Skin exposure: requirements to methods determining active ingredient of pesticides in washings

2019 ◽  
pp. 43-48
Author(s):  
V. N. Rakitskii ◽  
N. E. Fedorova ◽  
I. V. Bereznyak ◽  
N. G. Zavolokina ◽  
L. P. Muhina
Keyword(s):  
Lower Limit ◽  
Limit Of Detection ◽  
Solid Phase ◽  
Absorbed Dose ◽  
Ambient Air ◽  
Safety Coefficient ◽  
Limit Value ◽  
Calculated Risk ◽  
Nature Studies ◽  
Active Substances

The article presents results of studies exemplified by diquat on analysis concerning influence of lower limit value of quantitative assessment in washing sample for safety coefficient in exposure and in absorbed dose, if acting substance is absent in workplace ambient air samples and in dermal washings of workers. To control diquat in dermal washings, there is a method based on ion-pair liquid chromatography with ultraviolet detection (working wavelength 310 nm). To concentrate sample, cartridges for solid-phase extraction, containing ion exchange sorbent (Oasis MCX 6cc/500 mg), are used. Lower limit of assessment in washing sample — 0,15 micrograms. Experimentally set washing completeness is within range of 80–92%, standard deviation of repetition is 7,0% at most. The method created was tested in nature studies determining dermal exposure in workers subjected to 5 various preparations based on diquat dibromide when used for surface spraying from tractor and from aircraft. For lower limit of detection in washing sample (0,15 micrograms/washing), calculated risk value of exposure varied within 0,26–0,36; risk of absorbed dose was low — 0,23 (the allowable one ≤1). Findings are that present measuring methods which provide lower limit of detection 1 and 5 micrograms in washing sample could result in unallowable risk establishment even with absence of the substance in all samples of workplace air and dermal washings. The calculation formula suggested enables to give theoretic basis for requirements to lower limit of detecting active substances in dermal washing samples for evaluating risk of pesticides use in agriculture.

Determination of Sulfonylurea Herbicides in Grains by Capillary Electrophoresis

1995 ◽  
Vol 78 (4) ◽  
pp. 1091-1096 ◽  
Author(s):  
Alexander J Krynitsky ◽  
Douglas M Swtneford
Keyword(s):  
Capillary Electrophoresis ◽  
Lower Limit ◽  
Limit Of Detection ◽  
Solid Phase ◽  
Residue Analysis ◽  
High Sensitivity ◽  
Sulfonylurea Herbicides ◽  
Optical Cell ◽  
Liquid Chromatographic ◽  
Tribenuron Methyl

Abstract A capillary electrophoresis (CE) method was developed to separate and determine residues of 5 sulfonylurea herbicides in grains (wheat, barley, and corn). This work demonstrated the practicality of using CE for residue analysis of sulfonylureas. The method yielded good recoveries and adequate sensitivities at tolerance levels (0.05–0.1 ppm). The compounds investigated were metsulfuron methyl (Ally), thifensulfuron methyl (Harmony), chlorsulfuron (Glean), rimsulfuron (DPX-E9636), and tribenuron methyl (Express). Acetonitrile extracts of grain samples were partitioned with hexane and then cleaned up with cation exchange solid-phase extraction cartridges. Quantitation was performed by micellar electrokinetic capillary chromatography using a high-sensitivity optical cell. Average recoveries at the 0.05 ppm level ranged from 72.9 to 118.5%. The lower limit of detection was approximately 0.02 ppm, except for rimsulfuron and tribenuron methyl, for which the lower limit of detection was 0.035 ppm. The method was less complicated and showed better sensitivity than current single-analyte liquid chromatographic enforcement methods.

Development of Chemical Samples Preparation Method to Reduce the Lower Limit of Absorbed Dose Assessment by Electron Paramagnetic Resonance Spectrometry

2020 ◽  
Vol 65 (2) ◽  
pp. 50-56
Author(s):  
V. Pantelkin ◽  
V. Zhuravleva ◽  
A. Tsoviyanov
Keyword(s):  
Hydrazine Hydrate ◽  
Lower Limit ◽  
Chemical Treatment ◽  
Limit Of Detection ◽  
Absorbed Dose ◽  
Reducing Agents ◽  
Dose Assessment ◽  
Epr Spectra ◽  
Bone Material ◽  
Epr Signal

