Sensitive, reliable and simultaneous determination of Fingolimod and Citalopram drug molecules used in multiple sclerosis treatment based on magnetic solid phase extraction and HPLC-PDA.

An analytical methodology has been developed for trace amounts of Fingolimod (FIN) and Citalopram (CIT) drug molecules based on magnetic solid phase extraction (MSPE) and high performance liquid chromatographic determination with photodiode array detector (HPLC-DAD). Fingolimod is used in treatment of Multiple sclerosis (MS) disease and sometimes antidepressant drugs such as citalopram accompany to treatment. Both simultaneous analysis of these molecules and application of MSPE with a new adsorbent has been performed for first times. Fe3O4@L-Tyrosine magnetic particles has been synthetized and characterized as a new magnetic adsorbent. Experimental variables of MPSE were examined and optimized step by step such as pH, adsorption and desorption conditions, time effect, etc. Analytical parameters of the proposed method were studied and determined under optimized conditions according to international guidelines. HPLC analysis of FIN and CIT molecules was performed by isocratic elution of a mixture of 50 % Acetonitrile, 40 % pH:3 phosphate buffer and 10 % methanol with flow rate 1.0 mL min-1. The chosen wavelengths in PDA was determined as 238 nm for FIN and 213 nm for CIT. The limits of detection (LOD) for proposed method were 6.32 ng mL-1 for FIN and 6.85 ng mL-1 for CIT molecules. RSD % values were lower than 5.5 % in analysis of model solutions including 250 and 500 ng mL-1 of target molecules. Recovery values by means of synthetic urine and saliva samples were in the range of 95.7-105.4 % for both molecules.

Urgent first-step screening method for ketamine, phenobarbital, zopiclone, zolpidem, phenytoin and thiopental in adulterated soft drink.

Date-rape drugs given to victims through drinks without their knowledge in drug-facilitated sexual assaults and thefts (money, property and body organs), are important threats for the public. Detection in beverage residues gains importance, since some of them can be quickly eliminated from the body, till the victim understands what he/she has experienced, goes to the hospital and gives a urine sample for analysis. Here, date-rape drugs; ketamine, thiopental, phenobarbital, zolpidem, phenytoin and zopiclone were analyzed simultaneously in 1.00mL caffeine-based carbonated beverage residue, through direct injection, using a modified, economical emergency first-step screening method with high performance liquid chromatography-diode array detector (elution time: 11 minutes). Screening power of the method was qualitatively observed in sour cherry juice, sweet soda and beer with some additional experiments. Caffeine in caffeine-based carbonated beverage could also be detected simultaneously. LODs and LOQs were between 0.02-1.79 and 0.08-5.60µgmL-1. Repeatability and reproducibility values were <9.91%. HorRat values were between 0.184-0.500. As the first screening and quantitative study on the simultaneous analysis of these drugs in a beverage, it's important for solving the crimes committed using drugs in caffeine-based carbonated beverage residues found at the crime scene, when the use of these drugs is suspected after anamnesis and inspection.

An environment-friendly and rapid liquid-liquid microextraction based on new synthesized hydrophobic deep eutectic solvent for separation and preconcentration of erythrosine (E127) in biological and pharmaceutical samples.

In this study, a new deep eutectic solvent (DES) consist of tetrabuthylammonium bromide (TBABr) and 1-octanol at 1:2 M ratio was prepared for the first time and characterized by Fourier transform infrared spectroscopy (FT-IR), proton nuclear magnetic resonance (1H NMR) and carbon nuclear magnetic resonance (13C NMR) techniques. The new DES was used as an extraction solvent in the ultrasound assisted liquid-liquid microextraction (UA-LLME) of Erythrosine (E127) in blood, urine, pharmaceutical tablet and syrup samples. Accurate and sensitive determination of erythrosine was accomplished with the combination use of DES-UA-LLME and UV-Vis spectrophotometric detection. Before applying UA-LLME, while protein precipitation was applied to blood samples, pharmaceutical tablets were homogenized and dissolved in methanol. The proposed DES-UA-LLME/UV-VIS procedure was applied directly to urine, syrup sample and supernatant of blood and tablet samples with high recoveries in range of 90% and 100%. Erythrosine in the aqueous sample phase was extracted into 200 µL hydrophobic DES phase at pH 7.0. The effect of important analytical variables such as pH of sample solution, mol ratio of DES components, volume of DES, ultrasonic-based extraction time, sample volume and salt effect were optimized. The preconcentration factor (PF), limit of detection (LOD), intra-day and inter-day relative standard deviations (RSD, %) for the developed procedure were found as 40, 3.75 µg·L-1, 2.6% and 4.6%, respectively.

