Test determination of aluminum, beryllium, and cationic surfactants using phenolcarboxylic acids of the triphenylmethane series immobilized on cloths from synthetic and natural fibers

We consider the use of cloth matrices from viscose and cotton fibers bearing phenolcarboxylic acids of the triphenylmethane series immobilized by adsorption in chemical test methods of analysis. Chrome Azurol S, Sulfochrome, and Eriochrome Cyanine R were used for immobilization. It was found that the reagents are weakly retained on cellulose matrices. The degree of retention varied from 10 to 60%. It was observed that the reagent complexes of metal ions exhibited enhanced adsorbability on the matrices. Cloths with immobilized Chrome Azurol S were used in the test determination of 0.0005–0.5 mg/L beryllium and 0.0005–1.0 mg/L aluminum. When the reaction products were preconcentrated on the cloth from 100 mL of a test solution, the detection limit was 0.0001 mg/L. Procedures were developed for determining 0.1–100 mg/L aluminum and 0.02–0.6 mg/L beryllium in solutions using cloth test strips encapsulated into a polymeric film. It was demonstrated that Sulfochrome and Eriochrome Cyanine R immobilized on cloths can be used to determine 0.01–1 and 1–1000 mg/L cationic surfactants.     

Catalysis‐Electrochemical Detection of Horseradish Peroxidase at Zeptomole Level in Capillary Zone Electrophoresis

Capillary zone electrophoresis with catalysis‐electrochemical detection has been developed and applied to determining horseradish peroxidase (HRP) at zeptomole levels. In this method, an on‐line enzyme catalysis reactor with a reaction capillary was designed. Isoenzymes of HRP were separated by capillary zone electrophoresis, and then they catalyzed the enzyme substrate 3,3′,5,5′‐tetramethylbenzide (TMB(Red)) and H₂O₂ in the reaction capillary. The reaction product, TMB(Ox), could be determined using amperometric detection on a carbon fiber microdisk bundle electrode at the outlet of the reaction capillary. Because of enzyme amplification, a significant amount of TMB(Ox) could be produced for detection. Therefore, the limit of detection (LOD) of HRP is very low. The optimum conditions of the method are 1.5×10^?2 mol/L borate (pH 7.4) for the run buffer, 2×10^?3 mol/L for the concentration of H₂O₂, 2×10^?4 mol/L TMB(Red)+2.0×10^?2 mol/L citrate‐phosphate (pH 5.0) for the substrate solution, 40 cm for the liquid pressure height, 20 kV for the separation voltage, 100 mV for the detection potential. HRP could be measured with a detection limit of 4.8×10^?12 mol/L or 47.5 zmol (S/N=3). The linear range is from 2.40×10^?11 to 2.40×10^?8 mol/L. Using this method, commercial HRP was measured at zeptomole within ten minutes.     

Spectroscopic and electrochemical properties of Cu-dicyandiamide complex

Dicyandiamide(DICY) is a common ligand that exhibits low toxicity but can irritate the skin and eyes and cause methemoglobinemia on long-term exposure. Crystalline Cu-dicyandiamide(Cu-DICY) was obtained via facile synthesis and its molecular structure and theoretical Raman spectra were simulated by using density functional theory(DFT). The results suggested that the Cu~(2+) coordinates with two H_2 O molecules and two different DICY molecules(an imino DICY and an amino DICY). The stability constants of Cu-DICY were calculated, and the electrochemical properties were studied. Two electrochemical redox processes occur in Cu-DICY in an aqueous solution: a reversible reaction with a formal potential of 0.2 V vs.MSE and an irreversible reaction between –0.4 and –1.2 V vs. MSE. The standard rate constant k0 for the reversible reaction was estimated to be 7.6×10~(-3) cm/s. In addition, based on the reversible reaction of Cu-DICY, square wave voltammetry was used to rapidly determine the concentration of Cu(II) and the detection limit was 66.7 μg/L, which satisfies the detection limit requirements for copper in tap water(2 mg/L) as provided by the World Health Organization.     

Calculation of the detection limit in chemical test methods of analysis based on the principles of planar chromatography

Microsoft Office Excel and CorelDraw Graphics Suite were used for the statistical treatment of experimental data in the chemical test methods of analysis. A simple and available method for calculating the detection limit was demonstrated by the example of test systems for determining molybdenum(VI), bismuth( III), and titanium(IV). The use of Pantone Hexachrome Coated enabled us to construct calibration curves for the main color intensity of the reaction zone on the indicator matrix as a function of analyte concentration. The approximation of experimental data using the Microsoft Office Excel software was considered; it eliminated the complicated and laborious calculation of the coefficients of approximation equation and the correlation coefficient. It was found that, for the studied test systems, the detection limit was close to the determination limit. In the use of test strips, the detection limit for Mo(VI) and Bi(III) was 0.04 and 1.0 mg/L, respectively, and in the determination of Mo(VI) and Ti(IV) using a test facility, it was 0.03 and 0.02 mg/L, respectively.     

