Development of electrochemical DNA biosensor for Trichoderma harzianum based on ionic liquid/ZnO nanoparticles/chitosan/gold electrode

Electrochemical DNA biosensor was successfully developed by depositing the ionic liquid (e.g., 1-ethyl-3-methylimidazolium trifluoromethanesulfonate ([EMIM][Otf])), ZnO nanoparticles, and chitosan (CHIT) nanocomposite membrane on a modified gold electrode (AuE). The electrochemical properties of the [EMIM][Otf]/ZnO/CHIT/AuE for detection of DNA hybridization were studied. Under optimal conditions using cyclic voltammetry, the target DNA sequences could be detected in the concentration range of 1.0 × 10⁻¹⁸ to 1.82 × 10⁻⁴ mol L⁻¹, and with the detection limit of 1.0 × 10⁻¹⁹ mol L⁻¹. This DNA biosensor detection approaches provide a quick, sensitive, and convenient method to be used in the identification of Trichoderma harzianum.     

Electrodeposited nanogold decorated graphene modified carbon ionic liquid electrode for the electrochemical myoglobin biosensor

In this paper, a carbon ionic liquid electrode (CILE) was fabricated using ionic liquid 1-hexylpyridinium hexafluorophosphate as modifier, which was further in situ electrodeposited with graphene (GR) and gold nanoparticles step by step to get an Au/GR nanocomposite modified CILE. Myoglobin (Mb) was further immobilized on the Au/GR/CILE surface with Nafion film to get the modified electrode denoted as Nafion/Mb/Au/GR/CILE. Cyclic voltammetric experiments indicated that a pair of well-defined quasi-reversible redox peaks appeared in pH 3.0 phosphate buffer solution with the formal potential (E ^0′) located at ?0.197 V (vs. saturated calomel electrode), which was the typical characteristics of Mb heme Fe(III)/Fe(II) redox couples. Thus, the direct electron transfer rate between Mb and the modified electrode was promoted due to the high conductivity and increased surface area of Au/GR nanocomposite present on electrode surface. Based on the cyclic voltammetric data, the electrochemical parameters of Mb on the modified electrode were calculated. The Mb-modified electrode showed excellent electrocatalytic activities towards the reduction of trichloroacetic acid and H₂O₂ with wider linear range and lower detection limit. Using GR and Au nanoparticles modified CILE, a new third-generation electrochemical Mb biosensor was constructed with good stability and reproducibility.     

Investigations on some electrochemical aspects of lithium-ion ionic liquid/gel polymer battery systems

Electrochemical and interfacial characteristics of Li-ion battery system based on LiFePO₄ cathode and graphite anode with ionic liquid (IL) electrolytes have been investigated, both with and without addition of a small amount of polymer to the electrolyte. The IL electrolyte consisted of bis(fluorosulfonyl)imide (FSI) as anion and 1-ethyl-3-methyleimidazolium (EMI) or N-methyl-N-propylpyrrolidinium (Py13) as cation, and operated at ambient temperature. We reported previously that the SEI formation with IL was stabilized in the graphite anode at 80% coulombic efficiency (CE) in the first cycle, when FSI anion is used. In this work, we extend the study to the LiFePO₄ cathode material. Gel polymer with IL is one part of this study. The stepwise impedance spectroscopy was used to characterize the Li/IL-Gel polymer/LiFePO₄ at different states of charge. This technique revealed that the interface resistance was stabilized when the cathode is at 70% DoD (Depth of Discharge). The diffusion resistance is higher at the two extremes of discharge when monophase LiFePO₄ state (0%DoD and 100%DoD) obtains. When polymer is added to the IL, interface resistance is improved with 1 wt.% but results with IL alone are not improved for the case of 5 wt.% polymer added. Good cycling life stability was obtained with Li/IL-FSI/LiFePO₄ cells, with or without polymer. The first evaluation of the Li-ion cell, LiFePO₄/IL-FSI-(5 wt.%) gel polymer/graphite, has shown low first CE at 68.4% but it recovers in the third cycle, to 96.5%. Some capacity fade was noticed after 30 cycles. The rate capability of the Li-ion cell shows a stable capacity until 2 C discharge rate. Dedicated to Professor J.O’ M. Bockris, whose contributions to electrochemistry are inestimable and indelible, on his eighty-fifth birthday.     

