The authors describe an ultrasonic-assisted headspace method for solid phase micro-extraction (UA-HS-SPME) of 7 polychlorinated biphenyls (PCBs) with codes PCB28, PCB52, PCB101, PCB118, PCB138, PCB153 and PCB180. The coating is based on a poly-dopamine metal-organic framework [PDA-MIL-53(Fe)] on a stainless steel wire. The coating can be prepared and evenly deposited on the stainless fiber by dipping the PDA fiber into a solution of MIL-53(Fe). The assay is also environmentally friendly because water is used as the solvent. The effects of extraction time, addition of salts, pH value and power of ultrasonic power were optimized. The coating is found to possess a high selectivity and adsorption capacity for PCBs compared to commercial SPME fibers such as the divinylbenzene/carboxen/polydimethylsiloxane fibers. Following desorption, the PCBs were quantified by GC-MS. The detection limits are between 50 and 90 pg?g?1 of PCBs in soil. The fibers can be easily prepared, and the batch-to-batch reproducibility (RDS) is <10% (for n = 6). The fibers are inexpensive, re-usable and can be easily manipulated, and particularly well suited for screening polychlorinated biphenyls in soil.
Graphical abstract Schematic of the preparation of an extraction fiber using stainless steel wire as substrate, PDA as adhesive, and MIL-53(Fe) as the adsorbent. It was applied to the extraction of PCBs from soil. The fiber is durable and inexpensive.
ZnO nanoflakes (ZnONFs) were electrochemically grown on a nickel-titanium alloy (NiTi) wire for use in solid-phase microextraction. Prior to the growth of ZnONFs, the NiTi wire was hydrothermally treated for in-situ growth of TiO2/NiO nanoflakes as a seeding base. The applied potential was used to control the dimensions of vertically oriented hexagonal ZnONFs. After annealing at 600 °C, the resulting fiber display fairly selective affinity for polychlorinated biphenyls (PCBs) and polycyclic aromatic hydrocarbons. The fibers were applied to the preconcentration of PCBs which then were quantified by HPLC with UV detection. Compared to commercial polydimethylsiloxane coatings, the new coating displays high extraction capability, rapid extraction kinetics and superior cycling stability. This is assumed to be due to its high surface-to-volume ratio, double-sided open access structure, and enhanced structural stability. The assay excels by (a) a wide analytical range (0.10 to 200 μg L?1 of PCBs), (b) low limits of detection (20–17 ng L?1), and (c) low standard deviations for the single fiber repeatability (<9.8%) and for the fiber-to-fiber reproducibility (<7.5%). Satisfactory accuracy and precision were achieved when PCBs were determined by this method in spiked rain water, river water and wastewater samples.
Graphical abstract ZnO nanoflakes were fabricated on a superelastic nickel-titanium alloy wire in desired orientation with enhanced extraction capability and good extraction selectivity. The fabricated fiber was suitable for the determination of PCBs in environmental water samples
A graphene based bucky gel-coated stainless steel fiber was prepared and applied to headspace solid phase microextraction of volatile organic compounds. Graphene was mixed with an ionic liquid to produce a bucky gel that displays the attractive features of both compounds. It can be directly deposited on an etched stainless steel wire to give the fiber for use in extraction of benzene, toluene, ethylbenzene and xylene (BTEX) isomers. The presence of graphene favors the π-interaction between the sorbent and aromatic analytes. The sorbent is thermally stable up to 300 °C and can be used more than 50 times. It was characterized by field emission scanning electron microscopy, FT-IR spectroscopy and thermogravimetric analysis. Under optimized conditions, linear responses were found in the range of 0.11–5000 μg L?1 for toluene, 0.15–5000 for benzene and o-xylene, 0.17–5000 for m- and?p-xylene and 0.20–5000 for ethylbenzene. Limits of detection are between 0.03 and 0.06 μg L?1 (at an S/N ratio of 3). The run-to-run RSDs are <5.8% (for n =?6), and fiber-to-fiber RSDs are 4.1–9.2% (n =?4). The method was successfully applied to the extraction of BTEX isomers in spiked urine samples and gave recoveries between 88 and 105%.
Graphical abstract Graphene based bucky gel (G-BG) was prepared by mixing an ionic liquid with graphene. It was physically deposited on stainless steel wire. The fiber was applied to the headspace solid phase microextraction (HS-SPME) of benzene, toluene, ethylbenzene and xylenes.
