Highly Sensitive Molecularly Imprinted Sensor Based on Platinum Thin‐film Microelectrode for Detection of Chloramphenicol in Food Samples

A highly sensitive and selective electrochemical biomimetic sensor was fabricated for fast detection of chloramphenicol (CAP) in honey and milk samples. Platinum thin‐film microelectrode (Pt TFME), which could provide unique electrochemical properties and achieve measurement using very limited solution volumes, was surface‐modified by electropolymerizing o‐phenylenediamine. Cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS) were used to characterize the preparation process of CAP‐imprinted poly(o‐phenylenediamine) film and rebinding ability of CAP into the imprinted cavities. The electrochemical properties of the sensor were further investigated with square wave voltammetry (SWV) by using K₃Fe(CN)₆ as an electroactive probe. The current difference of oxidation peaks of K₃Fe(CN)₆ had a good linear relationship with the concentration of CAP in the range of 0.9–10 nM. The detection limit was 0.39 nM based on the signal to noise ratio of 3. The developed sensor was successfully applied to determine CAP in honey and milk samples, and the result was in good agreement with that obtained by high performance liquid chromatography‐mass spectrometry (HPLC‐MS). The sensor showed high sensitivity and excellent selectivity to CAP in comparison to other structurally related and/or normally existing antibiotics, and demonstrated great promise for the rapid quantification of CAP in real food samples and field analysis.     

Cross‐Reactive Sensor Arrays for the Detection of Peptides in Aqueous Solution by Fluorescence Spectroscopy

A simple but powerful method for the sensing of peptides in aqueous solution has been developed. The transition‐metal complexes [PdCl₂(en)], [{RhCl₂Cp*}₂], and [{RuCl₂(p‐cymene)}₂] were combined with six different fluorescent dyes to build a cross‐reactive sensor array. The fluorescence response of the individual sensor units was based on competitive complexation reactions between the peptide analytes and the fluorescent dyes. The collective response of the sensor array in a time‐resolved fashion was used as an input for multivariate analyses. A sensor array comprised of only six metal–dye combinations was able to differentiate ten different dipeptides in buffered aqueous solution at a concentration of 50 μM . Furthermore, the cross‐reactive sensor could be used to obtain information about the identity and the quantity of the pharmacologically interesting dipeptides carnosine and homocarnosine in a complex biological matrix, such as deproteinized human blood serum. The sensor array was also able to sense longer peptides, which was demonstrated by differentiating mixtures of the nonapeptide bradykinin and the decapeptide kallidin.     

DNA sensor: A novel electrochemical gene detection method using carbon electrode immobilized DNA probes

Abstract

The authors have developed a novel, rapid, convenient, and specific gene detection method, named the ‘DNA sensor,’ using a graphite electrode loaded with DNA probes. Synthesized oligonucleotide (5-TGCAGTTCCGGTGGCTGATC-3′) complementary to oncogene v-myc was employed for a model probe. The oligonucleotide was chemically adsorbed on a basal plane pyrolytic graphite (BPPG) electrode. The sensor was able to be applied to a hybridization reaction (40°C) in a linearized pVM623 solution carrying the Pst I fragment of v-myc (1.5 kbp).

After the hybridization reaction, the sensor was immersed into an acridine orange solution (1 μM) and washed with a phosphate buffer (pH 7.0). Acridine orange intercalated between base pairs of the formed double stranded DNAs on the electrode. The anodic peak potential of acridine orange that interacted with the DNAs on the electrode was measured. The positive shift of the peak potential increased in proportional to the pVM623 concentration in the hybridization reaction. 10^?1 g/ml of pVM623 was able to be detected in the buffer solution using the sensor. This gene detection was completed within an hour.     

2-Methylimidazole-assisted Morphology Modulation of a Copper-based Metal-organic Framework Transducer for Enhanced Electrochemical Peroxidase-like Activity

A tailored metal-organic framework transducer material Cu−BDC(NH₂)@2-MI was synthesized with 2-methylimidazole as competitive ligand for the modulation of its morphology and catalytic activity. 2-MI effectively helped the deprotonation of 2-aminoterephthalic acid and enabled the fast generation of MOF crystals at room temperature. More importantly, this 2-MI-doped MOF exhibited well-tuned morphology and was able to assist efficient redox procedures in electrochemical H₂O₂ reduction. Therefore, a prototype H₂O₂ sensor can present decent linear ranges from 10 μM to 13.28 mM and a detection limit of 0.97 μM. This novel design could boost the utilization of proprietary MOFs materials out of laboratory.     