Purpose: Development of a method of chemical sample preparation to reduce the lower limit of the absorbed dose estimation by EPR spectrometry. Material and methods: The required number of bone samples was prepared to study the effect of chemical treatment of bone material samples in organic solvents on their EPR spectra. They were subjected to primary treatment to separate the bones from the remains of soft biological tissue, then a dense bone was isolated and its defatting was carried out. Further, a series of parallel experiments on chemical treatment of bone materials in solutions of three organic reducing agents (hydrazine hydrate, ethylenediamine and diethylenetriamine) were done to reduce the magnitude of the native signal when carrying out works on reconstruction of absorbed doses using EPR spectroscopy. Recording of EPR spectra was performed on the ELEXSYS E500 Bruker spectrometer equipped with a high-q cylindrical resonator SHQE. Irradiation of the samples was carried out on the X-ray biological unit RUB RUST-M1. Results: To reduce the lower limit of detection of the absorbed dose and improve the reliability of the assessment of the absorbed dose using the EPR method, it is required to reduce the native component of the EPR signal without affecting, if possible, the radiation component of the EPR signal. To achieve this effect, a chemical treatment in solutions of amines was proposed, which affect the collagen compounds that present in the bones and which are responsible for the appearance of a native signal in the EPR spectrum. After chemical treatment of bone material samples at 30°C for 30 minutes in a solution of different amines, there was a significant decrease in the amplitude of the native signal, which was: 4 for hydrazine hydrate, 3.3 for diethylenetriamine and 2.1 for ethylenediamine. For bone material samples that were subjected to the proposed chemical treatment in hydrazine hydrate, it is possible to confidently determine the amplitude of the radiation signal by a value of 2–3 Gy against the minimum dose values of 6–8 Gy for bone material samples that were not chemically treated. Conclusion: It was found that during the chemical treatment there is a significant reduction of the native signal in the spectra of EPR of bone materials, the decrease of the radiation signal at the same time was slightly. Comparison of the results of treatment of bone materials in three organic reducing agents showed that the best results are obtained by the use of hydrazine hydrate at a temperature of 30°C for 30 minutes.

Immunoradiometric Assay for the Calcium-Stabilized Conformation of Human Protein S

1987 ◽  
Vol 58 (04) ◽  
pp. 0998-1004 ◽  
Author(s):  
S R Poort ◽  
P P Deutz-Terlouw ◽  
A van Wijngaarden ◽  
R M Bertina
Keyword(s):  
Lower Limit ◽  
Anticoagulant Therapy ◽  
Oral Anticoagulant ◽  
Limit Of Detection ◽  
Solid Phase ◽  
Oral Anticoagulant Therapy ◽  
Protein S ◽  
Human Protein ◽  
Type I ◽  
Oral Anticoagulant Treatment

SummaryRabbit polyclonal anti-protein S serum was fractionated with immobilized human protein S to establish solid-phase immunoradiometric assays recognizing Ca(II)-dependent and NonCa(II)-dependent epitopes of human protein S. The two assays were specific for PS:Ca(II)Ag and PS:NonCa(II)Ag and highly sensitive with a lower limit of detection of about 2.5 ng/ml.PS:Ca(II)Ag and PS:NonCa(II)Ag levels were measured in immunopurified protein S, thrombin-modified protein S and chy-motrypsin-cleaved protein S. Only in chymotrypsin-cleaved protein S an important discrepancy between the two antigen levels was observed.Ranges for the concentration of PS:Ca(II)Ag and PS:NonCa(II)Ag and their ratio were established in plasma of healthy individuals (0.92 ± 0.13 U/ml, 0.98 ± 0.21 U/ml, 0.96 ± 0.17, respectively). In a group of patients using oral anticoagulant therapy the ratio PS:Ca(II) Ag/PS : NonCa(II)Ag decreased at increasing intensity of anticoagulation suggesting the presence of sub- and noncarboxylated protein S molecules.In plasma of patients with a hereditary type I protein S deficiency PS:Ca(II)Ag and PS:NonCa(II) Ag were reduced to the same extent: mean ratio 1.02 ± 0.12 in the group not on oral anticoagulant treatment and 0.94 ± 0.10 in the group on oral anticoagulant therapy. Analysis of patients with a history of unexplained thrombo-embolic disease did not reveal individual patients with a PS:Ca(II)Ag/PS:NonCa(II)Ag ratio below the lower limit of the normal range (mean ratio 1.05 ± 0.17), suggesting that the frequency of genetic protein S variants with defects in the Ca(II)-stabilized conformation is very low.

