A facile approach for synthesizing molecularly imprinted graphene for ultrasensitive and selective electrochemical detecting 4-nitrophenol

In this work, a novel and convenient strategy was developed to prepare molecularly imprinted polymers (MIPs) on the surface of graphene sheet. In this route, vinyl group functionalized graphene (GR/NVC) was first prepared by immobilizing 4-vinylcarbazole onto the surface of graphene via π–π interaction. The subsequent grafting copolymerization of methacrylic acid and ethylene glycol dimethacrylate in the presence of 4-nitrophenol (4-NP, template molecule) was carried out at GR/NVC surface, leading to the formation of GR/MIPs composite. The GR/MIPs composite was characterized by FTIR, fluorescence, TGA, SEM and AFM, and was used to fabricate electrochemical sensor for the detection of 4-NP. The electrochemical behavior of GR/MIPs sensor for 4-NP was investigated by cyclic voltammetry (CV) and differential pulse voltammetry (DPV). The effects of the preparation conditions, such as concentration of the NVC and template, the solution pH, and incubation time, were also optimized. Under optimized conditions, the DPV current response of GR/MIPs sensor was nearly 12 times than that of the GR/NIPs sensor. It also should be noted that as compared to traditional MIP, shorter response time and much higher current response were demonstrated. In addition, the GR/MIPs sensor could recognize 4-NP from its structural analogs, indicating the excellent selectivity of the GR/MIPs sensor. The peak current is linearly proportional to the concentration of 4-NP ranging from 0.01 μM to 100 μM and 200 μM to 1000 μM with a significantly low detection limit of 5 nM, a wider response range and lower detection limits as compared to most of the previously reported electrochemical sensors for 4-NP. Furthermore, the GR/MIPs sensor exhibits good stability with adequate reproducibility and has been successfully used to determine 4-NP in water samples.     

Analysis of parabens in cosmetics by low pressure liquid chromatography with monolithic column and chemiluminescent detection

This paper presents an application of chromatographic separation based on an ultra-short monolithic column and chemiluminescent detection in an FIA type instrument manifold for the determination of four paraben mixtures: methylparaben (MP), ethylparaben (EP), propylparaben (PP) and butylparaben (BP). The separation is achieved in 150 s using two consecutive carriers: first 12% ACN:water that changes 75 s after injection to 27% ACN:water. The detection is based on the oxidation of the hydrolysis product of parabens, p-hydroxybenzoic acid, with Ce(IV) in the presence of Rhodamine 6G which evokes chemiluminescence of sufficient intensity to enable a sensitive determination of these species. After optimization of the variables involved, the analytical method is characterized, displaying the following values for concentration ranges, detection limits and precision, as relative standard deviation at low concentration (0.15 mg l⁻¹)—MP: from 9.9 × 10⁻⁷ to 3.3 × 10⁻⁴ M; 1.9 × 10⁻⁸; 5.6%; EP: from 9.0 × 10⁻⁷ to 3.3 × 10⁻⁴ M; 2.8 × 10⁻⁸; 3.5%; PP: from 8.3 × 10⁻⁷ to 9.9 × 10⁻⁵ M; 2.3 × 10⁻⁸; 4.2%; and BP: from 7.7 × 10⁻⁷ to 9.9 × 10⁻⁵ M; 4.2 × 10⁻⁸ M; 6.2%. The method was applied and validated satisfactorily for the determination of these parabens in cosmetic samples, comparing the results against a liquid chromatography reference method.     