Non-enzymatic detection of hydrogen peroxide using a functionalized three-dimensional graphene electrode

A novel three-dimensional (3D) electrochemical sensor was developed for highly sensitive detection of hydrogen peroxide (H₂O₂). Monolithic and macroporous graphene foam grown by chemical vapor deposition (CVD) served as the electrode scaffold. Using in-situ polymerized polydopamine as the linker, the 3D electrode was functionalized with thionine molecules which can efficiently mediate the reduction of H₂O₂ at close proximity to the electrode surface. Such stable non-enzymatic sensor is able to detect H₂O₂ with a wide linear range (0.4 to 660 μM), high sensitivity (169.7 μA mM^− 1), low detection limit (80 nM), and fast response (reaching 95% of the steady current within 3 s). Furthermore, this sensor was used for real-time detection of dynamic release of H₂O₂ from live cancer cells in response to a pro-inflammatory stimulant.     

Sensitive and Visual Detection of Phosgene by a TICT-Based BODIPY Dye with 8-(o-Hydroxy)aniline as the Active Site

Phosgene and its substitutes (diphosgene and triphosgene) are widely utilized as chemical industrial materials and chemical warfare agents and pose a threat to public health and environmental safety due to their extreme toxicity. Research efforts have been directed to develop selective and sensitive detection methods for phosgene and its substitutes. In this paper, we have prepared two BODIPY-based fluorescent probes, o-Pah and o-Pha, which are two isomers with different active sites, ortho-aminohydroxy (3′,4′ or 4′,3′) phenyls at meso position of BODIPY, and compared their sensing performance toward triphosgene. The probe with o-(4′-amino-3′-hydroxyl), o-Pha, exhibits better sensing performance over the o-(3′-amino-4′-hydroxyl), o-Pah, for instance, a lower limit of detection (LOD) (0.34 nm vs. 1.2 nm ), and more rapid response (10 s vs. 200 s). Furthermore, based on the above comparative studies, a red-fluorescence probe o-Phae has been constructed through extending 3,5-conjugation of o-Pha. The probe o-Phae displays rapid response (60 s), high sensitivity to triphosgene (LOD=0.88 nm ), and high selectivity for triphosgene over relevant analytes including nitric oxide. Finally, a facile test strip for phosgene was fabricated by immobilizing o-Phae in a polyethylene oxide membrane for sensitive (<2 ppm) and selective detection of phosgene in the gas phase.     

Non‐enzymatic Fructose Sensor Based on Co3O4 Thin Film

In this study, we report on the selective of fructose on Co₃O₄ thin film electrode surface. A facile chemical solution deposition technique was used to fabricate Co₃O₄ thin film on fluorine doped tin oxide, FTO, glass. Electrode characterization was done using XRD, HRTEM, SEM, AFM, and EIS. The constructed sensor exhibited two distinctive linear ranges (0.021–1.74 mM; 1.74–∼15 mM) covering a wide linear range of up to ∼15 mM at an applied potential of +0.6 V vs Ag/AgCl in 0.1 M NaOH solution. The sensor demonstrated high, reproducible and repeatable (R.S.D of <5 %) sensitivity of 495 (lower concentration range) & 53 (higher concentration range) μA cm⁻² mM⁻¹. The sensor produced a low detection limit of ∼1.7 μM (S/N =3). The electrode was characterised by a fast response time of <6 s and long term stability. The repeatability and stability of the electrode resulted from the chemical stability of Co₃O₄ thin film. The sensor was highly selective towards fructose compared to the presence of other key interferences i. e. AA, AC, UA. The ease of the electrode fabrication coupled with good electrochemical activity makes Co₃O₄ thin film, a promising candidate for non‐enzymatic fructose detection.     

Humidity Sensing Properties of Flower‐Like VO2(B) and VO2(M) Nanostructures

VO₂(B) nanoflowers were synthesized via hydrothermal method, and VO₂(M) nanoflowers were obtained through heat‐transformation. Two sensors based on VO₂(B) and VO₂(M) nanoflowers were fabricated and their humidity characteristics were studied. It was found that these sensors exhibited fast response and recovery, perfect reproducibility and good stability. The VO₂(M) type sensor is more sensitive at high RH and can be used for high humidity detection. On the contrary, the VO₂(B) type sensor has a higher sensitivity at low RH, and can be used for low humidity detection, which is difficult for humidity sensors based on many other semiconductor oxides.     