Gas-chromatographic determination of aliphatic amines in natural surface water and wastewater

A procedure was developed for the gas-chromatographic determination of aliphatic amines C₇–C₂₀ with prederivatization by N-methyl-bis(trifluoroacetamide), in the concentration range of natural surface water, to 10^?4-1 mg/L, and wastewater, to 10^?3-1 mg/L. The conditions were optimized for the extraction preconcentration of aliphatic amines with toluene from natural surface water and wastewater. The detection limit for aliphatic amines at a signal-to-noise ratio of 3: 1 was 50 ng/L.     

An effective colorimetric and ratiometric fluorescent probe for bisulfite in aqueous solution

We have developed the first two-photon colorimetric and ratiometric fluorescent probe, BICO, for the detection of bisulfite (HSO₃⁻) in aqueous solution. The probe contains coumarin and benzimidazole moieties and can detect HSO₃⁻ based on the Michael addition reaction with a limit of detection 5.3 × 10⁻⁸ M in phosphate-buffered saline solution. The probe was used to detect bisulfite in tap water, sugar and dry white wine. Moreover, test strips were made and used easily. We successfully applied the probe to image living cells, using one-photon fluorescence imaging. BICO overcomes the limitations in sensitivity of previously reported probes and the solvation effect of bisulfite, which demonstrates its excellent value in practical application.     

Two-dimensional TiO2 (001) nanosheets as an effective photo-assisted recyclable sensor for the electrochemical detection of bisphenol A

Electrochemical detection is an efficient method for the detection of Bisphenol A (BPA). Herein, a sensitive photo-electrochemical sensor based on two-dimensional (2D) TiO₂ (001) nanosheets was fabricated and then used for BPA electrochemical detection. Upon light irradiation, the 2D TiO₂ (001) nanosheets electrode provided a lower detection limit of BPA detection compared with an ambient electrochemical determination. The low detection limit is ∼5.37 nmol/L (S/N = 3). Furthermore, profiting from the photoelectric characteristics, the 2D TiO₂ (001) nanosheets electrode exhibits a nice regeneration property. After 45 min of light irradiation, the electrochemical signal was regenerated from 14.7% to 82.9% of the original signal at the 6^th cycle. This is attributed to the non-selective OH mediation produced by the 2D TiO₂ (001) nanosheets mineralizing anodic polymeric products and resuming surface reactive sites. This investigation indicates that photo-assistance is an efficient method to improve the electrochemical sensor for detecting BPA in water environments.     

Field determination of fluoride in drinking water using a polymeric aluminium complex of 5-(2-carboxyphenylazo)-8-hydroxyquinoline impregnated paper

A simple field method which allows the determination of fluoride in drinking water with a small handheld instrument called Arsenator was developed. Arsenator is a commercially available instrument which was used successfully for reliable determination of arsenic. In the proposed method the functionality of the Arsenator which is based on a photometric measurement of a spot on the reagent paper is expanded to analyse fluoride. A polymeric aluminium complex of 5-(2-carboxyphenylazo)-8-hydroxyquinoline (LH₂) has been prepared as a new specific reagent for fluoride. Job's method of continuous variation was adopted for the determination of the composition of the coloured complex, which was further characterized by UV-VIS spectroscopic studies. The molar absorptivity of the complex formation is 8.48?×?10³?L?mol^?1?cm^?1 at 410?nm. The coloured complex reacts with fluoride on an impregnated paper where its colour changes are dependent on the concentration of fluoride in water samples. The change in the colour was measured using the Arsenator. The method allows a reliable determination of fluoride in the range 0.3 to 2.0?mg?L^?1. Further spectophotometric determinations of fluoride in drinking water were also studied. The determination is based on the reaction of aluminium complex with fluoride in the examined samples. Beer's law is obeyed in the range 0.3 to 2.0?mg?L^?1 of fluoride at 495?nm. Sensitivity, detection limit and quantitation limit of the method were found to be 0.251?±?0.007?µg^?1?mL, 0.1?mg?L^?1 and 0.3?mg?L^?1, respectively. The optimum reaction conditions and other analytical conditions were evaluated. The effect of interfering ions on the determination is described. There is no interference by nitrate or chloride. Sulphate interfered only at high concentrations which are not expected in drinking water.     

