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A SiO2-coumarin nanohybrid was investigated for its Cu(II) sensing performance in aqueous media, and in comparison with the Cu(II)-selective coumarin used alone. Fluorescence of both coumarin itself and the nanohybrid, λex/λem 435/481 nm, was selectively quenched by Cu(II) when tested against a range of multivalent cations. The nanohybrid had enhanced Cu(II) sensing properties when compared to the coumarin including (i) improved limit of detection from μM-level (0.48 μM) of Cu(II) using coumarin alone to nM-level (0.033 μM) and (ii) an extended linear detection range of 0.033–260 μM (0.0005–4.1 mg/mL) Cu(II) compared to 0.48–55 μM for the coumarin itself. The lower limit of detection and extended range were achieved with a smaller amount of coumarin and no traces of organic solvents used to help coumarin dissolution. Characterization suggested that under applied test conditions at pH = 5, SiO2 nanoparticles with negative surface charges adsorbed coumarin and then (when present) Cu(II) ions. The SiO2-coumarin nanohybrid was then applied for the determination of Cu(II) levels in aqueous soil extracts reaching over 94% recovery rates when used against the standard soil analysis method by inductively coupled plasma mass spectrometry (ICP-MS). [ABSTRACT FROM AUTHOR]

A selectively modified porous metal/carbon nanocomposite was fabricated to enhance the enrichment of low-abundance phosphopeptides from biological samples. The carbon matrix derived from the metal-organic framework provides a suitable pore size to allow the diffusion of peptides, while the deliberately modified metal nanoparticles within the pores enhance their interaction with the phosphopeptides. This nanocomposite shows extremely high enrichment selectivity for phosphopeptides in the MALDI-TOF MS detection, even when the molar ratio of α-casein digests versus bovine serum albumin digests was up to about 1:20,000. By combining such nanocomposite with nano-LC-MS/MS, 4556 unique phosphopeptides were identified with high selectivity (95.2%) from HeLa cell extracts. Furthermore, phosphopeptides from prostate tissue digests were also determined. A total of 277 and 1242 phosphopeptides were identified from normal and tumor tissues of a patient with prostate cancer, respectively. This indicates that phosphorylation and prostate cancer can be related to each other. [ABSTRACT FROM AUTHOR]

An enzyme-free, metal-free, and preconcentration-free electrochemical sensor for pentachlorophenol assay has been fabricated. The interface of the sensor is based on a hollow zeolitic imidazolate framework–derived mesoporous carbon material (denoted as HZC/SPCE). The sensor exhibits linear amperometric response upon pentachlorophenol at 0.82 V (vs. Ag/AgCl) in the concentration range 0.001 to 26.8 mg L−1 (3.75 × 10−8~1.006 × 10−4 M) (R2 = 0.997). The sensitivity of HZC/SPCE is 3.53 × 102 μA mM−1 cm−2 with a detection limit of 2.05 × 10−9 M (S/N = 3) for pentachlorophenol. The method has been applied to the determination of pentachlorophenol in spiked food packaging samples with recoveries in the range 92.0 to 107.0%. [ABSTRACT FROM AUTHOR]

The authors describe a photometric method for the determination of free cholesterol based on the oxidation of cholesterol by the catalytic action of the enzyme cholesterol oxidase. The hydrogen peroxide formed is used to oxidize the chromogenic compound 3,3′,5,5′-tetramethylbenzidine (TMB) by exploiting the peroxidase-like activity of carbon nanotube-supported Prussian blue (PB). This enzyme mimic was synthesized from a mixture of ferric chloride and hexacyanoferrate(III) in the presence of intrinsically reducing multi-walled carbon nanotubes. The composite can trigger the formation of a blue-green dye from TMB in the presence of HO. The findings were exploited to design a photometric (652 nm) assay that has a linear response in the 4 to 100 μM cholesterol concentration range and a 3 μM detection limit. The practicability of the method was verified by the successful analysis of free cholesterol in human blood samples. [ABSTRACT FROM AUTHOR]

Three ferrites of type MFeO (where M is bivalent Fe, Co or Mn) dispersed on multi-walled carbon nanotubes (MWCNTs) were prepared by a coprecipitation method. Their electrocatalytic properties toward the reduction of HO at pH 7.4 were systematically compared. Catalytic reduction rates at an applied potential of −0.4 V (vs. Ag/AgCl) and pseudo Michaelis-Menten constants show the electrocatalytic ability to follows the order FeO > CoFeO > MnFeO. This diversity is attributed to the differences in the M(II) used and its occupancy on the lattice surface. The sensitivities are 120.98 ± 0.15, 48.45 ± 0.23 and 32.25 ± 0.27 μA cm mM, and the limits of detection are 0.98, 2.59 and 5.64 μM of HO (at an S/N ratio of 3). [Figure not available: see fulltext.] [ABSTRACT FROM AUTHOR]

We have synthesized nitrogen-doped graphene nanoribbons (N-GrNRs) by unzipping multi-walled carbon nanotubes (CNTs) under strongly oxidizing conditions and subsequent doping with nitrogen by a low-temperature hydrothermal method. The N-GNRs were characterized by transmission electron microscopy, X-ray diffraction, X-ray photoelectron spectroscopy and Raman spectroscopy, and assembled on a disposable screen-printed carbon electrode to give a sensor for HO that was characterized by cyclic voltammetry, electrochemical impedance spectroscopy, chronocoulometry and chronoamperometry. The nano-modified electrode displays enhanced electron transfer ability, and has a large active surface and a large number of catalytically active sites that originate from the presence of nitrogen atoms. This results in a catalytic activity towards HO reduction at near-neutral pH values that is distinctly improved compared to electrodes modified with CNTs or unzipped (non-doped) CNTs only. At a working potential of −0.4 V (vs. Ag/AgCl), the amperometric responses to HO cover the 5 to 2785 μM concentration range, with a limit of detection as low as 1.72 μM. This enzyme-free electrochemical sensor exhibits outstanding selectivity and long-term stability for HO detection. [Figure not available: see fulltext.] [ABSTRACT FROM AUTHOR]