Toxicity Assessment of Cyanide and Tetramethylene Disulfotetramine （Tetramine） Using Luminescent Bacteria Vibrio-qinghaiensis and PbO= Electrochemical Sensor

The toxicities of cyanide and tetramethylene disulfotetramine （tetramine） were evaluated by two methods of luminescent bacteria and PbO2 electrochemical sensor. Vibrio-qinghaiensis, a kind of luminescent bacteria, can produce bioluminescence and the bioluminescence was decreased with the addition of toxicants. The toxicities of cyanide and tetrarnine were expressed as 10 min-EC50 value, which was the concentration of chemical that reduces the light output by 50% after contact for 10 min. Nano PbO2 modified electrode, a rapid toxicity determination method was also described in this work. By the PbO2 modified electrode, the current responses of Escherichia coli （E. coli） were changed with the addition of toxicants. The value of 10 min-EC50 was also provided with the PbO2 electrochemical sensor. Compared with the 10 min-EC50 and detection limits （38.38 and 0.60 μg/mL for cyanide, 0.24 and 0.02 μg/mL for tetramine） with luminescent bacteria, the PbO2 sensor provided a simple and convenient method with lower 10 min-EC50 and detection limits （26.37 and 0.52 μg/mL for cyanide, 0.21 and 0.01 μg/mL for tetramine） and fast response time.     

Prussian Blue Modified Submicron Structured Gold Electrodes for Amperometric Hydrogen Peroxide Sensing

In this work, we present a simple and effective approach for fabricating sub‐micron structured gold (SM−Au) electrodes by chemically etching the magnetron co‐sputtered gold film in KI solution for certain time. Such electrodes with a large surface area to volume ratio were used as the matrix for electrochemical deposition of Prussian blue (PB) to develop an electrochemical hydrogen peroxide sensor. Experimental characterization using scanning electron microscope and atomic force microscope shows that the thickness of PB layer on SM−Au electrode is around 140 nm, and is composited with cubic PB nanocrystals. The electrochemical performance of the designed sensor, studied using cyclic voltammograms and chronoamperometry methods, suggests that the sensor based on SM−Au/PB electrode presents the direct electron transfer of PB particle towards SM−Au film, and exhibits fast response, wide linearity, low detection limit and high stability. Under the optimized conditions, the sensitivity of the developed sensor for the detection of H₂O₂ reaches the value of 512 mA cm⁻² M⁻¹ with a linear range from 1 μM to 4.5 mM.     

A Novel Hg(II) PVC Membrane Sensor Based on Simple Ionophore Ethylenediamine Bis‐Thiophenecarboxaldehyde

Abstract

A mercury (II) ion‐selective polyvinyl chloride (PVC) membrane sensor based on ethylenediamine bisthiophenecarboxaldehyde (EDBT) as a novel nitrogen‐ and sulfur‐containing sensing material was successfully developed. The ionophore was produced through Schiff's base formation between ethylenediamine and 2‐thiophenecarboxaldehyde. These two reagents have the advantages of low cost and simple chemical compounds. Ortho‐nitro phenyl pentyl ether (o‐NPPE) as solvent and sodium tetraphenyl borate (NaTPB) as a lipophilic salt were chosen. The sensor exhibited a good linear response of 30.0±0.4 mV per decade within the concentration range of 10^?7–10^?2 and a detection limit of 7.0×10^?8 mol L^?1 Hg(II). The sensor showed good selectivity and fast response for the mercury (II) ion with respect to some alkali, alkaline earth, transition, and heavy metal ions. The EDBT–based sensor was suitable for aqueous solutions of pH range from 2.0 to 4.5. It can be used for about 3 months without any considerable divergence in potential. The formation constant of ionophore complex with Hg(II) ion was calculated by using the segmented sandwich membrane method. The structure of both the ionophore and its Hg(II) complex were examined using infrared spectra and elemental analysis. The proposed sensor was applied for the determination of Hg(II) content in some dental amulgum alloys and as an indicator electrode for potentiometric titration of Hg(II) ion with EDTA solution, as well as with I^?, OH^?, and IO₃ ^? ions. In addition, the solubility products of the previous ions were determined by using this sensor.     

Photodecomposition of Chloroform Catalyzed by Unmodified MCM‐41 Mesoporous Silica

Unactivated MCM‐41 mesoporous silica catalyzes the photodecomposition of chloroform to phosgene and hydrogen chloride under near‐UV (λ > 360 nm) irradiation. The rate of photodecomposition increases toward an asymptotic limit as the O₂ partial pressure is increased. Deuterochloroform does not decompose under the same experimental conditions. Low concentrations of both cyclohexane and ethanol quench the photodecomposition, whereas water, up to its solubility limit, does not. Dissolved tetraalkylammonium salts suppress photodecomposition. The data are consistent with a mechanism in which light absorption by an SiO₂ defect yields an electron‐deficient oxygen atom, which then abstracts hydrogen from chloroform. The resulting CCl₃ radicals react with oxygen to form a peroxy radical that decomposes, eventually yielding phosgene and hydrogen chloride.     