对羟基苯甲酸酯分子印迹电化学传感器的研制

利用分子印迹技术,以对羟基苯甲酸乙酯为模板分子,甲基丙烯酸为单体,在玻碳电极表面原位聚合分子印迹聚合物敏感膜.采用方波伏安法对对羟基苯甲酸乙酯在该印迹电极上的电化学行为进行了研究,当响应时间为15 min时,0.95 V(vs SCE)处的峰电流与对羟基苯甲酸乙酯的浓度在2.0×10-6 ～2.0×10-4 mol/L范围内呈线性关系,检出限(S/N=3)为1.0 μmol/L,而相同条件下,对羟基苯甲酸乙酯在控制电极上的响应非常小并对浓度变化不灵敏;同时在印迹电极上氧化峰电位较在裸电极上发生了微弱正移.同一支印迹电极对对羟基苯甲酸乙酯响应值的RSD为4.3%(n=10).该印迹电极对尼泊金酯类具有良好的选择性,对对羟基苯甲酸甲酯、丙酯以及丁酯的选择性系数分别为1.89、1.70和2.01;对结构相似的苯酚、对羟基苯甲酸、对氨基苯甲酸等响应不灵敏,对结构差异较大的如维生素C等几乎无响应.用该分子印迹电极对实际样品进行分析,加标回收率大于90%.     

Potentiometric stripping analysis of methyl and ethyl parathion employing carbon nanoparticles and halloysite nanoclay modified carbon paste electrode

Carbon nanoparticles (CNPs) and halloysite nanoclay (HNC) modified carbon paste electrode (HNC–CNP–CPE) was developed for the determination of methyl parathion (MP) and ethyl parathion (EP). The electrochemical behavior of these molecules was investigated employing cyclic voltammetry (CV), chronocoulometry (CC), electrochemical impedance spectroscopy (EIS) and potentiometric stripping analysis (PSA). After optimization of analytical conditions employing this electrode at pH 5.0 in acetate buffer (0.1 M), the peak currents were found to vary linearly with its concentration in the range of 1.55 × 10⁻⁹ to 3.67 × 10⁻⁶ M and 1.21 × 10⁻⁹ to 4.92 × 10⁻⁶ M for MP and EP, respectively. The detection limits (S/N = 3) of 4.70 × 10⁻¹⁰ M and 3.67 × 10⁻¹⁰ M were obtained for MP and EP, respectively, using PSA. The prepared modified electrode showed several advantages such as simple preparation method, high sensitivity, very low detection limits and excellent reproducibility. The proposed method was employed for the determination of MP and EP in fruits, vegetables, water and soil samples.     

Synthetic approaches to parabens molecularly imprinted polymers and their applications to the solid-phase extraction of river water samples

In this paper we describe the synthesis, characterisation and use of two distinct molecularly imprinted polymers (MIPs) prepared using esters of p-hydroxybenzoic acid (parabens) as templates: one MIP was synthesised by precipitation polymerisation using a semi-covalent molecularly imprinting strategy with methyl paraben as the template/target (MIP 1); the second MIP was prepared in monolithic form through a conventional non-covalent molecular imprinting strategy, with butyl paraben as the template (MIP 2). MIP 1 recognized methyl paraben, showed cross-selectivity for other parabens analytes used in the study and higher affinity towards these compounds than did a non-imprinted control polymer. Similarly, MIP 2 demonstrated higher affinity towards paraben analytes than a non-imprinted control polymer.For the analysis of environmental water samples, a solid-phase extraction (SPE) protocol was developed using MIP 2 as sorbent, and results were compared to a SPE using a commercial sorbent (Oasis HLB). With MIP 2 as sorbent and butyl paraben as target, when percolating 500 mL of river water spiked at 1 μg L⁻¹ through the SPE cartridge, and using 1 mL of isopropanol as cleaning solvent, a higher recovery of butyl 4-hydroxybenzoate (butyl paraben) and a cleaner chromatogram where achievable when using the MIP compared to the commercial sorbent.     