Green synthesis of magnetic carbon nanodot/graphene oxide hybrid material (Fe3O4@C-nanodot@GO) for magnetic solid phase extraction of ibuprofen in human blood samples prior to HPLC-DAD determination.

In this study, a green production method was used to obtain magnetic carbon nanodot/graphene oxide hybrid material (Fe3O4@C-nanodot@GO) for the magnetic solid phase extraction (MSPE) of ibuprofen (IBU) in human plasma prior to HPLC-DAD determination. For the first time in the literature, Fe3O4@C-nanodot@GO hybrid material was synthesized and used as an adsorbent. C-nanodots were produced from pasteurized cow milk by using a simple and cheap hydrothermal method. After production of the C-nanodots and GO, Fe3O4@C-nanodot@GO hybrid material was fabricated in green solvent medium by using an one-step hydrothermal method. The method was based on the simple separation, preconcentration and analysis of ibuprofen by using MSPE-HPLC-DAD combination. The concentration changes of ibuprofen in human bloods against time were successfully monitored by using this combined method. For this purpose, blood samples were taken from volunteers at certain intervals after the administration of a certain dose of ibuprofen, and the MSPE method was used to monitor the concentration changes of ibuprofen in the blood samples. Experimental variables affecting the extraction efficiency of IBU such as sample solution pH, amount of adsorbent, extraction time, eluent type and volume were studied and optimized in the details. The characterization studies for the Fe3O4@C-nanodot@GO were carried out by X-ray diffraction spectrometry (XRD), Fourier transform infrared spectrometry (FT-IR), Raman spectrometry (Raman), energy dispersive x-ray (EDX), vibrating sample magnetometry (VSM) and scanning electron microscopy (SEM) techniques. Under the optimum experimental conditions, the limit of detection (LOD) was 8.0 ng mL-1 and the recoveries at three spiked levels in human plasma were ranged from 91.0% to 95.0% with the relative standard deviation (RSD %) less than 4.0 % (n = 6). The results show that together use of MSPE with HPLC-DAD provides a simple and rapid analysis of ibuprofen in human plasma samples.

Assessment of perfluoroalkyl substances levels in tap and bottled water samples from Turkey.

Perfluoroalkyl and polyfluoroalkyl substances (PFASs) draw considerable attention for their potential toxic effects in humans and environment. Drinking water is accepted as one of the major exposure pathways for PFASs. In this study, we measured concentrations of 10 perfluoroalkyl substances in 94 tap water samples collected in two different sampling periods (August 2017 and February 2018) from 33 provinces of Turkey, as well as in 26 different brands of plastic and glass-bottled water samples sold in supermarkets in Turkey. Perfluorohexanoic acid (PFHxA), perfluorobutane sulfonate (PFBS) and perfluoropentanoic acid (PFPeA) were the most frequently detected PFASs in the samples of tap waters. The maximum concentrations in tap waters were measured as 2.90, 2.37, 2.18, 2.04, and 1.93 ng/L, for PFHxA, perfluorooctanoic acid (PFOA), perfluorohexane sulfonate (PFHxS), perfluorooctane sulfonate (PFOS), and perfluorobutanoic acid (PFBA), respectively. The most abundant perfluorinated chemical in tap water samples was PFBA with 17%, followed by PFOS (13%), PFBS (12%), perfluoroheptanoic acid (PFHpA) (11%), PFHxA (11%), and PFOA (11%). The total PFASs concentration in tap water ranged from 0.08 to 11.27 ng/L. As regards bottled waters, the concentrations of PFASs were generally lower than those in tap water samples. These results revealed that tap water samples in Turkey might be considered generally safe based on the established guidelines around the world. However, due to their persistence and potential to accumulate and reach higher concentrations in the environment, careful monitoring of PFASs in all types of water is critical.

Synthesis of gold and silver nanoparticles using flavonoid quercetin and their effects on lipopolysaccharide induced inflammatory response in microglial cells.

