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This review (with 177 refs) gives an overview on nanomaterial-based methods for the determination of uranyl ion (UO 2 2+ ) by different types of transducers. Following an introduction into the field, a first large section covers the fundamentals of selective recognition of uranyl ion by receptors such as antibodies, aptamers, DNAzymes, peptides, microorganisms, organic ionophores (such as salophens, catechols, phenanthrolines, annulenes, benzo-substituted macrocyclic diamides, organophosphorus receptors, calixarenes, crown ethers, cryptands and β-diketones), by ion imprinted polymers, and by functionalized nanomaterials. A second large section covers the various kinds of nanomaterials (NMs) used, specifically on NMs for electrochemical signal amplification, on NMs acting as signal tags or carriers for signal tags, on fluorescent NMs, on NMs for colorimetric assays, on light scattering NMs, on NMs for surface enhanced Raman scattering (SERS)-based assays and wireless magnetoelastic detection systems. We then discuss detection strategies, with subsections on electrochemical methods (including ion-selective and potentiometric systems, voltammetric systems and impedimetric systems). Further sections treat colorimetric, fluorometric, resonance light scattering-based, SERS-based and photoacoustic methods, and wireless magnetoelastic detection. The current state of the art is summarized, and current challenges are discussed at the end. Graphical abstract An overview is given on nanomaterial-based methods for the detection of uranyl ion by different types of transducers (such as electrochemical, optical, photoacoustic, magnetoelastic, etc) along with a critical discussion of their limitations, benefits and application to real samples.

A highly sensitive new method is described for performing dispersive microextractions. It is making use of a magnetic carbon nanocomposite and two miscible organic solvents. The method was applied to simultaneous extraction of 32 polychlorinated biphenyls (PCBs) prior to their quantitation by gas chromatography with electron capture detection. The effects of pH value of sample for both micro solid phase extraction and dispersive liquid-liquid microextraction, of the amount of sorbent, extraction time, type and volume of the miscible organic solvents and of salt addition were optimized. Figures of merit obtained under optimized conditions (sample solution: 500 ml, volume of disperser solvent, ACN, 1.5 mL; volume of extraction solvent, TCB, 30 μL; extraction time: 50 min, 20 mg magnetic sorbent, centrifuge, 5 min, 4000 rpm), include (a) preconcentration factors between 10,880 and 34,000; (b) repeatabilities of ≤14.9%, (c) detection limits between 0.01 and 0.2 ng kg-1, and (d) linear dynamic ranges from 0.05 to 100 ng kg - 1. The method was applied to the simultaneous analysis of residues in (spiked) real samples of fish, milk, packing sheet, and tap waters. Some of the analytes were found to be present in fish samples. The method is simple, rapid, and more sensitive than any of the previously reported ones. Graphical abstract Schematic presentation of simultaneous extraction of 32 polychlorinated biphenyls (PCBs) by using magnetic carbon nanocomposites (MCNs) based dispersive microextraction (M-SPE), subsequent dispersive liquid-liquid microextraction (DLLME) with two miscible stripping solvents, and quantitation by GC-μECD.

This review (with 340 refs) focuses on methods for specific and sensitive detection of metabolites for diagnostic purposes, with particular emphasis on electrochemical nanomaterial-based sensors. It also covers novel candidate metabolites as potential biomarkers for diseases such as neurodegenerative diseases, autism spectrum disorder and hepatitis. Following an introduction into the field of metabolic biomarkers, a first major section classifies electrochemical biosensors according to the bioreceptor type (enzymatic, immuno, apta and peptide based sensors). A next section covers applications of nanomaterials in electrochemical biosensing (with subsections on the classification of nanomaterials, electrochemical approaches for signal generation and amplification using nanomaterials, and on nanomaterials as tags). A next large sections treats candidate metabolic biomarkers for diagnosis of diseases (in the context with metabolomics), with subsections on biomarkers for neurodegenerative diseases, autism spectrum disorder and hepatitis. The Conclusion addresses current challenges and future perspectives. Graphical abstract This review focuses on the recent developments in electrochemical biosensors based on the use of nanomaterials for the detection of metabolic biomarkers. It covers the critical metabolites for some diseases such as neurodegenerative diseases, autism spectrum disorder and hepatitis.

