Surface modification prepared porous copper oxide/(Cu-S)n metal-organic framework/reduced graphene oxide hierarchical structure for highly selective electrochemical quercetin detection.

Electrochemical alkalization of (Cu-S)n metal-organic framework (MOF) and graphene oxide ((Cu-S)n MOF/GO) composite yields a new CuO/(Cu-S)n MOF/RGO (reduced GO) composite with porous morphology on screen printed carbon electrode (SPCE) which facilitated the electron transfer properties in electrochemical quercetin (QUE) detection. A selective QUE detection ability has been demonstrated by the constructed electrochemical sensor (CuO/(Cu-S)n MOF/RGO/SPCE), which also has a broad dynamic range of 0.5 to 115 µM in pH 3 by differential pulse voltammetry. The detection limit is 0.083 µM (S/N = 3). In this study, it was  observed that the real samples contained 0.34 mg mL-1 and 27.7 µg g-1 QUE in wine and onion, respectively.

Nanocarbon material-supported conducting poly(melamine) nanoparticle-modified screen-printed carbon electrodes for highly sensitive determination of nitrofuran drugs by adsorptive stripping voltammetry.

The toxicity of nitrofuran drugs has attracted great attention, and the reported electroanalytical methods suffered limited sensitivity. In this work, a sensitive electrochemical assay in the cathodic region is developed to determine four nitrofuran derivatives, including nitrofurantoin (NFT), nitrofurazone (NFZ), furaltadone (FTD), and furazolidone (FZD). The screen-printed carbon electrode (SPCE) was used as the electrode substrate, and the sensing surface was composed of multi-walled carbon nanotube (MWCNT) and conducting poly(melamine) (PME). The overoxidation-pretreated MWCNTs affect the surface morphology of the electrodeposited PME and, thus, the interaction with nitrofuran drugs. The characteristics of the nanocomposite-modified electrode surfaces were well characterized by field emission scanning electron microscopy (FE-SEM), X-ray photoelectron spectroscopy (XPS), and surface water contact angle experiments. The nanocomposite-modified electrodes exhibited excellent adsorption and electrochemical reduction of nitrofurans by cyclic voltammetry. The proposed assay exhibited a linear range of sub-micro to micro molar concentrations for the four drugs under the optimized differential pulse voltammetric (DPV) technique. The detection limits were found to be in the nanomolar ranges. The developed assay was applied to detect NFT in two real samples, and the results showed good recoveries that ranged from 99.0 to 104.8% and 98.0 to 103.2% for milk and lake water samples, respectively. Graphical abstract ᅟ.

Differential innate immune signalling via Ca(2+) sensor protein kinases.

Innate immunity represents the first line of inducible defence against microbial infection in plants and animals. In both kingdoms, recognition of pathogen- or microbe-associated molecular patterns (PAMPs or MAMPs, respectively), such as flagellin, initiates convergent signalling pathways involving mitogen-activated protein kinase (MAPK) cascades and global transcriptional changes to boost immunity. Although Ca(2+) has long been recognized as an essential and conserved primary mediator in plant defence responses, how Ca(2+) signals are sensed and relayed into early MAMP signalling is unknown. Using a functional genomic screen and genome-wide gene expression profiling, here we show that four calcium-dependent protein kinases (CDPKs) are Ca(2+)-sensor protein kinases critical for transcriptional reprogramming in plant innate immune signalling. Unexpectedly, CDPKs and MAPK cascades act differentially in four MAMP-mediated regulatory programs to control early genes involved in the synthesis of defence peptides and metabolites, cell wall modifications and redox signalling. Transcriptome profile comparison suggests that CDPKs are the convergence point of signalling triggered by most MAMPs. Double, triple and quadruple cpk mutant plants display progressively diminished oxidative burst and gene activation induced by the 22-amino-acid peptide flg22, as well as compromised pathogen defence. In contrast to negative roles of calmodulin and a calmodulin-activated transcription factor in plant defence, the present study reveals Ca(2+) signalling complexity and demonstrates key positive roles of specific CDPKs in initial MAMP signalling.

