Ultrasensitive electrochemical sensor for p-nitrophenyl organophosphates based on ordered mesoporous carbons at low potential without deoxygenization

p-Nitrophenyl organophosphates (OPs) including paraoxon, parathion and methyl parathion, etc, are highly poisonous OPs, for which sensitive and rapid detection method is most needed. In this work, an ultrasensitive electrochemical sensor for the determination of p-nitrophenyl OPs was developed based on ordered mesoporous carbons (OMCs) modified glassy carbon electrode (GCE) (OMCs/GCE). The electrochemical behavior and reaction mechanism of p-nitrophenyl OPs at OMCs/GCE was elaborated by taking paraoxon as an example. Experimental conditions such as buffer pH, preconcentration potential and time were optimized. By using differential pulse voltammetry, the current response of the sensor at −0.085 V was linear with concentration within 0.01–1.00 μM and 1.00–20 μM paraoxon. Similar linear ranges of 0.015–0.5 μM and 0.5–10 μM were found for parathion, and 0.01–0.5 μM and 0.5–10 μM for methyl parathion. The low limits of detection were evaluated to be 1.9 nM for paraoxon, 3.4 nM for parathion and 2.1 nM for methyl parathion (S/N = 3). Common interfering species had no interference to the detection of p-nitrophenyl OPs. The sensor can be applicable to real samples measurement. Therefore, a simple, sensitive, reproducible and cost-effective electrochemical sensor was proposed for the fast direct determination of trace p-nitrophenyl OPs at low potential without deoxygenization.     

Simultaneous determination of ascorbic acid,dopamine and uric acid based on tryptophan functionalized graphene

A new type of tryptophan-functionalized graphene nanocomposite (Trp-GR) was synthesized by utilizing a facile ultrasonic method via π–π conjugate action between graphene (GR) and tryptophan (Trp) molecule. The material as prepared had well dispersivity in water and better conductivity than pure GR. The surface morphology of Trp-GR was characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM) and Raman spectroscopy. The electrochemical behaviors of ascorbic acid (AA), dopamine (DA), and uric acid (UA) were investigated by cyclic voltammetry (CV) on the surface of Trp-GR. The separation of the oxidation peak potentials for AA–DA, DA–UA and UA–AA was about 182 mV, 125 mV and 307 mV, which allowed simultaneously determining AA, DA, and UA. Differential pulse voltammetery (DPV) was used for the determination of AA, DA, and UA in their mixture. Under optimum conditions, the linear response ranges for the determination of AA, DA, and UA were 0.2–12.9 mM, 0.5–110 μM, and 10–1000 μM, with the detection limits (S/N = 3) of 10.09 μM, 0.29 μM and 1.24 μM, respectively. Furthermore, the modified electrode was investigated for real sample analysis.     

Simultaneous determination of dopamine,ascorbic acid and uric acid with electrospun carbon nanofibers modified electrode

A novel carbon-nanofiber-modified carbon-paste electrode (CNF-CPE) was employed for the simultaneous determination of dopamine (DA), ascorbic acid (AA) and uric acid (UA) with good selectivity and high sensitivity. The CNFs were prepared by combination of electrospinning technique with thermal treatment method and were used without any pretreatment. In application to determination of DA, AA and UA in the ternary mixture, the pristine CNF-CPE exhibited well-separated differential pulse voltammetric peaks with high catalytic current. Low detection limits of 0.04 μM, 2 μM and 0.2 μM for DA, AA and UA were obtained, with the linear calibration curves over the concentration range 0.04–5.6 μM, 2–64 μM and 0.8–16.8 μM, respectively.     