Ammonia Gas Sensor Using Polypyrrole‐Coated TiO2/ZnO Nanofibers

Highly porous polypyrrole (PPy)‐coated TiO₂/ZnO nanofibrous mat has been successfully synthesized. The core TiO₂/ZnO nanofibers have an average diameter of ca. 100 nm and the shell of ultrathin PPy layer has a thickness of ca. 7 nm. The NH₃ gas sensor using the as‐prepared material exhibited a fast response over a wide dynamic range and high sensitivity with a detection limit of 60 ppb (S/N=3). Compared to conventional pristine PPy film, the improved performance in NH₃ detection can be attributed to the free access of NH₃ to PPy and a minimized gas diffusion resistance through the ultrathin PPy layer.     

A Hydrogen Peroxide Sensor Based on Silver Nanoparticles Biosynthesized by Bacillus subtilis

In this study, silver nanoparticles （AgNPs） were biosynthesized by Bacillus subtilis and used to construct a nonenzymatic hydrogen peroxide （H202） sensor, Scanning electron microscopy, transmission electron microscopy and energy dispersive spectroscopy confirmed that the AgNPs were prepared successfully with spherical morphol- ogy. The electrochemical properties of the resulted sensor were investigated by cyclic voltammetry, chronoam- perometry and electrochemical impedance spectroscopy. It was found that the sensor exhibited good electrocatalytic activity towards H202 reduction with a wider linear range from 0.05 to 120 mmol.L-1, a detection limit of 8 gmol.L-1 and a fast response time less than 2 s. The sensor exhibited good selectivity for H202 determination in the presence of glucose, acetaminophen, ascorbic acid and uric acid.     

Molecularly imprinted polymer-based electrochemical sensor for the sensitive detection of glyphosate herbicide

A sensitive electrochemical molecularly imprinted sensor was developed for the detection of glyphosate (Gly), by electropolymerisation of p-aminothiophenol-functionalised gold nanoparticles in the presence of Gly as template molecule. The extraction of the template leads to the formation of cavities that are able to specifically recognise and bind Gly through hydrogen bonds between Gly molecules and aniline moieties. The performance of the developed sensor for the detection of Gly was investigated by linear sweep voltammetry using a hexacyanoferrate/hexacyanoferrite solution as redox probe, the electron transfer rate increasing when concentration of Gly increases, due to a p-doping effect. The molecularly imprinted sensor exhibits a broad linear range, between 1 pg/L and 1 µg/L and a quantification limit of 0.8 pg/L. The selectivity of the proposed sensor was investigated towards the binding of Gly metabolite, aminomethylphosphonic acid, revealing excellent selectivity towards Gly. The developed sensor was successfully applied to detect Gly in tap water samples.     

A Nonenzymatic Glucose Sensor Using Nanoporous Platinum Electrodes Prepared by Electrochemical Alloying/Dealloying in a Water‐Insensitive Zinc Chloride‐1‐Ethyl‐3‐Methylimidazolium Chloride Ionic Liquid

We report here a nonenzymatic sensor by using a nanoporous platinum electrode to detect glucose directly. The electrode was fabricated by electrochemical deposition and dissolution of PtZn alloy in zinc chloride‐1‐ethyl‐3‐methylimidazolium chloride (ZnCl₂‐EMIC) ionic liquid. Both SEM and electrochemical studies showed the evidences for the nanoporous characteristics of the as‐prepared Pt electrodes. Amperometric measurements allow observation of the electrochemical oxidation of glucose at 0.4 V (vs. Ag/AgCl) in pH 7.4 phosphate buffer solution. The sensor also demonstrates significant reproducibility in glucose detection; the higher the roughness factor of the Pt electrode, the lower the detection limit of glucose. The interfering species such as ascorbic acid and p‐acetamidophenol can be avoided by using a Pt electrode with a high roughness factor of 151. Overall, the nanoporous Pt electrode is promising for enzymeless detection of glucose at physiological condition.     