Electrochemical and microfabrication strategies for remotely operated smart chemical sensors: Application of anodic stripping coulometry to calibration-free measurements of copper and mercury

Remote unattended sensor networks are increasingly sought after to monitor the drinking water distribution grid, industrial wastewater effluents, and even rivers and lakes. One of the biggest challenges for application of such sensors is the issue of in-field device calibration. With this challenge in mind, we report here the use of anodic stripping coulometry (ASC) as the basis of a calibration-free micro-fabricated electrochemical sensor (CF-MES) for heavy metal determinations. The sensor platform consisted of a photo-lithographically patterned gold working electrode on SiO₂ substrate, which was housed within a custom stopped-flow thin-layer cell, with a total volume of 2–4 μL. The behavior of this platform was characterized by fluorescent particle microscopy and electrochemical studies utilizing Fe(CN)₆^3−/4− as a model analyte. The average charge obtained for oxidation of 500 μM ferrocyanide after 60 s over a 10 month period was 176 μC, corresponding to a volume of 3.65 μL (RSD = 2.4%). The response of the platform to copper concentrations ranging from 50 to 7500 ppb was evaluated, and the ASC results showed a linear dependence of charge on copper concentrations with excellent reproducibility (RSD ≤ 2.5%) and accuracy for most concentrations (≤5–10% error). The platform was also used to determine copper and mercury mixtures, where the total metallic content was measurable with excellent reproducibility (RSD ≤ 4%) and accuracy (≤6% error).     

Ag ion irradiated based sensor for the electrochemical determination of epinephrine and 5-hydroxytryptamine in human biological fluids

A promising and highly sensitive voltammetric method has been developed for the first time for the determination of epinephrine (EP) and 5-hydroxytryptamine (5-HT) using 120 MeV Ag ion irradiated multi-walled carbon nano tube (MWCNT) based sensor. The MWCNT were irradiated at various fluences of 1e12, 3e12 and 1e13 ions cm⁻² using palletron accelerator. The simultaneous determination of EP and 5-HT has been carried out in phosphate buffer solution of pH 7.20 using square wave voltammetry and cyclic voltammetry. Experimental results suggested that irradiation of MWCNT by Ag ions enhanced the electrocatalytic activity due to increase in effective surface area and insertion of Ag ions, leading to a remarkable enhancement in peak currents and shift of peak potentials to less positive values as compared to the unirradiated MWCNT (pristine). The developed sensor exhibited a linear relationship between peak current and concentration of EP and 5-HT in the range 0.1–105 μM with detection limit (3σ/b) of 2 nM and 0.75 nM, respectively. The practical utility of irradiation based MWCNT sensor has been demonstrated for the determination of EP and 5-HT in human urine and blood samples.     

Simultaneous determination, by capillary zone electrophoresis, of multiple components of different industrial products

Summary Four parabens (esters of 4-hydroxybenzoic acid), effective preservatives against the growth of bacteria, yeast, and mold in numerous industrial products, have been used in this work as model compounds to demonstrate the resolving power of capillary electrophoresis (CE). The simultaneous determination of methyl-(MP), ethyl-(EP), propyl-(PP), and butylparaben (BP) was achieved by capillary zone electrophoresis (CZE) with UV diode-array detection at 294 nm. When run voltage, temperature, and electrolyte concentration and pH were optimized the most effective separation was achieved within 7 min by use of 50 cm (effective length) fused silica capillary tubing and operation at 25kV and 20°C. Background electrolyte comprising 35 mM tetraborate buffer adjusted to pH 10.0 gave the best results. The limits of detection of the optimized method ranged from 0.65 μg mL⁻¹ for BP to 0.81 μg mL⁻¹ for MP; the relative standard deviation was between 0.35 and 0.50%. These results showed that the method enables the determination of the four parabens in commerially available cosmetic and pharmaceutical preparations containing some of the parabens and in an unidentified canned berry fruit juice.     