Simultaneous determination of three chloroacetic acids,three herbicides,and 12 anions in water by ion chromatography

An ion chromatography method was developed for the simultaneous detection of three soluble herbicides (glyphosate, bentazone and picloram), three chlorine disinfection byproducts (monochloroacetic acid, dichloroacetic acid and trichloroacetic acid) and 12 anions in water (Cl^–, Br^–, SO₄^2–, CO₃^2–, ClO₃^–, ClO₄^–, BrO₃^–, PO₄^3–, NO₂^–, NO₃^–, CH₃COO^– and COO^–). High linearity (r² > 0.996) was observed for all target analytes for each respective concentration range. The limit of detection and limit of quantitation were between 0.21–0.85 and 0.06–25.46 μg/L, respectively. However, the interference effect of Cl^–, NO₃^–, SO₄^2– and CO₃^2– on some target analytes must be considered during the analysis. Sample pre‐treatment by a hydrogen column (H‐column) required to reduce the negative effect of CO₃^2–. Additionally, sample pre‐treatment by a sliver–hydrogen column (Ag–H‐column) is required when Cl^– > 100 mg/L and SO₄^2– < 50 mg/L, and pre‐treatment by both a barium column (Ba‐column) and an H‐column is required when Cl^– > 100 mg/L and SO₄^2– > 50 mg/L. When Cl^– > 100 mg/L, SO₄^2– > 50 mg/L and CO₃^2– > 20 mg/L, the sample pre‐treatment by either an Ag–H–Ba‐column or an Ag–H‐column and Ba‐column is required to minimize interference.     

A visual test method for determining selenium(IV) with indigocarmine immobilized on silica

A solid reagent based on silica successively modified by quaternary ammonium salt and indigocarmine is proposed for the test determination of selenium(IV). The detection limit for selenium is found to be 10 μg/L using catalytic reaction of the reduction of immobilized indigocarmine by sulfide as an indicator reaction. The calibration graph is linear in the range of selenium concentrations from 50 to 400 μg/L. Alkali and alkaline-earth metals, NH ₄ ⁺ , Cl^?, NO ₃ ^? , and SO ₄ ^2? do not interfere with the determination of selenium. The interference from heavy metals is eliminated by introducing EDTA. The procedure was tested in determining selenium in preparations of vitamins and biologically active supplement.     

Determination of Selenium(IV) by Stripping Voltammetry at a Mercury-Film Electrode

A procedure was proposed for the determination of selenium(IV) by stripping voltammetry on a mercury-film electrode at an electrolysis potential of +0.4 V versus the saturated silver–silver chloride reference electrode in a 1 M H₂SO₄ solution. The current of the cathodic peak is a linear function of the selenium(IV) concentration in the range from 5 × 10^–3 to 3 × 10^–1 mg/L (6.3 × 10^–8 to 3.8 × 10^–6 M) at a time of electrolysis of 30 s (t _el). The detection limit for selenium is 1 × 10^–4 mg/L (1.3 × 10^–9 M) at t _el = 300 s. It was shown that selenium(IV) can be determined in the presence of 10 mg/L Zn(II), 1 mg/L Cd(II), 0.5 mg/L Pb(II), and 0.2 mg/L Cu(II). A procedure for the determination of selenium in natural, mineral, and potable water was proposed.     

Aptamer-functionalized Ti3C2-MXene Nanosheets with One-step Potentiometric Detection of Programmed Death-ligand 1

This communication describes a simple sensitive one-step potentiometric aptasensing method for quantitative detection of a referenced therapeutic biomarker (programmed death-ligand 1, PD−L1). The aptasensor is constructed by modifying PD−L1-specific aptamer on Ti₃C₂-MXene nanosheets-functionalized electrode. Introduction of PD−L1 induces the specific reaction between PD−L1 and aptamer, thereby resulting in the change of spatial structures. The surface electric potential of modified electrode is shifted upon addition of PD−L1 proteins before and after the reaction of aptamer with the analyte. Interestingly, potentiometric aptamer with Ti₃C₂-MXene nanosheets can achieve a higher sensitivity and a lower detection limit toward target PD−L1 relative to aptamer-modified electrode. Experimental results indicated that the linear range and detection limit of using Ti₃C₂-MXene nanosheets were 0.01–100 ng mL⁻¹ and 7.8 pg mL⁻¹ PD−L1, respectively. Meanwhile, the specificity, reproducibility, storing stability and accuracy of potentiometric aptasensor are acceptable for the screening of PD−L1 in human serum samples.     