Rapid and sensitive chemiluminescent enzyme immunoassay for measuring tumor markers

1991 ◽  
Vol 37 (9) ◽  
pp. 1639-1644 ◽  
Author(s):  
I Nishizono ◽  
S Iida ◽  
N Suzuki ◽  
H Kawada ◽  
H Murakami ◽  
...  
Keyword(s):  
Alkaline Phosphatase ◽  
Carcinoembryonic Antigen ◽  
Enzyme Immunoassay ◽  
Tumor Markers ◽  
Lower Limit ◽  
Limit Of Detection ◽  
Solid Phase ◽  
Serum Samples ◽  
Coated Particles ◽  
Chemiluminescent Enzyme Immunoassay

Abstract We developed a chemiluminescent enzyme immunoassay (CLEIA) to quantify such tumor markers as carcinoembryonic antigen (CEA), alpha-fetoprotein (AFP), CA19-9, and CA125. We used a novel chemiluminescent substrate, a derivative of 1,2-dioxetane phosphate (AMPPD), to measure alkaline phosphatase as a labeling enzyme to Fab' fragments of antibody. Regardless of the solid phase, i.e., polystyrene beads (6 mm diameter) or ferrite-coated particles (0.3 microns diameter), the standard curves within the dynamic ranges of the conventional RIA or enzyme immunoassay (EIA) were linear in all cases except for those with AFP. Use of the ferrite particles further shortens the immunoreaction, so the assay can be performed in 30 min. In addition, the relationships between concentrations of the marker and chemiluminescent signals for CA19-9, CA125, and CEA were linear up to concentrations about 10-fold greater than the ordinary dynamic ranges. Intra- and interassay CVs (averages for individual analyte) were 2.2%-4.9% and 2.0%-5.8%, respectively. In an analysis of serum samples, results of the CLEIA correlated reasonably well with those of RIA or EIA. The lower limit of detection by CLEIA with ferrite particles was 390 arb. units/L for CA19-9, 990 arb. units/L for CA125, 0.06 micrograms/L for CEA, and 0.03 micrograms/L for AFP. Thus, the sensitivity increased to between two- and 10-fold that of RIA or colorimetric EIA, depending on the analytes.

Calcium/Copper alginate framework doped with CuO nano-particles as a novel adsorbent for micro-extraction of benzodiazepines from human serum

2020 ◽  
Vol 16 ◽  
Author(s):  
Nadereh Rahbar ◽  
Fatemeh Ahmadi ◽  
Zahra Ramezani ◽  
Masoumeh Nourani
Keyword(s):  
Human Serum ◽  
High Performance ◽  
Limit Of Detection ◽  
Solid Phase ◽  
Nano Particles ◽  
Limit Of Quantification ◽  
Analytical Methodology ◽  
Fiber Fabrication ◽  
Relative Standard ◽  
Green Procedure

Background: Sample preparation is one of the most challenging phases in pharmaceutical analysis, especially in biological matrices, affecting the whole analytical methodology. Objective: In this study, a new Ca(II)/Cu(II)/alginate/CuO nanoparticles hydrogel fiber (CCACHF) was synthesized through a simple, green procedure and applied for fiber micro solid phase extraction (FMSPE) of diazepam (DIZ) and oxazepam (OXZ) as model drugs prior to high-performance liquid chromatography-UV detection (HPLC-UV). Methods: Composition and morphology of the prepared fiber were characterized and the effect of main parameters on the fiber fabrication and extraction efficiency have been studied and optimized. Results: In optimal conditions, calibration curves were linear ranging between 0.1–500 µg L−1 with regression coefficients of 0.9938 and 0.9968. Limit of detection (LOD) (S/N=3) and limit of quantification (LOQ) (S/N=10) of the technique for DIZ and OXZ were 0.03 to 0.1 µg L−1. Within-day and between-day relative standard deviations (RSDs) for DIZ and OXZ were 6.0–12.5% and 3.3–9.4%, respectively. Conclusion: The fabricated adsorbent has been substantially employed to extraction of selected benzo-diazepines (BZDs) from human serum real specimens and the obtained recoveries were also satisfactory (82.1-109.7%).

Eco-Friendly Green Liquid Chromatographic Separations of a Novel Combination of Azelastine and Fluticasone in the Presence of their Pharmaceutical Dosage form Additives

2020 ◽  
Vol 16 (3) ◽  
pp. 277-286
Author(s):  
Amal A. El-Masry ◽  
Mohammed E. A. Hammouda ◽  
Dalia R. El-Wasseef ◽  
Saadia M. El-Ashry
Keyword(s):  
Lower Limit ◽  
Dosage Form ◽  
Limit Of Detection ◽  
Sodium Dodecyl ◽  
Uv Detection ◽  
Simultaneous Estimation ◽  
Limit Of Quantification ◽  
Chromatographic Separations ◽  
Pharmaceutical Dosage Form ◽  
Liquid Chromatographic

