immunosensor for the detection of carcinoembryonic antigen (CEA) that has a linear response over the 1.0 fg·mL?1 to 100 ng·mL?1 CEA concentration range with a 0.4 fg·mL?1 detection limit. The assay was applied to the determination of CEA in human serum samples.
Graphical abstract Schematic of the assay: GCE-glassy-carbon electrode, Ab- Antibody, BSA- Bovine serum albumin, Ag- Antigen. CdSe:Eu nanocrystals were used to design an ECL immunosensor for the detection of carcinoembryonic antigen.
A three-dimensional magnetic hollow porous raspberry-like hierarchical Co/Ni@carbon microspheres (3D Co/Ni@carbon) were synthesized by using a bimetal-organic framework (Co/Ni-MOF) as a precursor and subsequent calcination under nitrogen. The 3D Co/Ni@carbon is a novel solid phase extractant that displays outstanding extraction capability and separation efficiency for the pyrethroid pesticides ethofenprox and bifenthrin. This is ascribed to the beneficial effects of facile analyte transport (due to the presence of free pores), the abundant number of adsorption sites (which warrant efficient extraction), and the excellent structural stability of the material. The 3D Co/Ni@carbon was applied to dispersive magnetic solid-phase extraction (d-MSPE), and the two pyrethroids were quantified by HPLC (UV detection wavelength: 220 nm). The method has a high preconcentration factor (937–1012) and give recoveries that range between 85.6–106.9%, with RSDs (for n?=?5) of <6% in case of real samples.
Graphical abstract The hierarchical porous Co/Ni@carbon microsphere as adsorbent was fabricated, and it showed high extraction efficiency for two pyrethroids.
Reduced graphene oxide hollow microspheres (rGO HMS) were encapsulated with gold nanoparticles (AuNPs) by spray drying. Scanning electron microscopy, transmission electron microscopy, X-ray diffraction and Raman spectroscopy were used to characterize the AuNP/rGO HMS. When placed on a glassy carbon electrode (GCE), it exhibits excellent electrochemical catalytic properties towards the oxidation of nitrite. The electrocatalytic properties were studied using various electrochemical techniques. Compared to AuNP-decorated graphene sheet based electrodes documented in the literature, the one presented here provides a larger surface area. This enhances the catalytic activity towards nitrite. The electrode, typically operated at a working potential of 0.82 V (vs. SCE), has a linear response in the 5.0 μM to 2.6 mM nitrate concentration range, and a detection limit as low as 0.5 μM (at an S/N ratio of 3).
Graphical abstract Schematic presentation of the synthesis of graphene hollow microspheres encapsulated with of gold nanoparticles (AuNP/rGO HMS) through a spray drying technique. The material was applied to the electrochemical determination of nitrite.
A metal-organic framework (MOF) was designed and prepared from luminescent Tb(III), adenosine diphosphate (ADP) and bipyridyl (Bipy). Its green fluorescence at 545 nm is shown to enable the fluorometric detection of cyanide ion based on the principle of π-conjugation-induced fluorescence enhancement. The fluorescence of the probe is strongly increased by cyanide due to extended π-conjugation between probe MOF and cyanide which sensitizes the fluorescence of Tb(III). This effect can be used to quantify cyanide at levels as low as 30 nM in aqueous solution. The method was applied to the determination of cyanide in saliva samples. The lack of interference by acetate and fluoride is a specific feature of this method. The method based on the principle of π-conjugation-induced fluorescence enhancement provides a new sensing way for widely used fluorescence assays.
Graphical abstract A cyanide-selective Tb-ADP-Bipy MOF was designed and synthesized for the detection of cyanide based on the principle of π-conjugation-induced fluorescence enhancement.
Titanium dioxide nanoparticles (NPs) were synthesized by a sol-gel method from hexafluorotitanic acid using poly(ethylene glycol) as a capping agent. The crystal structure and morphology of the NPs were characterized by X-ray diffraction, FESEM, and TEM. The NPs were used to modify a graphite paste electrode for simultaneous determination of uric acid (UA) and guanine (GU). The effect of calcination temperature on crystal structure and electrocatalytic activity was investigated. The electrochemical responses to UA and GU at bare GP, TiO2–350/GP, and TiO2–600/GP electrodes were compared. The DPV oxidation peaks of UA and GU were found to be strongest at around 304 and 673 mV, respectively, against Ag/AgCl reference electrode, and this are well separated for effective simultaneous determination. UA and GU can be simultaneously determined by this method. Response is linear within the range 0.1–500 μM and 0.1–40 μM for UA and GU, respectively. The detection limits are 70 nM for UA and 50 nM for GU (at an S/N? ratio of?3). The TiO2–600/GP electrode showed excellent analytical performance when analyzing spiked urine and serum samples.
We report on a method for highly sensitive and selective colorimetric determination of Hg(II) via a signal amplification strategy. Cu@Au nanoparticles (NPs) are found to exhibit intrinsic peroxidase-like activity and can catalyze the oxidation of 3,3′,5,5′-tetramethylbenzidine by H2O2. This is accompanied by a solution color change from colorless to green (with an absorption peak at 655 nm). The catalytic capability of the Cu@Au NPs (pale green) is strongly enhanced by a Cu@Au-Hg trimetallic amalgam (bluish), and this effect can be applied directly to the determination of Hg(II). The limit of detection as observed with the unaided eye is 10 nM, which is at least one order of magnitude lower than that of the known AuNP-based colorimetric assay. Due to excellent specificity of the amalgamation process, the assay is highly selective for Hg(II) and is not interfered by other metal ions in up to 0.5 μM concentrations. This assay was successfully applied to the determination of Hg(II) in tap water. In view of these advantages, we expect this colorimetric method to become an attractive tool for the quantitation of Hg(II) in biological, environmental, and food samples.
Graphical Abstract Cu@Au nanoparticles (NPs) exhibit intrinsic peroxidase-like activity and can catalyze the oxidation of tetramethylbenzidine (TMB) by H2O2. This is accompanied by a color change of the solution from colorless to green.
A facile, one-pot green method is presented for the preparation of water-soluble luminescent copper nanoclusters (Cu-NCs) from copper dichloride and cysteine as the precursor and stabilizer, respectively. The Cu-NCs are characterized by high resolution transmission electron microscopy, X-ray photoelectron spectroscopy, fluorescence, UV–Vis, and Raman spectroscopy. The Cu-NCs have an average size of 3.5 nm and are stable in aqueous solution at least for 2 weeks. Under photo excitation with 365 nm light, the Cu-NCs display strong green fluorescence with the maximum of emission at 490 nm and a quantum yield of 5.6 %. Fluorescence is quenched by Cr(VI) ion, and this effect was exploited to develop a highly selective method for the determination of Cr(VI). The detection limit of this probe is as low as 43 nM.
Graphical Abstract A facile, one-pot, “green” synthetic route was developed for preparing water-soluble luminescent copper nanoclusters (CuNCs) by using copper chloride and cysteine as the precursor and stabilizer, respectively. Their fluorescence is quenched by Cr(VI) ion, and this is exploited in a sensitive assay for Cr(VI) ions.