This work introduces a new gradient fiber coating for microextraction of chlorobenzenes. Nanoclusters of organoclay-Cu(II) on a copper wire were fabricated by wireless electrofunctionalization. The resultant gradient coatings are more robust, and thermally and mechanically stable. Wireless electrofunctionalization was carried out in a bipolar cell under a constant deposition potential and using an ethanolic electrolyte solution containing stearic acid and montmorillonite. Stearic acid acts as an inexpensive and green coating while montmorillonite acts as a modifier to impart thermal stability. The gradient morphology of the nanoclusters was investigated by scanning electron microscopy, thermogravimetric analysis and energy dispersive X-ray spectroscopy. The coated wire was placed in a hollow needle and used for headspace in-tube microextraction (HS–ITME) of chlorobenzenes (CBs). Effects of various parameters affecting synthesis and extraction were optimized. Following extraction, the needles were directly inserted into the GC injector, and the CBs (chlorobenzene, 1,4-dichlorobenzene, 1,2-dichlorobenzene, 1,2,4-trichlorobenzene, 1,2,3,4-tetrachlorobenzene) were quantified by GC–MS. The limits of detection under optimized conditions range from 0.5 to 10 ng.L?1. The intra– and inter–day relative standard deviations (RSDs) (for n?=?10, 5 respectively) using a single fiber are 6–10 and 10–15%, respectively. The fiber–to–fiber RSDs (for n?=?3) is between 17 and 24%. The method was successfully applied to the extraction of CBs from real water samples, and relative recoveries are between 91 and 110%.
Graphical abstract A gradient coating of organoclay–Cu nanoclusters was fabricated on a copper wire by wireless electrofunctionalization. The oxidation of copper takes place at the anodic pole (red) while dissolved oxygen in ethanol solution is reduced at the cathodic pole (blue).
Carbon nanotubes were modified with magnetite nanoparticles, and 1,4-diazabicyclo[2.2.2]octane (DABCO) was then covalently attached to their surface. The resulting material is shown to be a viable sorbent for the preconcentration of the selective serotonin reuptake inhibitors citalopram, sertraline, fluvoxamine and fluoxetine via ultrasound-assisted magnetic solid phase extraction. The effects of pH value, sorbent dosage, eluent volume and salt concentration were optimized by central composite design and desirability function. The drugs were quantified by HPLC with UV detection. Detection limits are as low as 0.2, 0.25, 0.3, and 0.5 ng mL?1 for citalopram, sertraline, fluvoxamine and fluoxetine, respectively. The intra-day precisions (RSDs) are <4.0%. The method was applied to the determination of the selective serotonin reuptake inhibitors in plasma samples and gave recoveries of >91%. The sorbent can be reused 12 times without a noticeable decrease in extraction efficiency.
Graphical abstract Magnetic carbon nanotubes were modified with 1,4-diazabicyclo[2.2.2]octane (DABCO) with ionic liquid framework. Resulting material was used as a reusable and selective sorbent for preconcentration and extraction of antidepressant drugs from plasma samples.
A method is described for the determination of the polarity of mixed organic solvents by using the fluorescent probe Hostasol Red (HR) desposited on the outer surface of nanosized zeolite L. Organic solvents and their mixtures can be roughly classified according to their polarity with bare eyes and fluorometrically. Emission peaks range from 520 to 640 nm. Some solvents act as quenchers. The method is studied with series of protic and nonprotic solvents, and with selected mixtures of organic solvents.
Graphical abstract The dye Hostalene Red adsorbed on nanosized zeolite shows strong fluorescence solvatochromism. This can be exploited to quickly assess the polarity of solvents and solvent mixtures.
The authors describe four different kinds of sorbents for solid-phase extraction (SPE) and preconcentration of proteins from complex samples. All are based on the use of a poly(glycidyl-co-ethylene dimethacrylate) host monolith that was chemically functionalized by using two different ligands (ammonia and cysteamine). Gold nanoparticles (AuNPs) or silver NPs were then assembled to the amino or thiol groups. The resulting materials are shown to be viable stationary phases for use in SPE cartridges. The sorbents can selectively retain bovine serum albumin, and the thiol-modified sorbents containing AuNPs and AgNPs provide the highest recoveries (>90%) and satisfactory loading capacities (29.3 and 17.6 μg?mg?1 of sorbent, respectively). The applicability of these nanosorbents was demonstrated by preconcentrating viscotoxins from mistletoe extracts. The enriched fractions were subjected to MALDI-TOF analysis to underpin their selectivity.