Nucleolin is a multifunctional protein that is markedly overexpressed on the surface of most cancer cells. By taking advantage of the high affinity and specificity of the AS1411 aptamer for nucleolin, a signalling probe displacement electrochemical aptasensor was developed. The thiolated AS1411 aptamer was conjugated to hydroxyapatite nanorods (HApNRs) decorated with gold nanoparticles (AuNPs). To further increase the electrical conductivity of the interface, the ionic liquid 1-ethyl-3-methylimidazolium alanine with its high ion conductivity was placed on the electrode surface. Then, the aptamer was immobilized on the modified electrode and conjugated to signalling c-DNA tagged with AgNPs (c-DNA@AgNPs). In the presence of the MCF7 target cells, the signalling probe is displaced and released from the electrode surface. This leads to a decrease in the current that is proportional to the concentration of cancer cells in the range from 10 to 10 6 cells mL -1 , with a detection limit as low as 8 ± 2 cells mL -1 (n = 3) (based as 3σ/m, where σ is the standard deviation of the blank and m is the slope of the calibration plot). This method presents a promising tool for highly sensitive and selective detection of surface nucleolin on MCF7 cancer cells. Graphical abstract HApNR-AuNP-AS1411 aptamer nanocomposite as an electrochemical sensing interface was immobilized on the gold electrode surface and conjugated to signaling c-DNA tagged with AgNPs for determination of surface nucleolin on MCF7 cancer cells.

The authors describe an electrochemical method for aptamer-based determination of insulin at femtomolar concentrations. The surface of a screen printed electrode was modified with ordered mesoporous carbon that was chemically modified with 1,3,6,8-pyrenetetrasulfonate (TPS). The amino-terminated aptamer was then covalently linked to TPS via reactive sulfonyl chloride groups. Subsequently, the redox probe Methylene Blue (MB) was interacted into the aptamer. The MB-modified binds to insulin and this results in the release of MB and a decreased signal as obtained by differential pulse voltammetry, best at a working voltage of -0.3 V (versus silver pseudo-reference electrode). Insulin can be quantified by this method in the 1.0 fM to 10.0 pM concentration range, with a 0.18 fM limit of detection (at 3σ/slope). The assay was applied to the determination of insulin in spiked human serum samples. The method is highly sensitive, selective, stable, and has a wide analytical range. Graphical abstract The surface of a screen printed electrode was modified with ordered mesoporous carbon-1,3,6,8-pyrenetetrasulfonate. The amino-terminated aptamer was then linked to the 1,3,6,8-pyrenetetrasulfonate. Then, the Methylene Blue was interacted into the aptamer. The modified electrode was applied to the determination of insulin.

The purpose of this study was to develop a sensitive and simple method, based on dispersive derivatization liquid-liquid microextraction-gas chromatography-mass spectrometry (DDLLME-GC-MS) in scanning and selected-ion-monitoring (SIM) modes, for detection of 2-chlorovinylarsonous acid (CVAA) as a hydrolysis product and urinary metabolite of lewisite in urine samples. Chloroform (65 μL), methanol (500 μL), and ethanedithiol (10 μL) were used as extraction solvent, dispersive solvent, and derivatizing reagent, respectively. Critical conditions of the proposed method were optimized. The nucleophilic reactions of dithiol and monothiol compounds with CVAA were also studied using a competitive method. In view of the high affinity of trivalent arsenic for sulfhydryl groups, the interaction between CVAA and bis(2-chlorovinyl)arsonous acid (BCVAA) and free cysteine (Cys) was also investigated using liquid chromatography-electrospray ionization mass spectrometry (LC-ESI-MS). The interference of Cys, present in human urine, with the detection of CVAA was evaluated using dithiol and monothiol chemicals as derivatization agents. The developed method provided a preconcentration factor of 250, and limits of detection of 0.015 and 0.30 μg L(-1) in SIM and scanning modes, respectively. The calibration curves were linear over the concentration range of 1-400 μg L(-1) in full-scan mode. The relative standard deviation (RSD) values were calculated to be 5.5 and 3.2% at concentrations of 20 and 100 μg L(-1), respectively. Collision-induced dissociation studies of the major electron-impact (EI) ions were performed to confirm the proposed fragment structure of CVAA-dithiols derivatives. Results indicated that the developed method for analysis of CVAA is suitable not only for verification of human exposure to lewisite, but also for quantification of CVAA in urine samples.

A novel uranyl ion-selective bulk optode membrane, incorporating tri-n-octylphosphine oxide for cation recognition and a lipophilic chromoionophore dibenzoylmethane, has been prepared. The PVC membrane composition was optimized to result in the widest working concentration range. The response range of the proposed optode is 4.1 x 10(-6) to 2.0 x 10(-4) mol L(-1) UO2(2+). The probe works at pH 4.0. Ion interference is low and selectivity, reproducibility, and stability are good.

A silver-selective optode membrane incorporating hexathia-18-crown-6 for cation recognition and a lipophilic chromoionophore 1,2-benzo-3-octadecanoylimino-7-diethylaminophenoxazine for transduction has been prepared. The PVC membrane composition was optimized to result in the largest working concentration range. The response range of the proposed optode is 5.0 x 10(-9)-5.0 x 10(-5) mol L(-1) Ag(+) with a limit of detection of 1.0 x 10(-9) mol L(-1). The probe works well at pH 5.0 and revealed small ion interference and good selectivity, reproducibility and stability.