Electrodeposition of gold nanoclusters on overoxidized polypyrrole film modified glassy carbon electrode and its application for the simultaneous determination of epinephrine and uric acid under coexistence of ascorbic acid

A novel biosensor was fabricated by electrochemical deposition of gold nanoclusters on ultrathin overoxidized polypyrrole (PPyox) film, formed a nano-Au/PPyox composite on glassy carbon electrode (nano-Au/PPyox/GCE). The properties of the nanocomposite have been characterized by field emission scanning electron microscope (FE-SEM), X-ray photoelectron spectroscopy (XPS), powder X-ray diffraction (XRD) and electrochemical investigations. The nano-Au/PPyox/GCE had strongly catalytic activity toward the oxidation of epinephrine (EP), uric acid (UA) and ascorbic acid (AA), and resolved the overlapping voltammetric response of EP, UA and AA into three well-defined peaks with a large anodic peak difference. The catalytic peak currents obtained from differential pulse voltammetry increased linearly with increasing EP and UA concentrations in the range of 3.0 × 10⁻⁷ to 2.1 × 10⁻⁵ M and 5.0 × 10⁻⁸ to 2.8 × 10⁻⁵ M with a detection limit of 3.0 × 10⁻⁸ and 1.2 × 10⁻⁸ M (s/n = 3), respectively. The results showed that the modified electrode can selectively determine EP and UA in the coexistence of a large amount of AA. In addition, the sensor exhibited excellent sensitivity, selectivity and stability. The nano-Au/PPyox/GCE has been applied to determination of EP in epinephrine hydrochloride injection and UA in urine samples with satisfactory results.     

para-Sulfonatocalix[6]arene-modified silver nanoparticles electrodeposited on glassy carbon electrode: Preparation and electrochemical sensing of methyl parathion

In this paper, a new electrochemical sensor, based on modified silver nanoparticles, was fabricated using one-step electrodeposition approach. The para-sulfonatocalix[6]arene-modified silver nanoparticles coated on glassy carbon electrode (pSC₆-Ag NPs/GCE) was characterized by attenuated total reflection IR spectroscopy (ATR-IR), X-ray photoelectron spectroscopy (XPS) and scanning electron microscopy (SEM), etc. The pSC₆ as the host are highly efficient to capture organophosphates (OPs), which dramatically facilitates the enrichment of nitroaromatic OPs onto the electrochemical sensor surface. The combination of the host-guest supramolecular structure and the excellent electrochemical catalytic activities of the pSC₆-Ag NPs/GCE provides a fast, simple, and sensitive electrochemical method for detecting nitroaromatic OPs. In this work, methyl parathion (MP) was used as a nitroaromatic OP model for testing the proposed sensor. In comparison with Ag NPs-modified electrode, the cathodic peak current of MP was amplified significantly. Differential pulse voltammetry was used for the simultaneous determination of MP. Under optimum conditions, the current increased linearly with the increasing concentration of MP in the range of 0.01-80 μM, with a detection limit of 4.0 nM (S/N = 3). The fabrication reproducibility and stability of the sensor is better than that of enzyme-based electrodes. The possible underlying mechanism is discussed.     

The application of conducting polymer nanoparticle electrodes to the sensing of ascorbic acid

An ascorbic acid sensor was fabricated via the drop-casting of dodecylbenzene sulphonic acid (DBSA)-doped polyaniline nanoparticles onto a screen-printed carbon-paste electrode. The modified electrode was characterised with respect to the numbers of drop cast layers, optimum potential and operating pH. The sensor was found to be optimal at neutral pH and at 0 V vs. Ag/AgCl. Under these conditions, the sensor showed good selectivity and sensitivity in that it did not respond to a range of common interferents such as dopamine, acetaminophen, uric acid and citric acid, but was capable of the detection of ascorbic acid at a sensitivity of 0.76 μA mM⁻¹ or 10.75 μA mM⁻¹ cm⁻² across a range from 0.5 to 8 mM (r² = 0.996, n = 6), and a limit of detection of 8.3 μM (S/N = 3). The sensor was compared to a range of other conducting polymer-based ascorbate sensors and found to be comparable or superior in terms of analytical performance.     