Graphical abstract Hybrid materials based on methacrylate polymers modified with gold or silver nanoparticles were used as sorbents for solid phase extraction and preconcentration of bovine serum albumin and mistletoe viscotoxins, this followed by MALDI-TOF analysis.
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.
The authors describe a new sorbent for amitraz and teflubenzuron pesticides. It consists of a platinum wire coated with polypyrrole-coated ZnO nanorods. The nanocomposite was prepared by a two-step process. In the first step, oriented ZnO nanorods were hydrothermally grown in situ on a platinum wire. Subsequently, oxidative vapor phase polymerization of pyrrole was performed on FeCl3-impregnated ZnO nanorods to give a porous polypyrrole film. The organic/inorganic nanocomposite synthesized through hydrothermal deposition and chemical vapor deposition polymerization yields material with attractive properties. The coated wire was applied to solid-phase microextraction of amitraz (in the form of 2,4-dimethylaniline resulting from the hydrolysis of amitraz) and teflubenzuron. The effects of extraction temperature, extraction time, sample pH value and salt concentration were optimized. The analytes 2,4-dimethylaniline and teflubenzuron were then quantified by GC-MS. Under optimum conditions, the LODs range between 0.1 and 0.15 ng.mL?1. Relative standard deviations at two concentration are <8.3% for intraday precision and <10.3% for inter-day precision. In all cases, the fiber to fiber reproducibility is <12.2%. For both analytes the linear dynamic ranges are 0.5–300 ng.mL?1. The procedure was successfully applied to the analysis of spiked agricultural water samples.
Graphical abstract A novel inorganic/organic hybrid nanocomposite was synthesized through in situ hydrothermal deposition of ZnO nanorods and ten placing a thin layer of polypyrrole on them by chemical vapor deposition polymerization. This nanocomposite was applied to fabricate a solid-phase microextraction fiber for the extraction of amitraz and teflubenzuron pesticides residue from agricultural samples prior to their quantitation by GC-MS.
The authors introduce an arc ion plating method for the deposition of chromium oxide (Cr2O3) on a steel wire substrate, and its use as a coating for solid phase microextraction. The coating has a micro- and nano-scaled structure after annealing at 700 °C. It is found that Cr2O3 exhibits a good extraction capability for the aromatic hydrocarbons naphthalene, anthracene, fluorene, fluoranthene, and biphenyl. Following desorption by high temperature at 300 °C, the analytes were quantified by gas chromatography (GC). The limits of detection are in the range between 20 and 200 ng·L?1, and calibration plots are linear within a wide range (0.2 to 400 μg·L?1). The coating has excellent mechanical properties, with a hardness is as high as 31.7 GPa, and the adhesion strength between coating and substrate reaches 20.1 N (corresponding to the critical Hertzian contact stress of 10 GPa). This, along with the chemical and thermal stability of the Cr2O3 coating, endows the wire with a long operational life. It was used for at least 100 times without any obvious decline of extraction capability.
Graphical abstract An arc ion plating method was introduced for the deposition of chromium oxide (Cr2O3) on a steel wire substrate, and its use as a coating for solid phase microextraction with high mechanical strength, stability, and long operational lifetime.
A stainless steel fiber was coated with a gate-opening controlled metal-organic framework ZIF-7 via a sol-gel method and applied to the solid-phase microextraction of aldehydes (hexanal, heptanal, octanal, nonanal, decanal) from exhaled breath by lung cancer patients. The effects of temperature and time on the sorption and desorption were optimized. Under optimum condition, the modified fiber displays enrichment factors (typically ranging from 300 to 10,000), low limits of detection (0.61–0.84 μg L?1), and wide linear ranges of hexanal, heptanal (5–500 μg L?1) and octanal, nonanal, decanal (10–1000 μg L?1). The high extraction capability for aldehydes is thought to result from (a) the combined effects of the large surface area and the unique porous structure of the ZIF-7, (b) the hydrophobicity and gate-opening effect of the sorbent, (c) the high selectivity of the window, and (d) the presence of unsaturated metal-coordination sites. The coated fiber is thermally stable and can be re-used >150 times. The relative standard deviation (RSD) for six replicate extractions using a single fiber ranged from 1.4–15.3% for intra-day and 2.4–16.1% for inter-day. The fiber-to-fiber reproducibility for three fibers prepared in parallel was in the range of 2.4–12.6% (RSD). The method was applied to the extraction of aldehydes from real samples and to the quantitation by gas chromatography. Recoveries from spiked samples ranged from 84 to 113%.