A Turn‐On Fluorescence Chemosensor for Cyanide in Aqueous Media Based on a Nucleophilic Addition Reaction

We synthesized a new cyanide (CN ⁻) chemosensor CX based on a nucleophilic addition reaction prompted by cyanide ion, which could be used for highly selective and sensitive fluorescence turn‐on detection of cyanide in aqueous media. The CX showed selective fluorescence recognition for CN ⁻, the miscellaneous competitive anions (F⁻, Cl⁻, Br⁻, I⁻, AcO ⁻, H₂PO₄⁻, HSO₄⁻, ClO₄⁻, S^{2 −}, PO₄³⁻, CO₃²⁻ and SCN ⁻) did not lead to any significant interference. The detection limit of the sensor towards CN ⁻ is 1.15 × 10⁻⁷ mol•L⁻¹. The sensor has been successfully applied to estimate the cyanide ion in seeds of cherries. Test strips based on CX were fabricated, which could be used as a convenient and efficient CN ⁻ test kit to detect CN ⁻ in aqueous solution for “in‐the‐field” measurement.     

Electrocatalytic oxidation of nitric oxide at nano-TiO2/Nafion composite film modified glassy carbon electrode

A novel nanocrystalline TiO₂ (nano-TiO₂) and Nafion composite film modified glassy carbon electrode has been developed for the determination of nitric oxide (NO) radical in an aqueous solution. This modified electrode can be employed as a NO sensor with a low detection limit, fast response, high sensitivity and selectivity. Two apparent anodic peaks were observed at 0.67 and 0.95 V at the nano-TiO₂ modified glassy carbon electrode by differential pulse voltammetry (DPV). After further modification with a thin film of Nafion, which was capable of preventing some anionic interference such as nitrite and ascorbic acid, only one peak appeared and the peak current enhanced greatly. The chronocoulometric experimental results showed NO was oxidized by one-electron transfer reaction at the composite film modified electrode. The amperometric responses increased linearly with the concentrations of NO ranging from 3.6×10⁻⁷ mol/L to 5.4×10⁻⁵ mol/L. The detection limit was estimated to be 5.4×10⁻⁸ mol/L. In this sensor system, the modification film provides complete selectivity for NO over nitrite anions (NO₂⁻).     

甲基紫与肝素钠结合反应的电化学研究及分析应用

应用电化学分析法研究了在pH 1.5的酸性反应条件下肝素钠与甲基紫的结合反应. 甲基紫在滴汞电极上有一个不可逆的还原峰, 峰电位为－0.58 V (vs. SCE), 加入肝素钠后峰电位发生正移且峰电流下降, 利用电化学方法对电极反应过程进行了研究, 结果发现两者结合后生成了一种电化学活性的复合物, 导致溶液的电化学参数发生了变化, 求解出结合比为1∶3, 结合常数为2.47×10¹⁴, 对结合反应条件和电化学检测条件进行了优化, 在最佳条件下峰电流的降低同肝素钠的浓度在0.2～4.0 mg/L范围内呈线性关系, 线性回归方程为∆I_p″ (nA)＝－724.9＋1741.4c (mg/L) (n＝11, γ＝0.994), 检测限为0.072 mg/L. 将本方法应用于肝素钠样品的测定, 结果令人满意. 对常见干扰物质的影响进行了考察, 表明本方法具有较好的选择性.     

Electrodeposition of zinc oxide nanoparticles on multiwalled carbon nanotube-modified electrode for determination of caffeine in wastewater effluent

We report on the development of an electrochemical sensor based on electrodepositing zinc oxide on multiwalled carbon nanotube-modified glassy carbon electrode for the detection of caffeine in pharmaceutical wastewater effluents. The measurements were carried out using cyclic voltammetry, electrochemical impedance spectroscopy, chronoamperometry and differential pulse voltammetry (DPV). DPV measurements showed a linear relationship between oxidation peak current and concentration of caffeine in 0.1 M HClO₄ (pH 1.0) over the concentration range 0.00388–4.85 mg/L and a detection limit of 0.00194 mg/L. The diffusion coefficient and Langmuir adsorption constant for caffeine were calculated to be 3.25 × 10^?6 cm² s^?1 and 1.10 × 10³ M^?1, respectively. The sensor showed satisfactory results when applied to the detection of caffeine in wastewater effluents.     

