Microwave-assisted synthesis of graphene modified CuO nanoparticles for voltammetric enzyme-free sensing of glucose at biological pH values.

The effect of graphene nanosheets on the glucose sensing performance of CuO powders was investigated. CuO and graphene-modified CuO nanoparticles (NPs) were fabricated by microwave-assisted synthesis and characterized by X-ray diffraction, transmission electron microscopy and X-ray photoelectron spectroscopy. The material was placed on a glassy carbon electrode (GCE) which then was characterized by cyclic voltammetry and chronoamperometry with respect to the capability of sensing glucose both at pH 13 and pH 7.4. The results revealed that the modified GCE has a fast and selective linear response to glucose at pH 13 that covers the 0.21 µM to 12 mM concentration range, with a 0.21 µM low detection limit. The presence of graphene nanosheets results in an improved sensitivity which is to 700 µA mM-1 cm-2. In solution of pH 7.4, the respective data are a linear analytical range from 5 to 14 mM; a 5 µM LOD and a sensitivity of 37.63 µA mM-1 cm-2 at working potential of -0.05 V (vs. Ag/AgCl) and scan rate of 50 mV s-1. Ascorbic acid, dopamine, uric acid, sucrose, maltose and fructose do not interfere. Graphical abstract ᅟ.

Electrochemical detection of nanomolar dopamine in the presence of neurophysiological concentration of ascorbic acid and uric acid using charge-coated carbon nanotubes via facile and green preparation.

Negatively charged multi-walled carbon nanotubes (MWCNTs) were prepared using simple sonication technique with non-toxic citric acid (CA) for the electrochemical detection of dopamine (DA). CA/MWCNTs were placed on glassy carbon (GC) electrodes by drop-casting method and then electrochemical determinations of DA were performed in the presence of highly concentrated ascorbic acid (AA). For the comparison of the charge effect on MWCNTs surface, positively charged polyethyleneimine (PEI)/MWCNT/GC electrode and pristine MWCNT/GC electrode were also prepared. Contrary to conventional GC electrode, all three types of MWCNT modified electrodes (CA/MWCNT/GC, PEI/MWCNT/GC, and pristine MWCNT/GC) can discriminate ~µM of DA from 1mM AA using cyclic voltammetry (CV) and differential pulse voltammetry (DPV) due to the inherent electrocatalytic effect of MWCNTs. Compared to positively charged PEI/MWCNT/GC and pristine MWCNT/GC electrodes, negatively charged CA/MWCNT/GC electrode remarkably enhanced the electrochemical sensitivity and selectivity of DA, showing the linear relationship between DPV signal and DA concentration in the range of 10-1000nM even in the presence of ~10(5) times concentrated AA, which is attributed to the synergistic effect of the electrostatic interaction between cationic DA molecules and negatively charged MWCNTs and the inherent electrocatalytic property of MWCNT. As a result, the limit of detection (LOD) of DA for CA/MWCNT/GC electrode was 4.2nM, which is 5.2 and 16.5 times better than those for MWCNT/GC electrode and PEI/MWCNT/GC electrode even in the presence of 1mM AA. This LOD value for DA at CA/MWCNT/GC electrode is one of the lowest values compared to the previous reports and is low enough for the early diagnosis of neurological disorder in the presence of physiological AA concentration (~0.5mM). In addition, the high selectivity and sensitivity of DA at CA/MWCNT/GC electrode were well kept even in the presence of both 1mM AA and 10µM uric acid (UA) as similar as neurophysiological concentration.

Particle size control of Pd/C for improved electrocatalytic activity in a formic acid oxidation.

Carbon-supported Pd electrocatalyst is prepared by an improved aqueous impregnation method applying a reducing agent of HCHO and an acidic sedimentation promoter of HCl. We investigate the effect of a solution pH on the zeta potential of both Pd particles and carbon support. The opposite sign of zeta potential results in uniform dispersion of Pd on carbon surface without aggregation problem. TEM analysis shows that optimal solution pH of 4.27 adjusted by NaOH provides a mean particle diameter of 3.2 nm with narrow size distribution. Cyclic voltammograms indicate that home-made Pd/C catalyst exhibits significantly higher electrochemical active surface area and better stability compared with commercial 40 wt.% Pd/C in a formic acid oxidation.

Evaluation of electrogenerated chemiluminescence from a neutral Ir(III) complex for quantitative analysis in flowing streams.