Fabrication of bacteriochlorin shell/gold core nanoparticles for the sensitive determination of trichlosan using differential pulse voltammetry.

The triclosan contamination in daily life has attracted great attention, and there is rare electroanalytical assay based on π-system dyes. In this work, a facile preparation and electroanalytical application of an organic dispersion containing bacteriochlorin dyes (LS11) and gold nanoparticles (AuNPs) was proposed. The organic-inorganic hybrid nanocomposites were characterized by transmission electron microscope (TEM) showing a core-shell structure with a uniform layer of dye molecules. The as-prepared nanocomposites were successfully coated onto glassy carbon electrodes, and the surface characteristics of the top most layer of the modified electrodes were examined by atomic force microscopy (AFM), field emission scanning electron microscopy (FE-SEM) and water contact angle experiments. The nanocomposite film-modified electrodes exhibited good electrochemical activity towards oxidation of triclosan. The oxidation of adsorbed triclosan occurred at a reduced overpotential, and the anodic current responses under a pre-concentration step prior to the potential scan were used for quantitative analysis. A good linear relationship from 0.01 µM to 0.5 µM was obtained using differential pulse voltammetry. The sensitivity and detection limit (S/N = 3) were 23.69 µA µM-1 and 0.03 µM, respectively. The proposed assay was applied to detect triclosan in two personal hygiene products using standard addition method, and the results showed good recoveries that ranged from 96.6% to 101.5% and from 99.3% to 103.8% for a toothpaste sample and a hand wash sample, respectively. A reference HPLC-UV method was used to evaluate the proposed electroanalytical method, and a good agreement was achieved.

A novel electroanalytical assay for sulfamethazine determination in food samples based on conducting polymer nanocomposite-modified electrodes.

The toxicity of sulfa drugs has attracted great attention, and the reported electrochemical methods for sulfa drugs usually employ a high oxidation potential. In this work, a one-pot synthesized conducting polymer nanocomposite containing poly(3,4-ethylenedioxythiophene) (PEDOT) and MnO2 was cast on a screen-printed carbon electrode (SPCE), and the modified electrode showed superior electrochemical activity over a bare electrode for sulfamethazine (SMZ) determination. The SMZ detection was based on the electrochemical oxidation product, which showed an adsorptive property and exhibited a redox couple at 0.39V in pH 3 phosphate buffer solutions (PBS). The electrode surfaces were well characterized by the water contact angle technique, Raman spectroscopy, X-ray photoelectron spectroscopy (XPS), field emission scanning electron microscopy (FE-SEM), atomic force microscopy (AFM) and cyclic voltammetry. By the use of square wave voltammetry (SWV), a wide linear response to SMZ, from 1.0µM to 500µM, was obtained. The sensitivity and detection limits (S/N = 3) were 0.115µAµM-1 and 0.16µM, respectively. The proposed method and a reference high-performance liquid chromatographic method (HPLC) were applied for the determination of SMZ in two real samples using the standard addition method, and satisfactory recoveries and good agreement were obtained.

Reusable electrochemical sensor for bisphenol A based on ionic liquid functionalized conducting polymer platform.

The toxicity of bisphenol A (BPA) has attracted considerable attention, and the reported electrochemical sensors for BPA need further improvement in reusability due to serious surface fouling. In this study, a composite film is designed aiming to provide both an accurate and repeatable platform for BPA determination. The conducting poly(3,4-ethylenedioxythiophene) film (PEDOT) and ionic liquid 1-butyl-3-methylimidazolium bromide (BMIMBr) were modified onto screen-printed carbon electrodes (SPCE) by electropolymerization and drop/spin methods, respectively. The surface characteristics of the composite film were characterized by field emission scanning electron microscopy (FE-SEM), X-ray photoelectron spectroscopy (XPS) and surface water contact angle experiments. The composite film-modified electrodes exhibited a linear response to BPA in the range of 0.1-500µM in pH 7.0 phosphate buffer solution (PBS) under optimized flow-injection amperometry. The method sensitivity and detection limit (S/N=3) were 0.2661µA µM(-1) (2.419µA µM(-1)cm(-2)) and 0.02µM, respectively. A relative standard deviation of 1.95% was obtained for 77 successive measurements of 10µM BPA, and the repeatability outperformed previously reported work. The proposed method was applied to detect BPA released from plastic water bottles using the standard addition method, and satisfactory recoveries were obtained. The electrochemical assay was validated by comparison with the chromatographic method, and the results showed good agreement between the two methods.