Determination of organophosphate pesticides at a carbon nanotube/organophosphorus hydrolase electrochemical biosensor

An amperometric biosensor for oganophosphorus (OP) pesticides based on a carbon nanotube (CNT)-modified transducer and an organophosphorus hydrolase (OPH) biocatalyst is described. A bilayer approach with the OPH layer atop of the CNT film was used for preparing the CNT/OPH biosensor. The CNT layer leads to a greatly improved anodic detection of the enzymatically generated p-nitrophenol product, including higher sensitivity and stability. The sensor performance was optimized with respect to the surface modification and operating conditions. Under the optimal conditions the biosensor was used to measure as low as 0.15 μM paraoxon and 0.8 μM methyl parathion with sensitivities of 25 and 6 nA/μM, respectively.     

Highly stable electrochemical oxidation of phenolic compounds at carbon ionic liquid electrode

A carbon ionic liquid electrode (CILE) was used for the investigation of the electrochemical oxidation of phenolic compounds in acidic media using cyclic voltammetry, chronoamperometry and square wave voltammetry techniques. The results indicate that, contrary to many other electrodes, the oxidation of phenolic compounds on CILE is highly stable and does not result in electrode fouling. Cyclic voltammetry showed that phenolic compounds such as phenol, 2,4-dichlorophenol and catechol were oxidized at CILE and remained electroactive after multiple cycles and at high concentrations of phenol. The cyclic voltammetric response of the CILE is very stable with more than 99% of the initial activity remaining after 20 s of stirring of a 0.5 mM solution of phenol.     

Evaluation of antioxidative capacity via measurement of the damage of DNA using an electrochemical biosensor and an ionic liquid solvent

We report on the electrodeposition of palladium nanomaterials in choline chloride–based ionic liquid ethaline. A glassy carbon electrode (GCE) was modified with cobalt nanoparticles (acting as sacrificial templates) and a GCE modified with palladium nanoparticles (PdNPs) were fabricated and used to study the electrocatalytic oxidation of hydrazine (N₂H₄). Scanning electron microscopy revealed that the PdNP modified GCE has a uniform morphology. Zero current potentiometry was used for in-situ probing the changes in interfacial potential of the oxidation of hydrazine. An amperometric study showed that the PdNP modified GCE possesses excellent electrocatalytic activity towards N₂H₄. The modified electrode displays a fast response (<2 s), high sensitivity (74.9 μA m(mol L^?1)^?1?cm^?2) and broad linearity in the range from 0.1 to 800 μmol L^?1 with a detection limit of 0.03 μmol L^?1 (S/N?=?3).

Copper oxide nanoparticles and ionic liquid modified carbon electrode for the non-enzymatic electrochemical sensing of hydrogen peroxide

The direct electrocatalytic reduction of hydrogen peroxide in alkaline medium at a carbon ionic liquid electrode modified with copper oxide nanoparticles was investigated. The electrode was prepared by mixing graphite particles, ionic liquid (n-octylpyridium hexafluorophosphate) and copper oxide nanoparticles. Unlike the film-modified electrode, the fabrication of this electrode is simple and highly reproducible. The combination of the good conductivity of the ionic liquid and the high catalytic activity of the nanoparticles resulted in an electrode with attractive properties for the determination of hydrogen peroxide. The concentration of NaOH and the loading of copper oxide nanoparticles were optimized. The linear range for the determination of hydrogen peroxide is from 1.0 μM to 2.5 mM, the detection limit is 0.5 μM. High stability, sensitivity, selectivity and reproducibility, fast response, the ease of preparation, and surface renewal made the electrode well suitable for the determination of hydrogen peroxide in real samples.     

Poly(methylene blue) functionalized graphene modified carbon ionic liquid electrode for the electrochemical detection of dopamine

An ionic liquid 1-butylpyridinium hexafluorophosphate based carbon ionic liquid electrode (CILE) was used as the substrate electrode and a poly(methylene blue) (PMB) functionalized graphene (GR) composite film was co-electrodeposited on CILE surface by cyclic voltammetry. The PMB–GR/CILE exhibited better electrochemical performances with higher conductivity and lower electron transfer resistance. Electrochemical behavior of dopamine (DA) was further investigated by cyclic voltammetry and a pair of well-defined redox peaks appeared with the peak-to-peak separation (ΔE_p) as 0.058 V in 0.1 mol L⁻¹ pH 6.0 phosphate buffer solution, which proved a fast quasi-reversible electron transfer process on the modified electrode. Electrochemical parameters of DA on PMB–GR/CILE were calculated with the electron transfer number as 1.83, the charge transfer coefficients as 0.70, the apparent heterogeneous electron transfer rate constant as 1.72 s⁻¹ and the diffusional coefficient (D) as 3.45 × 10⁻⁴ cm² s⁻¹, respectively. Under the optimal conditions with differential pulse voltammetric measurement, the linear relationship between the oxidation peak current of DA and its concentration was obtained in the range from 0.02 to 800.0 μmol L⁻¹ with the detection limit as 5.6 nmol L⁻¹ (3σ). The coexisting substances exhibited no interference and PMB–GR/CILE was applied to the detection of DA injection samples and human urine samples with satisfactory results.     