The screen-printed three-electrode system was applied to fabricate a new type of disposable amperometric xanthine oxidase biosensor. Carbon-working, carbon-counter and Ag/AgCl reference electrodes were all manually printed on the polyethylene terephthalate substrate forming the screen-printed three-electrode system by the conventional screen-printing process. As a mediator, Prussian blue could not only catalyze the electrochemical reduction of hydrogen peroxide produced from the enzyme reaction, but also keep the favorable potential around 0 V. The optimum operational conditions, including pH, potential and temperature, were investigated. The sensitivities of xanthine and hypoxanthine detections were 13.83 mA/M and 25.56 mA/M, respectively. A linear relationship was obtained in the concentration range between 0.10 μM and 4.98 μM for xanthine and between 0.50 μM and 3.98 μM for hypoxanthine. The small Michaelis-menten constant value of the xanthine oxidase biosensor was calculated to be 3.90 μM. The results indicate that the fabricated xanthine oxidase biosensor is effective and sensitive for the detection of xanthine and hypoxanthine. [ABSTRACT FROM AUTHOR]

An electrochemical DNA biosensor for specific-sequences detection of Vibrio parahaemolyticus (VP) was fabricated. A single-stranded 20-mer oligonucleotide (ssDNA) and 6-mercapto-1-hexanol (MCH) were immobilized via a thiol linker on gold disk electrodes by self-assembling. The ssDNA underwent hybridization in a hybridization solution containing complementary or non-complementary or single base pair mismatched DNA sequences of VP. Examination of changes in response to these three target DNAs showed that the developed biosensor had a high selectivity and sensitivity. [ABSTRACT FROM AUTHOR]

A hydrophilic interaction liquid chromatography (HILIC) material with application in glycoproteomics was obtained by sequential deposition of polyethyleneimine (PEI) and hyaluronic acid (HA) on a negatively charged substrate by means of electrostatic self-assembly. This kind of surface modification endows the material with excellent hydrophilicity and warrants efficient glycopeptides enrichment. The feasibility of this enrichment was verified by using dendritic mesoporous silica nanoparticles (DMSNs) and magnetic graphene oxide (MagG) as negatively charged substrates for PEI and HA adhesion. The two final products (DMSNs@PEI@HA and MagG@PEI@HA) exhibit high enrichment selectivity (molar ratios of IgG and BSA digests = 1:500 and 1:1000), sensitivity (detection limit, 2 fmol/μL), recovery (>90%) and enrichment capacity (300 mg/g). When using DMSNs@PEI@HA, 419 N-glycopeptides derived from 105 glycoproteins were identified. When using MagG@PEI@HA, 376 N-glycopeptides derived from 102 glycoproteins were identified, both from a 2 μL serum sample. This is better than by methods described in previous reports. [ABSTRACT FROM AUTHOR]

The authors present a colorimetric method for the evaluation of the hydroxyl radical scavenging capability of antioxidants by exploiting carbon-confined mixed cobalt oxide nanoparticles (denoted as C-confined CoOx NPs) as a novel peroxidase mimic. The nanozyme can be prepared from the metal-organic framework ZIF-67 by calcination at a moderate temperature. It exhibits peroxidase-mimicking activity and catalyzes the oxidation of colorless 3,3′,5,5′-tetramethylbenzidine (TMB) to form a blue product in the presence of H2O2 via generation of hydroxyl radicals. However, in the presence of an antioxidant, the color reaction is suppressed due to scavenging of hydroxyl radicals by the antioxidant. Based on this principle, the hydroxy radical scavenging ability of glutathione (GSH), cysteine (Cys), tannic acid (TA) and tea polyphenols (TP) was assessed. It was found that these antioxidants can scavenge hydroxyl radicals in the following decreasing order: TA>Cys>GSH>TP. The assay was also used to quantify the antioxidative power of common fruit extracts. [ABSTRACT FROM AUTHOR]

Two kinds of carbon-based nanozymes were constructed from the same precursor of zeolitic imidazolate framework-8 (ZIF-8) for O2•− determination. Hollow carbon cubic nanomaterial (labelled as HCC) was obtained by chemically etching ZIF-8 with tannic acid and a subsequent calcination. A porous carbon cubic nanomaterial (labelled as PCC) was prepared by directly pyrolysis. Then HCC and PCC were immobilized on the surface of screen printed carbon electrodes (SPCE), fabricating HCC and PCC modified electrodes (denoted as HCC/SPCE and PCC/SPCE). HCC/SPCE, best operated at −0.5 V (vs. Ag/AgCl), has a sensitivity of 6.55 × 102 nA μM−1 cm−2 with a detection limit of 207 nM (at S/N = 3) for O2•− sensing. And PCC/SPCE, best operated at −0.4 V (vs. Ag/AgCl), exhibited a superior performance for O2•− detection with a sensitivity of 1.14 × 103 nA μM−1 cm−2 and a low detection limit of 140 nM (at S/N = 3). The two sensors possess excellent reproducibility and stability. They were used to sense O2•− released from HeLa cells. [ABSTRACT FROM AUTHOR]