Though recently Ir(III) complexes have attracted much interest in electrochemiluminescent (ECL) analysis due to their high emission in various wavelengths, there were a few studies reported on its analytical applications. In this study, we evaluate the ECL from (pq)(2)Ir(acac) (pq = 2-phenylquinolate, acac = acetylacetonate) for the use in flow injection analysis. An aqueous solution of the analyte and (pq)(2)Ir(acac) passes through the reaction/observation cell, and then ECL reaction is generated by electrochemical initiation on the analyte and (pq)(2)Ir(acac). Tri-n-propylamine (TPrA) is used as a representative analyte for evaluation. Additionally, a comparison is made of the relative ECL intensities obtained for a variety of analytes including oxalate, amino acids, aliphatic amines, and NADH. The (pq)(2)Ir(acac) produces efficient ECL upon TPrA exhibiting the limit of detection of 5 nM with a linear range of 3 orders of magnitude in concentration whereas 20 nM is observed in the conventional Ru(bpy)(3)(2+) system. It shows particular sensitivity advantages for oxalate, proline, and tartaric acid. The ECL generation upon various analytes proposes direct applicability of (pq)(2)Ir(acac) as a post-column detection tool.

Electrochemically programmed chemodosimeter on ultrathin platinum films.

We demonstrate electrochemically controlled release of chemodosimeters attached to ultrathin patterned platinum electrodes. Fluorescence and electrochemical methods have been employed for the detection of chemodosimeter modification/desorption and Cu(2+) binding/removal.

Electrogenerated chemiluminescent anion sensing: selective recognition and sensing of pyrophosphate.

Recently, significant advances have been made independently in electrogenerated chemiluminescence (ECL) analysis and supramolecular anion sensing. Herein, we demonstrate a new proof of concept for ECL-based pyrophosphate (PPi) sensing, where the emission intensity is changed by electrochemical turn-on. The ECL PPi sensor (1-2Zn) consists of two orthogonally bonded moieties: boron dipyrromethene (ECL reporter) and a phenoxo-bridged bis(Zn(2+)-dipicolylamine) complex (PPi receptor). The presence of PPi is confirmed from the change in the intensity of green ECL generated from the former when PPi is selectively recognized by the latter. During PPi recognition, changes are caused in the electronic states of the receptor, and this stimulates the attenuation of ECL intensity. The electrochemical "on-off" triggering of light emission upon anion binding forms the basis of a new anion sensing strategy. We expect that green-colored ECL sensing would offer an advantage to current ECL analysis.

Chiral gold nanoparticle-based electrochemical sensor for enantioselective recognition of 3,4-dihydroxyphenylalanine.

The enantioselective recognition of 3,4-dihydroxyphenylalanine using penicillamine-modified gold nanoparticles has been investigated. Smaller gold nanoparticles with one enantiomeric ligand facilitate the redox reaction of only one enantiomer of 3,4-dihydroxyphenylalanine, with cross inversion for the gold nanoparticles with the other enantiomeric ligand.

Enhanced electrogenerated chemiluminescence of a ruthenium tris(2,2')bipyridyl/tripropylamine system on a boron-doped diamond nanograss array.

Significant enhancement of the ECL signals from the Ru(bpy)(3)(2+)/TPA system was achieved when using a BDD nanograss array, mainly because of the highly facile oxidation of TPA. The facile oxidation of TPA is due to the superior properties of the BDD nanograss array, such as improved electrocatalytic activity and accelerated electron transfer.

Highly sensitive gold nanoparticle-based colorimetric sensing of mercury(II) through simple ligand exchange reaction in aqueous media.

A strategy for the rational design of a novel colorimetric sensor based on dithioerythritol-modified gold nanoparticles for the selective recognition of Hg2+ in aqueous media is presented. This approach relies on the combination of gold nanoparticles with Hg2+ through sulfur-Hg2+-sulfur interaction. The gold nanoparticles showed high selectivity toward Hg2+ with binding-induced red shift in the absorption spectra, with no response to major interfering cations such as Pb2+, Cd2+, and Cu2+ in the presence of ethylenediamine tetraacetic acid. The system responds to Hg2+ with a detection limit of 100 nM and might open a new avenue for the development of Hg2+ sensing probes.

Electrochemical detection of dopamine in the presence of ascorbic acid using graphene modified electrodes.