Comparative study for the analysis of parabens by micellar electrokinetic capillary chromatography with and without large-volume sample stacking technique

The separation and determination of four parabens (methyl, ethyl, propyl, and butyl p-hydroxybenzoate) which are commonly used as preservatives in cosmetic products, by micellar electrokinetic capillary chromatography (MEKC) with and without large-volume sample stacking (LVSS) technique were compared. As an effective on-line concentration technique, LVSS was successfully combined with MEKC to determine neutral parabens in an acidic media. The effects of some typical parameters such as sample volume, buffer pH, temperature, and concentration of surfactant were examined. The detection limits for this LVSS-MEKC method were found to be 3.0 × 10⁻⁷ M for each of the parabens based on the signal-to-noise ratio of 3, which were around 300 times lower than normal MEKC technique. The curves of peak response versus concentration were linear from 1.0 × 10⁻⁶ to 5.0 × 10⁻⁵ M with regression coefficients of 0.9987, 0.9960, 0.9925 and 0.9864, respectively. A simple and easy-manipulative sample preparation method was developed and validated by analyzing commercially available cosmetic samples. It was found that with current sample preparation process and instrumentation system, 0.5 g of sample is enough for the analysis of parabens preservatives in cosmetic product with satisfactory results.     

Determination of personal care products in sewage sludge by pressurized liquid extraction and ultra high performance liquid chromatography–tandem mass spectrometry

This paper describes a method for the determination of a group of personal care products including four UV filters, four preservatives and two antimicrobials in sewage sludge. The method combines pressurized liquid extraction and ultra high performance liquid chromatography–tandem mass spectrometry. Most of the parameters that affect the extraction step such as temperature, pressure, static extraction time, number of cycles, purge time and flush volume were optimized using a fractional experimental design. In the chromatographic step, the compounds were detected by using tandem mass spectrometry with a triple quadrupole analyzer with electrospray ionization in positive and negative modes. The use of small diameter particles (1.8 μm) in the chromatographic column allowed the compounds to be eluted in 9 min. The entire process took a total of 39 min. All recoveries were higher than 72% except for 2,4-dihydroxybenzophenone (a UV filter), whose recovery was 30%. The repeatability and reproducibility between days expressed as RSD (%) (n = 3) were less than 8% and 13%, respectively. The LODs and LOQs were lower than 8 μg/kg and 12.5 μg/kg of dry weight (d.w.), respectively. When the method was applied to determine the compounds in sewage sludge from a domestic sewage treatment plant, triclosan (an antimicrobial) and octocrylene (a UV filter) showed the highest levels, 1490 μg/kg (d.w.) and 1842 μg/kg (d.w.), respectively. This paper describes for the first time the determination of parabens and two UV filters (octyldimethyl-p-aminobenzoic acid and benzophenone-3) in sewage sludge.     

Clozapine imprinted polymers: synthesis, characterization and application for drug assay in human serum

A variety of molecularly imprinted polymers (MIPs) against clozapine (CLZ) were synthesized and their recognition properties were compared with blank non-imprinted polymers. Methacrylic acid (MAA) was used as a functional monomer and Chloroform or tetrahydrofuran (THF) were applied as polymerization solvents. Chloroform as the solvent and MAA/CLZ ratio of 5 was selected as optimized polymerization condition. In Scatchard analysis of MIP-CLZ interactions, two classes of binding sites were found in MIP—high affinity (KD = 14.5 μM) and low affinity (KD = 322.5 μM) binding sites. The polymer was evaluated as a selective sorbent in molecularly imprinted solid-phase extraction (MISPE) of CLZ from human serum. The MISPE procedure was developed and optimized with a recovery of 88-102%. The intra- and inter-day precision values were less than 1.36% and 2.5%, respectively. The selectivity of MISPE for CLZ was studied in comparison with some drugs. These drugs could be present with CLZ, simultaneously in serum of patients. The data indicated that the imprinted polymer had a good selectivity and affinity for CLZ and could be used for selective extraction and analysis of CLZ in human serum.     