Simultaneous determination of ascorbic acid,dopamine, uric acid and tryptophan on gold nanoparticles/overoxidized-polyimidazole composite modified glassy carbon electrode

A novel electrode was developed through electrodepositing gold nanoparticles (GNPs) on overoxidized-polyimidazole (PImox) film modified glassy carbon electrode (GCE). The combination of GNPs and the PImox film endowed the GNPs/PImox/GCE with good biological compatibility, high selectivity and sensitivity and excellent electrochemical catalytic activities towards ascorbic acid (AA), dopamine (DA), uric acid (UA) and tryptophan (Trp). In the fourfold co-existence system, the peak separations between AA–DA, DA–UA and UA–Trp were large up to 186, 165 and 285 mV, respectively. The calibration curves for AA, DA and UA were obtained in the range of 210.0–1010.0 μM, 5.0–268.0 μM and 6.0–486.0 μM with detection limits (S/N = 3) of 2.0 μM, 0.08 μM and 0.5 μM, respectively. Two linear calibrations for Trp were obtained over ranges of 3.0–34.0 μM and 84.0–464.0 μM with detection limit (S/N = 3) of 0.7 μM. In addition, the modified electrode was applied to detect AA, DA, UA and Trp in samples using standard addition method with satisfactory results.     

Synthesis and application of fluorescent N,S co-doped carbon dots based on on-off-on quenching mode for the collaboration detection of iron ions and ascorbic acid

Nitrogen and sulfur co-doped carbon dots (NS-CDs) were synthesized by one-step solvothermal method using oleic acid as the medium, ʟ-cystine and citric acid monohydrate as precursors. Based on the “on-off-on” fluorescence quenching mode, a novel method was established for determination of both Fe³⁺ and ascorbic acid. The synthesized NS-CDs can be employed as fluorescence chemical sensors for the direct determination of free iron in the aqueous phase and indirect determination of the ascorbic acid contents of vitamin C tablets with linear ranges of 0–10 μM (n = 3) and 0–30 μM (n = 3), and detection limits of 36.6 and 102.5 nM, respectively. These results demonstrate that the proposed method exhibits good selectivity and linearity.     

Highly selective and sensitive simple sensor based on electrochemically treated nano polypyrrole-sodium dodecyl sulphate film for the detection of para-nitrophenol

An ultrasensitive and highly selective electrochemical sensor for the determination of p-nitrophenol (p-NP) was developed based on electrochemically treated nano polypyrrole/sodium dodecyl sulphate film (ENPPy/SDS film) modified glassy carbon electrode. The nano polypyrrole/sodium dodecyl sulphate film (NPPy/SDS film) was prepared and treated electrochemically in phosphate buffer solution. The surface morphology and elemental analysis of treated and untreated NPPy/SDS film were characterized by FESEM and EDX analysis, respectively. Wettability of polymer films were analysed by contact angle test. The hydrophilic nature of the polymer film decreased after electrochemical treatment. Effect of the pH of electrolyte and thickness of the ENPPy/SDS film on determination of p-NP was optimised by cyclic voltammetry. Under the optimised conditions, the p-NP was determined from the oxidation peak of p-hydroxyaminophenol which was formed from the reduction of p-NP in the reduction segment of cyclic voltammetry. A very good linear detection range (from 0.1 nM to 100 μM) and the best LOD (0.1 nM) were obtained for p-NP with very good selectivity. This detection limit is below to the allowed limit in drinking water, 0.43 μM, proposed by the U.S. Environmental Protection Agency (EPA) and earlier reports. Moreover, ENPPy/SDS film based sensor exhibits high sensitivity (4.4546 μA μM⁻¹) to p-NP. Experimental results show that it is a fast and simple sensor for p-NP.     

A novel quantification method for analysis of twenty natural amino acids in human serum based on N-phosphorylation labeling using reversed-phase liquid chromatography–tandem mass spectrometry

A novel method based on the strategy of N-phosphorylation labeling is described for quantification of twenty natural amino acids in human serum by reversed-phase liquid chromatography–electrospray tandem mass spectrometry (RP-LC/ESI-MS). The derivatization reaction was easily performed in one-pot reaction under mild conditions within 30 min. The reaction mixture was then evaporated to dryness, redissolved, desalted by C18 SPE. The twenty N-phosphoryl amino acids were separated on an RP-C18 column within 20 min by isocratic elution (0.1% formic acid–acetonitrile, v/v 7:3). At the same time, multiple reaction monitoring (MRM) MS enabled quantitation of twenty natural amino with the LOD of 0.0005–0.15 μM and LOQ of 0.0020–0.5 μM in human serum. The linear range was from 0.025 to 25 μM (except Cys and Trp) with R > 0.99. The recovery range was determined to be 85.5–117.4% with the relative standard deviation (RSD) in the range of 1.3–13.9%. All twenty amino acids were successfully detected in human serum samples with the concentration from 5.7 to 577.9 μM, which indicates potential of the developed method for determination of amino acids in complex biological samples, hence for screening of amino acid metabolite related diseases.     