Electrochemical determination of paraquat using a DNA-modified carbon ionic liquid electrode

Deoxyribonucleic acid (DNA) was electrochemically deposited on a carbon ionic liquid electrode to give a biosensor with excellent redox activity towards paraquat as shown by cyclic voltammetry and differential pulse voltammetry. Experimental conditions were optimized with respect to sensing paraquat by varying the electrochemical parameters, solution pH, and accumulation time of DNA. Under the optimized conditions, a linear relation exists between the reduction peak current and the concentration of paraquat in the range from 5?×?10^?8 mol L^?1 to 7?×?10^?5 mol L^?1, with a detection limit of 3.6?×?10^?9 mol L^?1. The utility of the method is illustrated by successful analysis of paraquat in spiked real water samples.

Development of dimethyl sulfoxide biosensor using a mediator immobilized enzyme electrode

A mediator immobilized dimethyl sulfoxide (DMSO) sensor using DMSO reductase (DMSO-R) was constructed. Methyl viologen (MV) was used as a mediator and immobilized on a glassy carbon (GC) electrode with Nafion polymer. DMSO-R from Rhodobacter sphaeroides f. sp. denitrificans was retained by a dialysis film on the modified GC electrode. The amperometric signal in response to DMSO was observed. The linear range of the calibration curve for DMSO was between 0 and 600 microM. The response time was within 100 s and the relative standard deviation was 4% at 200 microM DMSO (n = 4). To eliminate the background noise derived from oxygen in samples, the glucose oxidase-catalase retained DMSO sensor was also examined.     

Sol/gel transition and liquid crystal transition of HPC in ionic liquid

This work uses an ionic liquid (IL), 1-butyl-3-methylimidazolium acetate, as a solvent to study the sol/gel transition (SGT) and liquid crystal transition (LCT) of hydroxypropylcellulose (HPC) solution. The LCT concentration of HPC at room temperature is 7 wt%, which is slightly higher than its SGT concentration of 6 wt%. For HPC concentrations of over 7 wt%, three rheological approaches were utilized, and the parameters relaxation time, hysteresis ratio and loss modulus (G″) are measured to determine the LCT temperature. The relaxation study concludes that the LC-critical concentration of HPC is 7 wt%. When HPC exceeds 7 wt%, the LC transition temperatures, ranging from 45 to 51 °C, can be measured and are proportional to the HPC concentration. The rheological results are then confirmed by making observations under a polarized optical microscope. All results are highly mutually consistent. Most significantly, the rheological parameters adopted herein can be used as good indicators of the LC transition. Of those indicators, G″ changes distinctly at the LCT point, and can thus be suggested to be the most helpful indicator in determining the LCT temperature.     

Novel ionic liquid electrolyte for electrochemical double layer capacitors

A novel oxygen containing spiro ammonium salt, oxazolidine-3-spiro-1’-pyrrolidinium tetrafluoroborate (OPBF₄) was synthesized using an innovative technique for use as electrolyte in electrochemical double layer capacitors (EDLC). Comparison of OPBF₄ with commercially available, tetraethyl ammonium tetrafluoroborate (TEABF₄) showed higher voltage window and higher capacitance for the OPBF₄ compound. Moreover, molarity of 3 M was produced with OPBF₄ as compared to a maximum of 1.5 M for TEABF₄ in acetonitrile (AN). This is especially important to enable the fabrication of higher energy density EDLC. This is the first report of testing OPBF₄ compound in an EDLC device, and it qualifies as a reasonable alternative to TEABF₄ for high performance ultracapacitors.     

Electrochemical deoxyribonucleic acid biosensor based on the self-assembly film with nanogold decorated on ionic liquid modified carbon paste electrode