Graphical abstract A metal-organic framework ZIF-7 coated stainless steel fiber was prepared via sol-gel method. The self-made fiber was applied in the solid phase microextraction of aldehydes from exhaled breath of lung cancer patients.
A sorbent for selective extraction of phosphoproteins was obtained by immobilization of a Ce(IV)-substituted polyoxometalate on ethylenediamine-functionalized graphene oxide (CeEGO). The resulting composites exhibit an adsorption capacity of 981 mg g?1 for β-casein due to the synergistic effect of metal-affinity interaction between Ce(IV) and phosphate groups and π-stacking interaction between the polyoxometalate framework and the phosphate groups. The results of LC-MS and SDS-PAGE analysis show that the CeEGO composites can be applied to the extraction of phosphoproteins from protein mixture, and as little as 50 μg mL?1 of the phosphoprotein β-casein can be detected by SDS-PAGE. It was also applied to the extraction of β-casein from spiked biological samples such as drinking milk, whole blood and swine heart tissue extract.
Graphical abstract An efficient sorbent is obtained by immobilization of a Ce(IV)-substituted polyoxometalate on ethylenediamine-functionalized graphene oxide (CeEGO). The resulting composites exhibit highly selective capture capacity towards phosphoproteins due to the synergistic effect of metal-affinity interaction between Ce(IV) and phosphate groups and π-stacking interaction between the polyoxometalate framework and the phosphate groups.
This article reviews the progress made in the past 5 years in the field of direct and non-enzymatic electrochemical sensing of glucose. Following a brief discussion of the merits and limitations of enzymatic glucose sensors, we discuss the history of unraveling the mechanism of direct oxidation of glucose and theories of non-enzymatic electrocatalysis. We then review non-enzymatic glucose electrodes based on the use of the metals platinum, gold, nickel, copper, of alloys and bimetals, of carbon materials (including graphene and graphene-based composites), and of metal-metal oxides and layered double hydroxides. This review contains more than 200 refs.
Figure This article reviews the history of unraveling the mechanism of direct electrochemical glucose oxidation and the attempts to successfully develop non-enzymatic electrochemical glucose sensors over the past 5 years.
An electrochemical approach is introduced for synthesis of carbon dots (CDs) by exfoliating graphite rods at a voltage of 15 V in an electrolyte consisting of a mixture of water and two ionic liquids. It is found that the size of the CDs can be tuned by varying the fraction of water in the mixed electrolyte; CDs in sizes of 4.9, 4.1 and 3.1 nm are obtained if the electrolyte contains water in fractions of 24, 38 and 56 %, respectively. The CDs have a quantum yield of almost 10 % and display the typical excitation wavelength-dependent maxima of photoluminescence, strongest at excitation/emission wavelengths of 360/440 nm. Fourier transform infrared and X-ray photoelectron spectroscopy show the CDs to have oxygen functional groups on their surface which strongly improve solubility. The CDs were applied to image cells of the electricity-producing bacteria Shewanellaoneidensis MR-1.
Graphical Abstract An electrochemical approach is introduced to synthesize carbon dots by exfoliating graphite rods in mixed electrolyte of water and ionic liquids. The increasing size of carbon dots was realized by reducing the volume of water in the mixed electrolyte. The carbon dots were used to fluorescently image the electricity-producing bacterium Shewanellaoneidensis MR-1.
We describe a high-performance nitric oxide (NO) sensor by using a nanocomposite consisting of platinum-tungsten alloy nanoparticles, sheets of reduced graphene oxide and an ionic liquid (PtW/rGO-IL) that was deposited onto the surface of a glassy carbon (GC) electrode. The modified GC electrode exhibits excellent electrocatalytic activity toward the oxidation of NO with a strong peak at 0.78 V vs. Ag/AgCl due to the synergistic effects of bimetallic PtW nanoparticles, reduced graphene oxide nanosheets and an ionic liquid. The sensor possesses a detection limit as low as 0.13 nM, high sensitivity (3.01 μA μM?1 cm2), and good selectivity over electroactive interferents that may exist in biological systems. The sensor was tested to selectively distinguish NO in actual human serum and urine samples, confirming potential practical applications. In our perception, the approach described here may be extended to the fabrication of various kind of composites made from metal nanostructures, graphene and ionic liquids for medical and environmental analysis.