Trace determination of vanadium(V) using anodic adsorptive voltammetry at a glassy carbon electrode modified with multi-walled carbon nanotubes

A glassy carbon electrode modified with multi-walled carbon nanotubes (MWCNT) was prepared and the determination of trace amount of vanadium(V) based on the anodic adsorptive voltammetry of the vanadium-alizarin red S (ARS) complex is described for the first time. The results show that the sensitivity and the selectivity of the method are excellent. The second derivative linear scan voltammograms of the complex were recorded using a polarographic analyzer in the range from 0 to 1,000 mV (vs. SCE). It was found that the complex can be adsorbed on the surface of the electrode, yielding a peak at about 706 mV, corresponding to the oxidation of ARS in the complex. The peak current increases linearly with the V(V) concentration in the range of 6.0 nM to ∼1.0 μM (4.0 μM ARS), 2.0 μM∼10 μM (40 μM ARS) and the detection limit (at S/N = 3) was 2.0 nM (accumulation time 120 s). The method was successfully applied to the determination of trace amounts of vanadium in water samples.

     

Facile synthesis of graphene hybrid tube-like structure for simultaneous detection of ascorbic acid,dopamine, uric acid and tryptophan

In the present work, a tube-like structure of graphene hybrid as modifier to fabricate electrode for simultaneous detection of ascorbic acid (AA), dopamine (DA), uric acid (UA) and tryptophan (Trp) was reported. The hybrid was synthesized by a simple method based on graphene sheets (GS) and 3,4,9,10-perylenetetracarboxylic acid (PTCA) via π–π stacking interaction under ultrasonic condition. The combination of GS and PTCA could effectively improve the dispersion of GS, owing to PTCA with the carboxylic-functionalized interface. Comparing with pure GS or PTCA modified electrode, GS–PTCA displayed high catalytic activity and selectivity toward the oxidation of AA, DA, UA, and Trp. Moreover, cyclic voltammetry, different pulse voltammetry and scanning electron microscopy were employed to characterize the sensors. The experiment results showed that the linear response range for simultaneous detection of AA, DA, UA, and Trp were 20–420 μM, 0.40–374 μM, 4–544 μM and 0.40–138 μM, respectively, and the detection limits were 5.60 μM, 0.13 μM, 0.92 μM and 0.06 μM (S/N = 3). Importantly, the proposed method offers promise for simple, rapid, selective and cost-effective analysis of small biomolecules.     

One-pot electrochemical synthesis of functionalized fluorescent carbon dots and their selective sensing for mercury ion

We propose a simple, economical, and one-pot method to synthesize water-soluble functionalized fluorescent carbon dots (C-Dots) through electrochemical carbonization of sodium citrate and urea. The as-prepared C-Dots have good photostability and exhibit a high quantum yield of 11.9%. The sizes of the C-Dots are mainly distributed in the range of 1.0–3.5 nm with an average size of 2.4 nm. It has been further used as a novel label-free sensing probe for selective detection of Hg²⁺ ions with detection limit as low as 3.3 nM. The detection linear range is 0.01–10 μM. The as-prepared C-Dots are also successfully applied for the determination of Hg²⁺ in real water samples.     