Development of a group selective molecularly imprinted polymers based solid phase extraction of malachite green from fish water and fish feed samples

A group selective molecularly imprinted solid phase extraction (MISPE) for malachite green (MG) from fish water and fish feed samples was developed. Using MG as template molecule, methacrylic acid as functional monomer, ethylene glycoldimethacrylate as linking agent and bulk polymerization as synthetic method, the molecularly imprinted polymers (MIPs) were synthesized and characterized with rebinding experiment. The Scatchard polt's analysis revealed that the template-polymer system showed the two-site binding behavior with dissociation constants of 0.3194 μmol L⁻¹ and 15.70 μmol L⁻¹, respectively. MG and two structurally related compounds, leucomalachite green (LMG) and crystal violet (CV) were employed for selectivity test. The MIPs exhibited the highest selective rebinding to MG, but also displayed 83.0% and 87.5% of cross-reactivity with LMG and CV, demonstrating that MIPs could be used as group recognition sorbents in solid phase extraction. The extraction conditions of MISPE column for MG were optimized. Tap water samples spiked with MG at concentration of 0.5-10 ng mL⁻¹ were extracted by MISPE column and analyzed by high performance liquid chromatography. The recoveries of MISPE column for MG extraction were found to be 76.8-93.7% with the relative standard deviations of 2.12-10.09%, indicating the feasibility of the prepared MIPs for MG extraction. No detectable MG was observed in one fish farming water sample and two fish feed samples; while the MG concentrations in two pet fishpond water samples were found at 1.50 ng mL⁻¹ and 0.67 ng mL⁻¹, respectively.     

Ultrasensitive electrochemical sensor for p-nitrophenyl organophosphates based on ordered mesoporous carbons at low potential without deoxygenization

p-Nitrophenyl organophosphates (OPs) including paraoxon, parathion and methyl parathion, etc, are highly poisonous OPs, for which sensitive and rapid detection method is most needed. In this work, an ultrasensitive electrochemical sensor for the determination of p-nitrophenyl OPs was developed based on ordered mesoporous carbons (OMCs) modified glassy carbon electrode (GCE) (OMCs/GCE). The electrochemical behavior and reaction mechanism of p-nitrophenyl OPs at OMCs/GCE was elaborated by taking paraoxon as an example. Experimental conditions such as buffer pH, preconcentration potential and time were optimized. By using differential pulse voltammetry, the current response of the sensor at −0.085 V was linear with concentration within 0.01–1.00 μM and 1.00–20 μM paraoxon. Similar linear ranges of 0.015–0.5 μM and 0.5–10 μM were found for parathion, and 0.01–0.5 μM and 0.5–10 μM for methyl parathion. The low limits of detection were evaluated to be 1.9 nM for paraoxon, 3.4 nM for parathion and 2.1 nM for methyl parathion (S/N = 3). Common interfering species had no interference to the detection of p-nitrophenyl OPs. The sensor can be applicable to real samples measurement. Therefore, a simple, sensitive, reproducible and cost-effective electrochemical sensor was proposed for the fast direct determination of trace p-nitrophenyl OPs at low potential without deoxygenization.     

Reusable and robust high sensitive non-enzymatic glucose sensor based on Ni(OH)2 nanoparticles

Nickel hydroxide nanoparticles were successfully electrodeposited on graphite electrode (Gr/NiONP) and employed as a robust non-enzymatic glucose sensor. The results of cyclic voltammetry (CV) and chronoamperometry demonstrated that the Gr/NiONP electrode displayed high electrocatalytic activity toward glucose. The oxidation current is directly related to the glucose concentration from 1 μM to 15 mM. Besides, the glucose sensor displayed high sensitivity (2400 μA mM⁻¹ cm⁻²) with a detection limit of 0.53 μM (S/N = 3) in basic solution. Moreover, the sensor showed excellent selectivity, reproducibility and stability properties. The relative standard deviation is 1.2% for 10 successive measurements in 16 μM glucose. Interestingly, the signal for glucose was maintained at 95% of its initial value even after 6 months of storage under ambient conditions. Gr/NiONP electrode has also been tested to detect glucose in human serum with satisfactory results.     