Astraphloxin Cyanine Dye as a Reagent for the Selective Extraction-Photometric Determination of Trace Mercury(II)

A procedure was developed for the extraction-photometric determination of low concentrations of mercury(II) in aqueous solutions. It is based on the reaction of the Hg Br ₃ ^? acidocomplex with the Astraphloxin cationic dye to give an ion pair extracted with toluene. The detection limit for mercury is 0.015 mg/L. Effects of a number of heavy metal cations on determining mercury(II) were studied. It was shown that these effects appear in the presence of 500-fold molar amounts of interferents. The procedure was used for determining mercury(II) in the presence of 200-fold molar amounts of some heavy metal cations. The relative standard deviation was no worse than 5%.     

Paracetamol Sensor Based on Molecular Imprinting by Photosensitive Polymers

A voltammetric paracetamol sensor based on molecularly imprinted polymeric (MIP) micelles was prepared by direct electrodeposition. The MIP micelles were prepared via macromolecule self‐assembly of an amphiphilic photocrosslinkable copolymer using paracetamol as the template molecule. The resultant molecularly imprinted polymeric micelles swelled with increasing pH, and the disassociation of the micelles occurred at pH above approximately 7.4. A robust MIP film with good solvent resistance was formed on the electrode surface by anodic electrodeposition of the MIP micelles and subsequent photocrosslinking, resulting in the fabrication of a MIP electrochemical sensor for detecting paracetamol. The resultant sensor showed good response and selectivity towards paracetamol. In addition, a wide linear range from 0.01 mmol/L to 8 mmol/L and a low detection limit of 1×10^?6 mol/L for paracetamol detection was demonstrated based on this sensor. The MIP sensor also showed good stability and reversibility which was applied to determine paracetamol commercial tablets.     

Determination of Hg2+ in Tap Water Based on the Electrochemiluminescence of Ru(phen)32+ and Thymine at Bare and Graphene Oxide‐Modified Glassy Carbon Electrodes

The electrochemiluminescence (ECL) of the Ru(phen)₃²⁺/thymine (T) system at bare and graphene oxide (GO)‐modified glassy carbon (GC) electrodes was utilized to determine Hg²⁺ in tap water. The ECL intensity of Ru(phen)₃²⁺ was considerably enhanced by the addition of thymine because of the occurrence of ECL reaction between them. Subsequently, the ECL intensity of Ru(phen)₃²⁺/T system rapidly decreased with the addition of Hg²⁺ because of the formation of a T‐Hg²⁺‐T complex. A linear response (R²=0.9914) was obtained over a Hg²⁺ concentration range of 1.0×10^?9 mol/L to 1.0×10^?5 mol/L with a detection limit of 3.4×10^?10 mol/L at a bare GC electrode in 0.1 mol/L phosphate buffer (pH=8.0). The detection limit can be further reduced to 4.2×10^?12 mol/L after modification of the GC electrode by GO. To verify its applicability, the proposed method was utilized to determine Hg²⁺ in tap water and simulated wastewater. The method exhibited good reproducibility and stability and thus reveals the possibility of developing a novel ECL detection method for Hg²⁺.     

Preconcentration of albumin on silica with attached groups of polyoxyethylated isooctyl phenol

The potencies of silica with attached groups of polyoxyethylated isooctyl phenol (SiO ₂ -TX) as an adsorbent for the solid phase extraction (SPE) preconcentration of bovine serum albumin (BSA) in urine are examined. SiO₂-TX is shown to effectively extract BSA (up to 96%) as an ion associate with cationic (at pH 8) and anionic (at pH 1.5) surfactants. The maximal capacity of SiO₂-TX to BSA makes 33 mg/g in the presence of octylpyridinium bromide, 27 mg/g in the presence of cetyltrymethylammonium bromide or sodium dodecylsulfate with the linearity range in Henri’s area up to 23 and 20 mg/g of SiO₂-TX, respectively; the distribution coefficients attain 1.8 × 10³ mL/g. BSA is eluted quantitatively with 1–4 mL of acetonitrile containing NaOH, which makes possible the use of adsorbent for the reaction of protein with trifluoroethanol (TFE) before its photometric determination by the Lowry method. The influence of accompanying urine components is studied, i.e., urea, glucose, Na⁺, K⁺, Mg²⁺, chlorides, and phosphates, on the efficiency BSA extraction from model aqueous solutions on SiO₂-TX. The detection limit for BSA makes 4 mg/L and the analytical range, from 12 to 140 mg/L.