Dopamine plays a significant role in the function of human metabolism. It is important to develop sensitive sensor for the determination of dopamine without the interference by ascorbic acid. This paper reports the synthesis of graphene using a modified Hummer's method and its application for the electrochemical detection of dopamine. Electrochemical measurements were performed at glassy carbon electrode modified with graphene via drop-casting method. Cyclic voltammogram of ferri/ferrocyanide redox couple at graphene modified electrode showed an increased current intensity compared with glassy carbon electrode and graphite modified electrode. The decrease of charge transfer resistance was also analyzed by electrochemical impedance spectroscopy. The capacity of graphene modified electrode for selective detection of dopamine was confirmed in a sufficient amount of ascorbic acid (1 mM). The observed linear range for the determination of dopamine concentration was from 4 microM to 100 microM. The detection limit was estimated to be 2.64 microM.

Highly sensitive detection of DNA by electrogenerated chemiluminescence amplification using dendritic Ru(bpy)(3)(2+)-doped silica nanoparticles.

This study describes the development and characterization of a novel dendritic signal amplification strategy. It relies on the use of two different Ru(bpy)(3)(2+)-doped silica nanoparticles (Probe(1,2)RSNP and Probe(2c)RSNP) coated with complementary DNAs, which can be simply and conveniently self-assembled to build sandwich-type dendritic architectures on a gold grid. The performance of this dendritic amplification route was demonstrated in conjunction with the electrogenerated chemiluminescent (ECL) detection of the target DNA. Compared to normal amplification, dendritic amplification allowed a 5-fold enhancement of the ECL signals. The higher sensitivity allowed by the dendritic amplification route was attributed to the hybridization between the DNA (Probe(2)DNA) on Probe(1,2)RSNP (normal amplification) and the complementary DNA (Probe(2c) DNA) on the additional Probe(2c)RSNP. As low as 1 fM of 22-bp-long target DNA was clearly detected. The experimental results demonstrated that the ECL intensity achieved through dendritic amplification showed a good linear relationship with the concentration of the target DNA over a wide linear range (10 fM-10 pM).

A regenerative electrochemical sensor based on oligonucleotide for the selective determination of mercury(II).

We have developed a selective, sensitive, and re-usable electrochemical sensor for Hg2+ ion detection. This sensor is based on the Hg2+-induced conformational change of a single-stranded DNA (ssDNA) which involves an electroactive, ferrocene-labeled DNA hairpin structure and provides strategically the selective binding of a thymine-thymine mismatch for the Hg2+ ion. The ferrocene-labeled DNA is self-assembled through S-Au bonding on a polycrystalline gold electrode surface and the surface blocked with 3-mercapto-1-propanol to form a mixed monolayer. The modified electrode showed a voltammetric signal due to a one-step redox reaction of the surface-confined ferrocenyl moiety. The 'signal-on' upon mercury binding could be attributed to a change in the conformation of ferrocene-labeled DNA from an open structure to a restricted hairpin structure. The differential pulse voltammetry (DPV) of the modified electrode showed a linear response of the ferrocene oxidation signal with increase of Hg2+ concentration in the range between 0.1 and 2 microM with a detection limit of 0.1 microM. The molecular beacon mercury(II) ion sensor was amenable to regeneration by simply unfolding the ferrocene-labeled DNA in 10 microM cysteine, and could be regenerated with no loss in signal gain upon subsequent mercury(II) ion binding.

Fabrication of nanostructured materials using porous alumina template and their applications for sensing and electrocatalysis.

Ordered porous anodic aluminum oxide templates have been used extensively for the preparation of various functional nanostructures. Researches on these nanostructured materials for various purposes have received a tremendous attention during recent years. A review of the literature on the fabrication of nanostructured materials using ordered porous anodic aluminum oxide templates and their applications is presented. A survey of the preparation of anodic aluminum oxide films is given first, with an emphasis on highly ordered anodic aluminum oxide films, as the ordered structure is the key point to prepare nanomaterials with uniform morphology. Methods for the fabrication of nanostructured materials using ordered porous anodic aluminum oxide templates are presented next: including dip filling, ion-encountering reaction, electroplating, and chemical vapor deposition method. Several typical examples of each preparation method are given. Finally, overview of applications on these nanostructured materials is presented, particular emphasis is focused on the field of sensing and electrocatalysis.