Determination of energy metabolites in cancer cells by porous graphitic carbon liquid chromatography electrospray ionization mass spectrometry for the assessment of energy metabolism

A high performance liquid chromatography (HPLC) tandem mass spectrometric (MS/MS) method has been developed for the simultaneous determination of fifteen glucose, or acetate derived metabolites isolated from tumor cells. Glycolytic and tricarboxylic acid (TCA) cycle metabolites as well as acidic amino acids were separated on a HPLC porous graphitic carbon (PGC) column and simultaneously determined by means of triple quadrupole MS/MS using multiple reaction monitoring (MRM). Target compounds were eluted within 10 min with 8% v/v formic acid as an electronic modifier added to a 4:1 v/v methanol water mobile phase. The calibration is linear in the 1–100 μM concentration range for each analyte. The limit of detection ranges between 0.39 and 2.78 μM for the analytes concerned. To test the PGC–HPLC–MS/MS method in metabolomic studies, ZR-75.1 human mammary adenocarcinoma cells were labeled with U-¹³C glucose or 1-¹³C acetate. Applying the MRM mode, the incorporation of ¹³C into metabolites, isolated from the tumor cells, and derived from glucose or acetate, could be properly identified.     

Synthesis of Nitrogen Doped Multilayered Graphene Flakes: Selective Non‐enzymatic Electrochemical Determination of Dopamine and Uric Acid in presence of Ascorbic Acid.

Nitrogen doped multilayered graphene (NDMLG) is synthesized by annealing the black fluffy mass obtained by decomposing the complex prepared from Zn(OAc)₂, diethanolamine and triethanolamine. The NDMLG has been characterized by HRTEM, FESEM, XRD, XPS, Raman spectroscopy, BET which indicate formation of nitrogen doped multilayer graphene flakes with high surface area. NDMLG shows better electrochemical oxidation property towards Dopamine, Uric acid and Ascorbic acid. The linear response ranges for determination of DA, UA and AA are 0.5–150 µM, 3–60 µM and 80–2000 µM respectively and the detection limits (S/N=3) are 15 nM, 15 nM, 580 nM, respectively in the mixture.     

Simultaneous determination of atropine,anisodamine, and scopolamine in plant extract by nonaqueous capillary electrophoresis coupled with electrochemiluminescence and electrochemistry dual detection

A rapid and simple method was demonstrated for the analysis of atropine, anisodamine, and scopolamine by nonaqueous capillary electrophoresis (NACE) coupled with electrochemiluminescence (ECL) and electrochemistry (EC) dual detection. The mixture of acetonitrile (ACN) and 2-propanol containing 1 M acetic acid (HAc), 20 mM sodium acetate (NaAc), and 2.5 mM tetrabutylammonium perchlorate (TBAP) was used as the electrophoretic buffer. Although a short capillary of 18 cm was used, the decoupler was not needed and the separation efficiency was good. The linear ranges of atropine, anisodamine, and scopolamine were 0.5–50, 5–2000, and 50–2000 μM, respectively. For six replicate measurements of 100 μM scopolamine, 15 μM atropine, and 200 μM anisodamine, the RSDs of ECL intensity, EC current, and migration time were less than 3.6%, 4.5%, and 0.3%, respectively. In addition, because the organic buffer was used, the working electrode (Pt) was not easily fouled and did not need reactivation. The method was also applied for the determination of these three alkaloids in Flos daturae extract.     

Pulsed lasers versus continuous light sources in capillary electrophoresis and fluorescence detection studies: Photodegradation pathways and models

Pulsed lasers are widely used in capillary electrophoresis (CE) studies to provide laser induced fluorescence (LIF) detection. Unfortunately pulsed lasers do not give linear calibration curves over a wide range of concentrations. While this does not prevent their use in CE/LIF studies, the non-linear behavior must be understood. Using 7-hydroxycoumarin (7-HC) (10–5000 nM), Tamra (10–5000 nM) and tryptophan (1–200 μM) as dyes, we observe that continuous lasers and LEDs result in linear calibration curves, while pulsed lasers give polynomial ones. The effect is seen with both visible light (530 nm) and with UV light (355 nm, 266 nm). In this work we point out the formation of byproducts induced by pulsed laser upon irradiation of 7-HC. Their separation by CE using two Zeta LIF detectors clearly shows that this process is related to the first laser detection. All of these photodegradation products can be identified by an ESI-/MS investigation and correspond to at least two 7HC dimers. By using the photodegradation model proposed by Heywood and Farnsworth (2010) and by taking into account the 7-HC results and the fact that in our system we do not have a constant concentration of fluorophore, it is possible to propose a new photochemical model of fluorescence in LIF detection. The model, like the experiment, shows that it is difficult to obtain linear quantitation curves with pulsed lasers while UV-LEDs used in continuous mode have this advantage. They are a good alternative to UV pulsed lasers. An application involving the separation and linear quantification of oligosaccharides labeled with 2-aminobezoic acid is presented using HILIC and LED (365 nm) induced fluorescence.     