Background: The first highly sensitive, rapid and specific green microemulsion liquid chromatographic (MELC) method was established for the simultaneous estimation of fluticasone propionate (FLU) and azelastine HCl (AZL) in the presence of their pharmaceutical dosage form additives (phenylethyl alcohol (PEA) and benzalkonium chloride (BNZ)). Methods: The separation was performed on a C18 column using (o/w) microemulsion as a mobile phase which contains 0.2 M sodium dodecyl sulphate (SDS) as surfactant, 10% butanol as cosurfactant, 1% n-octanol as internal phase and 0.3% triethylamine (TEA) adjusted at pH 6 by 0.02 M phosphoric acid; with UV detection at 220 nm and programmed with flow rate of 1 mL/min. Results: The validation characteristics e.g. linearity, lower limit of quantification (LOQ), lower limit of detection (LOD), accuracy, precision, robustness and specificity were investigated. The proposed method showed linearity over the concentration range of (0.5-25 µg/mL) and (0.1-25 µg/mL) for FLU and AZL, respectively. Besides that, the method was adopted in a short chromatographic run with satisfactory resolution factors of (2.39, 3.78 and 6.74 between PEA/FLU, FLU/AZL and AZL/BNZ), respectively. The performed method was efficiently applied to pharmaceutical nasal spray with (mean recoveries ± SD) (99.80 ± 0.97) and (100.26 ± 0.96) for FLU and AZL, respectively. Conclusion: The suggested method was based on simultaneous determination of FLU and AZL in the presence of PEA and BNZ in pure form, laboratory synthetic mixture and its combined pharmaceutical dosage form using green MELC technique with UV detection. The proposed method appeared to be superior to the reported ones of being more sensitive and specific, as well as the separation was achieved with good performance in a relatively short analysis time (less than 7.5 min). Highly acceptable values of LOD and % RSD make this method superior to be used in quality control laboratories with of HPLC technique.

scholarly journals Graphite Studded with Facile-Synthesized Cu2O Nanoparticle-Based Cubes as a Novel Electrochemical Sensor for Highly Sensitive Voltametric Determination of Mebeverine Hydrochloride

Chemosensors ◽  
2021 ◽  
Vol 9 (2) ◽  
pp. 35
Author(s):  
Ahmed H. Naggar ◽  
Ahmed Kotb ◽  
Ahmed A. Gahlan ◽  
Mahmoud H. Mahross ◽  
Abd El-Aziz Y. El-Sayed ◽  
...  
Keyword(s):  
Electron Microscope ◽  
Lower Limit ◽  
Electrochemical Behavior ◽  
Cuprous Oxide ◽  
Density Functional ◽  
Limit Of Detection ◽  
Biological Fluids ◽  
Chemical Reduction ◽  
Anodic Stripping Voltammetry ◽  
Mebeverine Hydrochloride

Herein, a feasible chemical reduction method followed by intensive mixing was applied for the preparation of an attractive material based on graphite studded with cuprous oxide nanoparticle-based cubes (Cu2ONPs–C@G). Transmission electron microscope (TEM), scanning electron microscope (SEM), X-ray diffraction (XRD) and cyclic voltammetry (CV) were utilized for characterization. Cuprous oxide nanoparticles (Cu2ONPs), with a diameter range mainly distributed from 4 to 20 nm, aggregate to form microcubes (Cu2ONPs–C) with an average diameter of about 367 nm. Paste electrode was prepared using Cu2ONPs–C@G (Cu2ONPs–C@G/PE) for voltametric quantification of the musculotropic antispasmodic drug: mebeverine hydrochloride (MEB). The electrochemical behavior of MEB was studied using CV, and the optimum analytical parameters were investigated using square wave adsorptive anodic stripping voltammetry (SWAdASV). Moreover, density functional theory (DFT) was used to emphasize the ability of MEB to form a complex with Cu2+, confirming the suggested electrochemical behavior of MEB at Cu2ONPs–C@G/PE. With good stability and high reproducibility, SWAdASV of Cu2ONPs–C@G/PE shows successful quantification of MEB over the concentration range of 5.00 × 10−11–1.10 × 10−9 M with lower limit of detection (LOD) and lower limit of quantification (LOQ) values of 2.41 × 10−11 M and 8.05 × 10−11 M, respectively. Finally, accurate quantification of MEB in dosage forms (tablets) and biological fluids (spiked human urine and plasma samples) was achieved using Cu2ONPs-C@G/PE.