Enhancement of electrogenerated chemiluminescence and radical stability by peripheral multidonors on alkynylpyrene derivatives.

A very generous donor: The electrochemiluminescence (ECL) efficiency and radical stability of pyrene, a poor ECL luminophore, are markedly improved as the number of peripheral multidonor units increased in a series of compounds (see picture). Photophysical and electrochemical studies and theoretical calculations have contributed to the understanding of the ECL enhancement, which is a step forward in the development of new light-emitting materials.

Diazo-coupled calix[4]arenes for qualitative analytical screening of metal ions.

New chromogenic diazophenylcalix[4]arenes 1 and 2 were synthesized in cone conformation. Compound 1 with the ortho-carboxyl groups in CH(3)CN solution preferentially binds with alkaline earth and transition metal ions, whereas no significant changes in absorption spectra are observed in the presence of alkali metal ions. While 2 with the ortho-ester groups shows selective complexation properties towards transition metal ions over alkali and alkaline earth metal ions. The detection of metal ions gives rise to bathochromic shifts in the absorption spectra (from orange/yellow to red), which is clearly visible even to the naked eye. According to the selective color changes using both receptors upon cation complexation, one can set up a qualitative analytical routine to screen alkali, alkaline earth, and transition metal ions.

Transition metal ion selective ortho-ester diazophenylcalix[4]arene.

New chromogenic dizophenylcalix[4]arene 1 showing selective color change to transition metal ions over other alkaline and alkaline earth metal ions has been prepared in the cone conformation and tested for its usefulness.

Structure-selective recognition by voltammetry: enantiomeric determination of amines using azophenolic crowns in aprotic solvent.

The enantiomeric recognition of amines by voltammetry using electroactive macrocyclic molecules, nitroazophenolic crown ethers, is reported. The oxidation potential of the nitroazophenol moiety in nitroazophenols with 18-crown-6 sensitively depends on the structure of alkyl amines. Based on this phenomenon, enantiomeric amines and even the quantitative assay of the R/S ratio in enantiomeric mixtures can be selectively recognized by using 18-crown-6 azophenol (3-H) with chiral centers. In the case of phenylglycinol, the association constants (K) of 3-H for the R and S forms have an R/S value of 3.5. The peak potential of the R form in square-wave voltammograms reproducibly differs from that of the S form by 32 mV, within which the peak potential linearly varies with the enantiomeric ratio. Free energy perturbation and molecular dynamics simulation provide deeper understanding of the enantiomeric recognition in this system. The theoretical analysis indicates that the free energy difference between diastereomeric complexes agrees well with the experimental results, and the pi-pi or charge-charge interaction plays a key role in enantiomeric recognition.

Efficient electrogenerated chemiluminescence from cyclometalated iridium(III) complexes.

Very efficient electrogenerated chemiluminescence (ECL) phenomena were realized by deliberately tuning electron-transfer reactions from electrochemically generated electron donor to metal complex radical cations. By controlling the relative positions of HOMO and LUMO levels (oxidation potential and reduction potential) of Ir(III) complexes, we could obtain 77 times higher ECL from iridium(III) complexes in the presence of TPA than that of the Ru(bpy)32+/TPA system. This high ECL efficiency of new Ir(III) complexes can be used in many interesting applications such as sensors and luminescent devices.

Cesium ion-selective electrodes based on 1,3-alternate thiacalix[4]biscrown-6,6.

Four thiacalix[4]biscrown ethers with 1,3-alternate conformation were examined for the potentiometric responses in poly(vinyl chloride) membrane electrodes. Their potentiometric selectivities toward potassium and cesium ions over other alkali, alkaline earth, and transition metal ions were measured by the fixed interference method (FIM). Among the ionophores, 1,3-alternate thiacalix[4]biscrown-6,6 showed a high selectivity for cesium over potassium ion and so was optimized as a Cs(+)-selective electrode. The electrode exhibited a linear response with a near Nernstian slope of 57.6mV per decade in the concentration range of 1.0x10(-6) to 3.2x10(-2)M. It was suitable for use in aqueous solution in a wide range of pH 2.5-12.5 and had a fast response time of ca. 5s. On the basis of 1,3-alternate thiacalix[4]biscrown-6,6, the electrode has a wide linear range and selectivity for cesium ion over potassium ion ( log K (Cs (+ ),K (+))=- 3.7 ) better than those previously reported with other ionophores.