Synthesis and characterization of new selective Zn fluorescent probes for functionalization: in vitro Cell imaging applications

Herein the synthesis and characterization of new, lipophilic highly Zn²⁺-selective fluorescent probes are reported. High affinity for zinc (K_d 1.1–8.0 nM) over other biologically relevant metals and mixtures of metals was observed. Excitation at 360 nm afforded an emission spectrum with maximum at 530 nm for the zinc bound complex. The linear relationship between fluorescence intensity and zinc concentration indicates that FZnA-probes can be used for quantification. The probes have been synthesized in 28–45% overall yield and the feasibility for further functionalization with biologically relevant side chains has been demonstrated. In vitro studies using PC12 cells and 10 μM of one of the novel probes (FZnA-Ada) visualized endogenous labile Zn²⁺ after 45 min incubation time.     

Direct synthesis of nitrogen-doped graphene on platinum wire as a new fiber coating method for the solid-phase microextraction of BXes in water samples: Comparison of headspace and cold-fiber headspace modes

In this work, a new solid-phase microextraction fiber was prepared based on nitrogen-doped graphene (N-doped G). Moreover, a new strategy was proposed to solve problems dealt in direct coating of N-doped G. For this purpose, first, Graphene oxide (GO) was coated on Pt wire by electrophoretic deposition method. Then, chemical reduction of coated GO to N-doped G was accomplished by hydrazine and NH₃. The prepared fiber showed good mechanical and thermal stabilities. The obtained fiber was used in two different modes (conventional headspace solid-phase microextraction and cold-fiber headspace solid-phase microextraction (CF-HS-SPME)). Both modes were optimized and applied for the extraction of benzene and xylenes from different aqueous samples. All effective parameters including extraction time, salt content, stirring rate, and desorption time were optimized. The optimized CF-HS-SPME combined with GC-FID showed good limit of detections (LODs) (0.3–2.3 μg/L), limit of quantifications (LOQs) (1.0–7.0 μg/L) and linear ranges (1.0–5000 μg/L). The developed method was applied for the analysis of benzene and xylenes in rainwater and some wastewater samples.     

Fabrication and characterisation of high performance polypyrrole modified microarray sensor for ascorbic acid determination

In this study, gold microelectrode array (Au/MEA) with electrode of 12 μm diameter was fabricated by photolithography technique. Subsequently, polypyrrole (Ppy) modified gold microarrays sensor (Ppy/Au/MEA) was prepared by cyclic voltammetry technique. The deposition potential range and number of cycles were optimised in order to get optimum thickness of Ppy film. Scanning Electron Microscope and Atomic Force Microscope investigations reveal that Ppy coating formed at 3 cycles is porous with thickness of 1.5 μm which exhibiting high catalytic current for ascorbic acid (AA) in square wave technique (SWV). In contrast to earlier sensors designs, these Ppy/Au/MEA sensors exhibits lower detection limit (LOD) of 10 nm towards AA at physiological conditions. It also exhibits enhanced sensitivity (2.5 mA cm⁻² mM⁻¹) and long range of linear detection limit from 10 nm to 2.8 mM. In the same way, polypyrrole modified macro Au (Ppy/Au/MA) biosensor was also fabricated and its electro catalytic property towards AA was compared with that of Ppy/Au/MEA. The Ppy/Au/MA exhibits sensitivity of only 0.27 mA cm⁻² mM⁻¹, LOD of 5 μM and linear range of 10 μM to 2.2 mM. Hence, our investigations indicate that the Ppy/Au/MEA could serve as highly sensitive sensor for AA than any of the earlier designs. So, the Ppy/Au/MEA electrode was utilised for determination AA in a wide variety of real samples.     