An enzymeless organophosphate pesticide sensor using Au nanoparticle-decorated graphene hybrid nanosheet as solid-phase extraction

A sensitive enzymeless organophosphate pesticides (OPs) sensor is fabricated by using Au nanoparticles (AuNPs) decorated graphene nanosheets (GNs) modified glassy carbon electrode as solid phase extraction (SPE). Such a nanostructured composite film, combining the advantages of AuNPs with two dimensional GNs, dramatically facilitates the enrichment of nitroaromatic OPs onto the surface and realizes their stripping voltammetric detection of OPs by using methyl parathion (MP) as a model. The stripping voltammetric performances of captured MP were evaluated by cyclic voltammetric and square-wave voltammetric analysis. The combination of the nanoassembly of AuNPs-GNs, SPE, and stripping voltammetry provides a fast, simple, and sensitive electrochemical method for detecting nitroaromatic OPs. The stripping analysis is highly linear over the MP concentration ranges of 0.001-0.1and 0.2-1.0 μg mL⁻¹ with a detection limit of 0.6 ng mL⁻¹. This designed enzymeless sensor exhibits good reproducibility and acceptable stability.     

Comparison of particle size and flow rate optimization for chromatography using one-monomer molecularly imprinted polymers versus traditional non-covalent molecularly imprinted polymers

The dependence of enantio-selective chromatographic performance on particle size, as measured by separation factor, was investigated for one-monomer molecularly imprinted polymers (OMNiMIPs) compared to traditionally formed EGDMA/MAA molecularly imprinted polymers (MIPs). Five particle size ranges were compared (<20 μm, 20-25 μm, 25-38 μm, 38-45 μm, and 45-63 μm), revealing that the particle sizes above 25 μm provided the highest separation factor, and thus the best enantiomer separation, for both imprinted polymers. Other chromatographic parameters such as the number of theoretical plates and resolution exhibited only minor changes for the OMNiMIPs as the particle size changed, except for particles 20 μm and below. However, the number of theoretical plates and resolution for EGDMA/MAA are higher for particles in the 20-25 μm range. Thus, chromatographic factors for the EGDMA/MAA polymers are better in this range, despite better enantioselectivity for particle sizes above 25 μm. In contrast, OMNiMIPs generally show the most favorable performance for particle sizes in the 38-45 μm range. It was also found that decreasing flow rate resulted in improved enantioselectivity for both MIPs for all particle sizes.     

A novel sensor based on electropolymerization of β-cyclodextrin and l-arginine on carbon paste electrode for determination of fluoroquinolones

An electrochemical sensor for fluoroquinolones (FQs) based on polymerization of β-cyclodextrin (β-CD) and l-arginine (l-arg) modified carbon paste electrode (CPE) (P-β-CD-l-arg/CPE) was built for the first time. Synergistic effect of l-arg and β-CD was used to construct this sensor for quantification of these important antibiotics. Scanning electron microscope (SEM) image shows that polymer of β-CD and l-arg has been successfully modified on electrode. Electrochemical impedance spectroscopy (EIS) and cyclic voltammograms (CV) further indicate that polymer of β-CD and l-arg efficiently decreased the charge transfer resistance value of electrode and improved the electron transfer kinetic between analyte and electrode. Under the optimized conditions, this modified electrode was utilized to determine the concentrations of ciprofloxacin, ofloxacin, norfloxacin and gatifloxacin. The differential pulse voltammogram (DPV) exhibits the oxidation peak currents were linearly proportional to their concentration in the range of 0.05–100 μM for ciprofloxacin, 0.1–100 μM for ofloxacin, 0.1–40 μM for norfloxacin and 0.06–100 μM for gatifloxacin, respectively. This method was also successfully used to detect the concentrations of each drug in pharmaceutical formulations and human serum samples. In addition, this proposed fluoroquinolones sensor exhibited good reproducibility, long-term stability and fast current response.