Sensitive and selective determination of gallic acid in green tea samples based on an electrochemical platform of poly(melamine) film.

In this work, an electrochemical sensor coupled with an effective flow-injection amperometry (FIA) system is developed, targeting the determination of gallic acid (GA) in a mild neutral condition, in contrast to the existing electrochemical methods. The sensor is based on a thin electroactive poly(melamine) film immobilized on a pre-anodized screen-printed carbon electrode (SPCE*/PME). The characteristics of the sensing surface are well-characterized by field emission scanning electron microscopy (FE-SEM), X-ray photoelectron spectroscopy (XPS) and surface water contact angle experiments. The proposed assay exhibits a wide linear response to GA in both pH 3 and pH 7.0 phosphate buffer solutions (PBS) under the optimized flow-injection amperometry. The detection limit (S/N = 3) is 0.076 µM and 0.21 µM in the pH 3 and pH 7 solutions, respectively. A relative standard deviation (RSD) of 3.9% is obtained for 57 successive measurements of 50 µM GA in pH 7 solutions. Interference studies indicate that some inorganic salts, catechol, caffeine and ascorbic acid do not interfere with the GA assay. The interference effects from some orthodiphenolic compounds are also investigated. The proposed method and a conventional Folin-Ciocalteu method are applied to detect GA in green tea samples using the standard addition method, and satisfactory spiked recoveries are obtained.

Novel spectral and electrochemical characteristics of triphenylamine-bound zinc porphyrins and their intramolecular energy and electron transfer.

Porphine bearing triphenylamine (TPA) pendant groups and their zinc complexes, zinc meso-tetra-p-(di-p-phenylamino)phenylporphyrin (ZnTDPAPP) and zinc meso-tetra-p-(di-p-tolylamino)phenylporphyrin (ZnTDTAPP) are synthesized and their spectral and electrochemical characteristics are studied. Zinc meso-tetraphenylporphyrin (ZnTPP) and zinc meso-tetra-p-aminophenylporphyrin (ZnTAPP) are also used as reference complexes. The B and Q bands of ZnTDPAPP and ZnTDTAPP are located at higher wavelengths and the bandwidths become broader compared with those of ZnTPP and ZnTAPP, indicating the peripheral TPA affects the electronic configuration of zinc porphyrins. Upon excitation in CH2Cl2 at room temperature, the compounds exhibit intramolecular singlet energy transfer from the TPA to the porphyrin core, and emission from the porphyrins are observed. Both ZnTDPAPP and ZnTDTAPP are easier to be oxidized and harder to be reduced than ZnTPP, in agreement with the strong electron-donating effect of the TPA groups. Extra waves corresponding to the oxidation of TPA substituents are also observed. The cation radical ZnTDTAPP+* exhibits an absorption spectrum very different from the typical spectra for porphyrin cation radicals. The NIR absorption band at 1296 nm indicates the electron transfer occurs intramolecularly. The above results evince the ability of TPA to modulate the electronic structure of zinc porphyrins.

Calcium signaling through protein kinases. The Arabidopsis calcium-dependent protein kinase gene family.

In plants, numerous Ca(2+)-stimulated protein kinase activities occur through calcium-dependent protein kinases (CDPKs). These novel calcium sensors are likely to be crucial mediators of responses to diverse endogenous and environmental cues. However, the precise biological function(s) of most CDPKs remains elusive. The Arabidopsis genome is predicted to encode 34 different CDPKs. In this Update, we analyze the Arabidopsis CDPK gene family and review the expression, regulation, and possible functions of plant CDPKs. By combining emerging cellular and genomic technologies with genetic and biochemical approaches, the characterization of Arabidopsis CDPKs provides a valuable opportunity to understand the plant calcium-signaling network.