An electrochemical DNA biosensor was fabricated by self-assembling probe single-stranded DNA (ssDNA) with a nanogold decorated on ionic liquid modified carbon paste electrode (IL-CPE). IL-CPE was fabricated using 1-butylpyridinium hexafluorophosphate as the binder and the gold nanoparticles were electrodeposited on the surface of IL-CPE (Au/IL-CPE). Then mercaptoacetic acid was self-assembled on the Au/IL-CPE to obtain a layer of modified film, and the ssDNA probe was further covalently-linked with mercaptoacetic acid by the formation of carboxylate ester with the help of N-(3-dimethylamino-propyl)-N'-ethylcarbodiimide hydrochloride and N-hydroxysuccinimide. The hybridization reaction with the target ssDNA was monitored with methylene blue (MB) as the electrochemical indicator. Under the optimal conditions, differential pulse voltammetric responses of MB was proportional to the specific ssDNA arachis sequences in the concentration range from 1.0×10(-11) to 1.0×10(-6) mol L(-1) with the detection limit as 1.5×10(-12) mol L(-1) (3σ). This electrochemical DNA sensor exhibited good stability and selectivity with the discrimination ability of the one-base and three-base mismatched ssDNA sequences. The polymerase chain reaction product of arachis Arabinose operon D gene was successfully detected by the proposed method, which indicated that the electrochemical DNA sensor designed in this paper could be further used for the detection of specific ssDNA sequence.     

Development of a nanomechanical biosensor for analysis of endocrine disrupting chemicals

A nanomechanical transducer is developed to detect and screen endocrine disrupting chemicals (EDCs) combining fluidic sample injection and delivery with bioreceptor protein functionalized microcantilevers (MCs). The adverse affects of EDCs on the endocrine system of humans, livestock, and wildlife provides strong motivation for advances in analytical detection and monitoring techniques. The combination of protein receptors, which include estrogen receptor alpha (ER-alpha) and estrogen receptor beta (ER-beta), as well as monoclonal antibodies (Ab), with MC systems employing modified nanostructured surfaces provides for excellent nanomechanical response sensitivity and the inherent selectivity of biospecific receptor-EDC interactions. The observed ranking of binding interaction of the tested EDCs with ER-beta is diethylstilbestrol (DES) > 17-beta-estradiol > 17-alpha-estradiol > 2-OH-estrone > bisphenol A > p,p'-dichlorodiphenyldichloroethylene (p,p'-DDE) with measurements exhibiting intra-day RSDs of about 3%. A comparison of responses of three EDCs, which include 17-beta-estradiol, 17-alpha-estradiol, and 2-OH-estrone, with ER-beta and ER-alpha illustrates which estrogen receptor subtype provides the greatest sensitivity. Antibodies specific to a particular EDC can also be used for analyte specific screening. Calibration plots for a MC functionalized with anti-17-beta-estradiol Ab show responses in the range of 1 x 10(-11) through 1 x 10(-7) M for 17-beta-estradiol with a linear portion extending over two orders of magnitude in concentration.     

Functionalization of carbon nanotubes by electrochemical reduction of aryl diazonium salts: a bucky paper electrode.

Small-diameter (ca. 0.7 nm) single-wall carbon nanotubes are predicted to display enhanced reactivity relative to larger-diameter nanotubes due to increased curvature strain. The derivatization of these small-diameter nanotubes via electrochemical reduction of a variety of aryl diazonium salts is described. The estimated degree of functionalization is as high as one out of every 20 carbons in the nanotubes bearing a functionalized moiety. The functionalizing moieties can be removed by heating in an argon atmosphere. Nanotubes derivatized with a 4-tert-butylbenzene moiety were found to possess significantly improved solubility in organic solvents. Functionalization of the nanotubes with a molecular system that has exhibited switching and memory behavior is shown. This represents the marriage of wire-like nanotubes with molecular electronic devices.     

Nitrite electrochemical sensor for food analysis based on direct immobilization of hemoglobin on multi-walled carbon nanotube ionic liquid electrode

A novel nitrite biosensor was constructed by simultaneous immobilization of hemoglobin (Hb) and a room temperature ionic liquid, octylpyridinium chloride ([OcPy][Cl]), on multi-walled carbon ionic liquid electrode (MWILE). The direct electron transfer of Hb showed a pair of redox peaks with a formal potential of ?0.187 V vs. Ag/AgCl in pH 5.0 acetate buffer solution. Nitrite (NO₂ ^?) catalysis on the modified electrode was investigated by cyclic voltammetry and amperometry. The biosensor exhibited a wide linear range for NO₂ ^? detection from 0.01 to 15 mM, with a detection limit (3σ) of 1.46 μM. MWILE provided an excellent matrix for protein immobilization and biosensor fabrication which could be used for the determination of NO₂ ^? with a low detection limit, fast response, long linearity, and excellent sensitivity.     

Solid-state graphene-based supercapacitor with high-density energy storage using ionic liquid gel electrolyte: electrochemical properties and performance in storing solar electricity

Journal of Solid State Electrochemistry - The electrochemical properties and high-density energy storage performance of graphene nano-platelet-based solid-state electrical double-layer...