scholarly journals Application of an LC–MS/MS Method for the Simultaneous Quantification of Homovanillic Acid and Vanillylmandelic Acid for the Diagnosis and Follow-Up of Neuroblastoma in 357 Patients

Molecules ◽  
2021 ◽  
Vol 26 (11) ◽  
pp. 3470
Author(s):  
Narae Hwang ◽  
Eunbin Chong ◽  
Hyeonju Oh ◽  
Hee Won Cho ◽  
Ji Won Lee ◽  
...  
Keyword(s):  
Lower Limit ◽  
Large Scale ◽  
Homovanillic Acid ◽  
Limit Of Detection ◽  
Method Comparison ◽  
Vanillylmandelic Acid ◽  
Limit Of Quantification ◽  
Spot Urine ◽  
Minimal Sample ◽  
Clinical Biomarkers

Homovanillic acid (HVA) and vanillylmandelic acid (VMA) are end-stage metabolites of catecholamine and are clinical biomarkers for the diagnosis of neuroblastoma. For the first time in Korea, we implemented and validated a liquid chromatography tandem mass spectrometry (LC–MS/MS) assay to measure urinary concentrations of HVA and VMA according to Clinical and Laboratory Standards Institute guidelines. Our LC–MS/MS assay with minimal sample preparation was validated for linearity, lower limit of detection (LOD), lower limit of quantification (LLOQ), precision, accuracy, extraction recovery, carryover, matrix effect, and method comparison. A total of 1209 measurements was performed to measure HVA and VMA in spot urine between October 2019 and September 2020. The relationship between the two urinary markers, HVA and VMA, was analyzed and exhibited high agreement (89.1% agreement, kappa’s k = 0.6) and a strong correlation (Pearson’s r = 0.73). To our knowledge, this is the first study to utilize LC–MS/MS for simultaneous quantitation of spot urinary HVA and VMA and analyze the clinical application of both markers on a large scale for neuroblastoma patients.

Photon-counting microcolorimeter with 40-nl cuvette

1991 ◽  
Vol 261 (1) ◽  
pp. F203-F206
Author(s):  
T. L. Pallone
Keyword(s):  
Lower Limit ◽  
Plasma Volume ◽  
Fiber Optic ◽  
Limit Of Detection ◽  
Photon Counting ◽  
Injection Port ◽  
Photon Counter ◽  
Sample Injection ◽  
Lowry Assay

A colorimeter with a 40-nl cuvette has been constructed. The wall of standard capillary glass was perforated to produce a sample injection port. A section of the capillary glass was drawn to a length of 1/2 cm and 80 microns ID by heating on a microforge. This produced a cuvette volume of approximately 40 nl. Two fiber-optic filaments, 80 microns in diameter, were fixed into the cuvette to transmit and receive light from the sample. The output of the colorimeter was measured with a microscope photon-counting detection assembly. It has been shown that the colorimeter enables a reduction of the plasma volume requirements of the Lowry microprotein assay from several nanoliters to 60 pl. The linearity and reproducibility of the microcolorimeter when used with the Lowry assay has been verified. The colorimeter output is several orders of magnitude above the lower limit of detection of the photon counter.

Two Enzyme Immunoassays to Screen for 2,4-Dichlorophenoxyacetic Acid in Water

1987 ◽  
Vol 70 (5) ◽  
pp. 874-878 ◽  
Author(s):  
James Fleeker
Keyword(s):  
Limit Of Detection ◽  
Solid Phase ◽  
Dichlorophenoxyacetic Acid ◽  
Carrier Protein ◽  
Similar Response ◽  
Enzyme Immunoassays ◽  
Concentration Step ◽  
Chlorophenoxyacetic Acid ◽  
Phenoxy Herbicides ◽  
2,4 Dichlorophenoxyacetic Acid

Abstract Two solid-phase enzyme immunoassays were developed to measure 2,4-dichlorophenoxyacetic acid (2,4-D), using 2 sets of structurally distinct immunogens and enzyme ligands. The 2,4-D analog, 2-methyl- 4-chlorophenoxyacetic acid (MCPA), gave a similar response with both methods, whereas other phenoxy herbicides cross-reacted differently. In method A, the aromatic moiety of 2,4-D was distal from the carrier protein and labeled enzyme, whereas in method B, the acetic acid portion of the herbicide was distal. The use of both methods to screen for this herbicide in ground water and municipal and river water reduced the number of false-positive responses. Water sources having a low background response could be monitored with either method alone. When a concentration step, with disposable C18 extraction columns, was used, the limit of sensitivity was 5 ng/L,. Method A was the more sensitive of the 2 methods with a limit of detection of 10 j*g/L without the concentration step

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