A New Amperometric Biosensor Based on HRP/Nano-Au/L-Cysteine/Poly（o-Aminobenzoic acid）-Membrane-Modified Platinum Electrode for the Determination of Hydrogen Peroxide

The third generation amperometric biosensor for the determination of hydrogen peroxide （H2O2） has been described. For the fabrication of biosensor, o-aminobenzoic acid （oABA） was first electropolymerized on the surface of platinum （Pt） electrode as an electrostatic repulsion layer to reject interferences. Horseradish peroxidase （HRP） absorbed by nano-scaled particulate gold （nano-Au） was immobilized on the electrode modified with polymerized o-aminobenzoic acid （poABA） with L-cysteine as a linker to prepare a biosensor for the detection of H2O2. Amperometric detection of H2O2 was realized at a potential of ＋20 mV versus SCE. The resulting biosensor exhibited fast response, excellent reproducibility and sensibility, expanded linear range and low interferences. Temperature and pH dependence and stability of the sensor were investigated. The optimal sensor gave a linear response in the range of 2.99×10^-6 to 3.55×10^-3 mol·L^-1 to H2O2 with a sensibility of 0.0177 A·L^-1·mol^-1 and a detection limit （S/N = 3） of 4.3×10^-7 mol·L^-1. The biosensor demonstrated a 95% response within less than 10 s.     

A Novel Al(III)‐Selective Electrochemical Sensor Based on N,N′‐Bis(salicylidene)‐1,2‐phenylenediamine Complexes

A polyvinylchloride membrane sensor based on N,N′‐bis(salecylidene)‐1,2‐phenylenediamine (salophen) as membrane carrier was prepared and investigated as a Al³⁺‐selective electrode. The sensor exhibits a Nernstian response toward Al(III) over a wide concentration range (8.0×10^?7–3.0×10^?2 M), with a detection limit of 6.0×10^?7 M. The potentiometric response of the sensor is independent of the pH of the test solution in the pH range 3.2–4.5. The electrode possesses advantages of very fast response and high selectivity for Al³⁺ in comparison with alkali, alkaline earth and some heavy metal ions. The sensor was used as an indicator electrode, in the potentiometric titration of aluminum ion and in determination of Al³⁺ contents in drug, water and waste water samples.     

Development of an Amperometric Sensor Highly Selective For Dopamine and Analogous Compounds Determination Using Bis(2,2′‐Bipyridil) Copper(II) Chloride Complex

The use of [Cu(bipy)₂]Cl₂?6H₂O as a biomimetic catalyst in the construction of an amperometric sensor for dopamine determination is reported. The sensor was prepared modifying a glassy carbon electrode with a Nafion membrane doped with [Cu(bipy)₂]Cl₂?6H₂O complex. The sensor presented a higher response in 0.25 mol L^?1 phosphate buffer solution (pH 7.0), with an applied potential of ?50 mV (vs. SCE). In the optimized operational conditions, a linear response range between 35 and 240 μmol L^?1, with a sensitivity of 2.02±0.07 nA l μmoL^?1 cm^?2 and detection limit of 8.0 μmol L^?1 were typically observed for the sensor. The response time presented for this sensor was 0.5 s, presenting the same response for at least 40 successive measurements, with good repeatability (3.0%) expressed as relative standard deviation for n=6. The difference of the response between four sensor preparations was 4%. A detailed investigation about the sensor response for other sixteen phenolic compounds and interfering species were carried out. The sensor was applied in the determination of dopamine in pharmaceutical preparation with success.     

Design of a novel optical sensor for determination of trace amounts of copper by UV–visible spectrophotometry in real samples

A new optical chemical sensor is established for sensitive and selective spectrophotometric detection of copper based on the immobilization of 3‐(2‐methyl‐2,3‐dihydro‐1,3‐benzothiezol‐2‐yl)‐2H‐chromen‐2‐one on a triacetylcellulose membrane. Copper ions react with the immobilized ligand and cause an increase in the absorption of the membrane at 550 nm in universal buffer solution at pH = 6. The effects of pH, indicator concentration and reaction time on the immobilization of the ligand were studied. This optode exhibits a linear range of 7.0 × 10^?7 to 1 × 10^?4 mol l^?1 of copper ion concentration with a limit of detection of 3.0 × 10^?7 mol l^?1. The response time of the newly designed optode is within 3 min. The effect of different possible interfering species was investigated and it was found that the sensor has very good selectivity. The proposed sensor benefits from advantages such as low cost, high stability, low detection limit, fast response time, reproducibility, relatively long lifetime, and good selectivity for Cu²⁺ ion determination among a large number of alkali, alkaline earth, transition and heavy metal ions. The sensor can readily be regenerated with thiourea solution and its response is reversible and reproducible (relative standard deviation < 1.4%). The proposed optode was applied successfully for the determination of Cu(II) in various samples.