Graphical abstract Enhanced electrochemical sensing of nitric oxide (NO) is demonstrated by utilizing the synergistic effects of bimetallic PtW nanoparticles dispersed on reduced graphene oxide and ionic liquid nanocomposite.
This review (with 154 refs.) describes the current status of using molecularly imprinted polymers in the extraction and quantitation of illicit drugs and additives. The review starts with an introduction into some synthesis methods (lump MIPs, spherical MIPs, surface imprinting) of MIPs using illicit drugs and additives as templates. The next section covers applications, with subsections on the detection of illegal additives in food, of doping in sports, and of illicit addictive drugs. A particular focus is directed towards current limitations and challenges, on the optimization of methods for preparation of MIPs, their applicability to aqueous samples, the leakage of template molecules, and the identification of the best balance between adsorption capacity and selectivity factor. At last, the need for convincing characterization methods, the lack of uniform parameters for defining selectivity, and the merits and demerits of MIPs prepared using nanomaterials are addressed. Strategies are suggested to solve existing problems, and future developments are discussed with respect to a more widespread use in relevant fields.
Graphical abstract This review gives a comprehensive overview of the advances made in molecularly imprinting of polymers for use in the extraction and quantitation of illicit drugs and additives. Methods for syntheses, highlighted applications, limitations and current challenges are specifically addressed.
The authors report that the peroxidase-like activity of Au@Pt core-shell nanohybrids (Au@PtNHs) is selectively inhibited by cysteine. This finding has led to a highly sensitive colorimetric assay for cysteine that is based on the nanohybrid-catalyzed oxidation of TMB by H2O2 to form a blue product. The method has a detection limit of 5.0 nM and a linear range from 10 nM to 20 μM. The assay is highly selective over other amino acids. It was successfully applied to the determination of cysteine in an injection containing a mixture of amino acids.
Graphical abstract The peroxidase-like activity of Au@Pt core-shell nanohybrids (Au@PtNHs) is selectively inhibited by cysteine, enabling the determination of cysteine.
We describe a label-free electrochemical immunosensor for the carcinoembryonic antigen (CEA). It is based on a nanocomposite consisting of electrochemically reduced graphene oxide, gold nanoparticles (AuNPs), and poly(indole-6-carboxylic acid). Coupled to nanoparticle-amplification techniques and modified with ionic liquid (IL), this immunoassay shows high sensitivity and good selectivity for CEA. At the best working voltage of 0.95 V (vs. Ag/AgCl), the lower detection limit is 0.02 ng·mL?1, and the response to CEA is linear in the range from 0.02 to 90 ng·mL?1. The method was applied to the determination of CEA in spiked serum samples and gave recoveries in the range from 98.5 % to 102 %.
Graphical abstract A label-free electrochemical immunosensor was fabricated for the carcinoembryonic antigen (CEA) with a detection limit of 0.02 ng·mL?1. It is based on a nanocomposite consisting of electrochemically reduced graphene oxide (erGO), gold nanoparticles (Au NP), and poly(indole-6-carboxylic acid) (PICA).
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 silver ion imprinted polymer nanoparticles (mag-IIP-NPs) were prepared and used as a recognition element in electrochemical detection of silver(I). The procedure involves two steps: (a) the extraction of the Ag(I) by the mag-IIP-NPs, and (b) determination of the preconcentrated Ag(I) ions on the surface of the magneto carbon paste electrode (MCPE) using differential pulse voltammetry. The amount of sorbent, pH value of the sample solution, extraction time, supporting electrolyte, reduction potential and reduction time were optimized. Under optimal conditions and at a working voltage of +0.02 V (vs. Ag/AgCl), the method displays a linear response in the 0.05 to 150 μg?L?1 Ag(I) concentration range. Other features include a low detection limit (15 ng?L?1), a remarkable selectivity and good reproducibility (with an RSD of 4.7%). The results obtained with this analytical assay when analyzing different water samples were compared with the data obtained by GF-AAS, and the results agreed satisfactorily. In our perception, this approach also may be extended to electrochemical detection for other ions, and this makes it a widely applicable strategy for heavy metal ion analysis.