A highly uniform CuO@SiO2 porous sphere with improved electrochemical sensing performance for the accurate determination of vanillin in food samples

A porous sphere of CuO@SiO₂ was obtained by simple calcination of the copper silicate (CuSiO₃) sphere. The formation of the porous sphere was studied in detail with the support of various physical characterization techniques. The CuO@SiO₂ was coated on an electrode surface where it demonstrates high catalytic activity for the electro-oxidation of vanillin in phosphate buffer solution (PBS; pH 7.0). The modified electrode has good surface adsorption (1.861 × 10^?10 mol cm^?2) and rate constant (2.866 × 10⁵ cm³ mol^?1 s^?1) characteristics for vanillin detection. The CuO@SiO₂-modified surface exhibited good linear range (0.05 μM–1.2 μM and 6.2 to 111.2 μM), detection limit (53 nM), sensitivity (2.88 μA μM^?1 cm^?2), selectivity, stability, and reproducibility. The CuO@SiO₂-modified electrode was further examined for the determination of vanillin in real samples including biscuits and chocolates with satisfactory recoveries.     

Magnetic field assisted μ-solid phase extraction of anti-inflammatory and loop diuretic drugs by modified polybutylene terephthalate nanofibers

A magnetic nanocomposite consisting of nanoparticles–polybutylene terephthalate (MNPs–PBT) was electrospun and used as an extracting medium for an on-line μ-solid phase extraction (μ–SPE)–high performance liquid chromatography (HPLC) set–up with an ultraviolet (UV) detection system. Due to the magnetic property of the prepared nanofibers, the whole extraction procedure was implemented under an external magnetic field to enhance the extraction efficiencies. The developed method along with the synthesized nanocomposite were found to be appropriate for the determination of trace levels of selected drugs including furosemide, naproxen, diclofenac and clobetasol propionate in the urine sample. The prepared MNPs-PBT electrospun nanocomposite was characterized using the scanning electron microscopy (SEM), energy dispersive spectroscopy (EDX) and Fourier transform infrared (FT–IR) spectroscopy. The prepared magnetic fibers showed high porosity, which was another driving force for the extraction efficiency enhancement. Major parameters affecting the extraction efficiency of the selected drugs were optimized. The limits of detections (LOD) of the studied drugs were in the range of 0.4–1.6 μg L⁻¹ and the limits of quantification (LOQ) were 1–4 μg L⁻¹ under the optimized conditions. Relative standard deviation (RSD%) for three replicates at three concentration levels of 6, 100 and 400 μg L⁻¹ were 5.9–8.0% while acceptable linear range with two orders of magnitude was obtained (R² = 0.99). The method was validated by the determination of the selected drugs in urine samples and the results indicated that this method has sufficient potential for enrichment and determination of the desired drugs in the urine sample. The relative recovery values were found to be in the range of 78–91%. Implementing the developed on–line μ–SPE method under the external magnetic field induction, led to higher extraction efficiencies for the selected drugs with various diamagnetic properties.     

Determination of linear aliphatic aldehydes in heavy metal containing waters by high-performance liquid chromatography using 2,4-dinitrophenylhydrazine derivatization

A simple and sensitive method is described for the determination of picomolar amounts of C₁–C₉ linear aliphatic aldehydes in waters containing heavy metal ions. In this method, aldehydes were first derivatized with 2,4-dinitrophenylhydrazine (DNPH) at optimized pH 1.8 for 30 min and analyzed by HPLC with UV detector at 365 nm. Factors affecting the derivatization reaction of aldehydes and DNPH were investigated. Cupric ion, an example of heavy metals, is a common oxidative reagent, which may oxidize DNPH and greatly interfere with the determination of aldehydes. EDTA was used to effectively mask the interferences by heavy metal ions. The method detection limits for direct injection of derivatized most aldehydes except formaldehyde were of the order of 7–28 nM. The detection limit can be further lowered by using off-line C₁₈ adsorption cartridge enrichment. The recoveries of C₁–C₉ aldehydes were 93–115% with a relative standard deviation of 3.6–8.1% at the 0.1 μM level for aldehydes. The HPLC–DNPH method has been applied for determining aldehyde photoproducts from Cu(II)–amino acid complex systems.