Quercetin is a plant origin phytochemical with several pharmaceutical activities such as antioxidant, immunomodulatory, and anti-inflammatory effects. However, consumption of quercetin is limited due to its low aqueous solubility and poor bioavailability. The aim of the present study was to synthesize silver and gold nanoparticles of quercetin with a view to improve its aqueous phase solubility and investigate the effects on LPS-induced neuroinflammation in BV-2 microglial cells. The average size of silver and gold-quercetin nanoparticles was 53 and 27 nm, respectively. Absorption peaks in the UV-Vis spectra were observed at 555 and 405 nm for gold and silver-quercetin nanoparticles, respectively. The particle size and mapping of silver and gold-quercetin nanoparticles were also determined using a STEM detector. The inflammatory stimulation of the BV-2 cells with LPS caused an elevated release of proinflammatory prostaglandin, E2, nitric oxide (NO), upregulated cyclooxygenase-2, inducible NO synthase mRNA, and protein levels, which were markedly inhibited by the pretreatment with gold-quercetin nanoparticles (highly soluble in water) without causing any cytotoxic effects. The findings of the present study suggest that the potential of gold-quercetin nanoparticles are much better than quercetin and that gold-quercetin nanoparticles might provide protection against inflammatory neurodegenerative disease via suppression of acute microglial activation.

Report: Fast chromatographic screening method for 7 drugs of potential threat in drug facilitated crimes.

In cases where pharmaceuticals and pharmaceutical candidates are involved in drug facilitated crimes (DFC), like organ theft, robbery, rape and suicides, the analysis of drug powders or solution residues found in crime scenes may give idea on what the victims have ingested. An easy and fast simultaneous determination of 7 drugs; GHB (γ-hydroxybutyrate), GBL (γ-butyrolactone), norketamine, ketamine, fenobarbital, fenitoin and thiopental which have the potential to be used in DFC was performed. The method required no sample preparation and has 12 minutes elution time with a good chromatographic separation. The separation was carried out on a C18 monolithic column with UV detection at 215 and 237nm. All r2 values were ≥0.99 and the linear ranges were between 0.9956-1.0000. The LOD and LOQ values were between 0.56-5.55µgmL-1 and 1.69-16.82µgmL-1 respectively. The repeatability values were <7.35%. This is the first study in the simultaneous screening of the above mentioned drugs using HPLC.

Simultaneous analysis method for GHB, ketamine, norketamine, phenobarbital, thiopental, zolpidem, zopiclone and phenytoin in urine, using C18 poroshell column.

Date-rape drugs have the potential to be used in drug-facilitated sexual assault, organ theft and property theft. Since they are colorless, tasteless and odorless, victims can drink without noticing, when added to the beverages. These drugs must be detected in time, before they are cleared up from the biofluids. A simultaneous extraction and determination method in urine for GHB, ketamine, norketamine, phenobarbital, thiopental, zolpidem, zopiclone and phenytoin (an anticonvulsant and antiepileptic drug) with LC-MS/MS was developed for the first time with analytically acceptable recoveries and validated. A 4 steps liquid-liquid extraction was applied, using only 1.000mL urine. A new age commercial C18 poroshell column with high column efficiency was used for LC-MS/MS analysis with a fast isocratic elution as 5.5min. A new MS transition were introduced for barbital. 222.7>179.8 with the effect of acetonitrile. Recoveries (%) were between 80.98-99.27 for all analytes, except for GHB which was 71.46. LOD and LOQ values were found in the ranges of 0.59-49.50 and 9.20-80.80ngmL(-1) for all the analytes (except for GHB:3.44 and 6.00µgmL(-1)). HorRat values calculated (between 0.25-1.21), revealed that the inter-day and interanalist precisions (RSD%≤14.54%) acceptable. The simultaneous extraction and determination of these 8 analytes in urine is challenging because of the difficulty arising from the different chemical properties of some. Since the procedure can extract drugs from a wide range of polarity and pKa, it increases the window of detection. Group representatives from barbiturates, z-drugs, ketamine, phenytoin and polar acidic drugs (GHB) have been successfully analyzed in this study with low detection limits. The method is important from the point of determining the combined or single use of these drugs in crimes and finding out the reasons of deaths related to these drugs.

Comparison of Column Solid-Phase Extraction Procedures for Spectrophotometric Determination of E129 (Allura Red) in Foodstuff, Pharmaceutical, and Energy Drink Samples.

Two novel spectrophotometric determination procedures based on retention of Allura Red onto Amberlite XAD-1180 and XAD-16 resins for its preconcentration, purification, and separation were developed. Analytical parameters of the methods including pH, eluent type, sample volume, and sample and eluent flow rates, were investigated and optimized. Interference effects of some cations, anions, and widely used food dyes were also investigated. Detection limits of the two methods were found to be 1.2 and 1.5 µg/L for XAD-1180 and XAD-16 columns, respectively, under optimum conditions. Linear calibration curve ranges of the methods were 0.4-8.0 and 0.5-6.0 µg/mL of Allura Red for XAD-1180 and XAD-16 resins, respectively. Preconcentration factors were found as 80 for both the XAD-1180 and XAD-16 columns using maximum sample volume and minimum eluent volume. RSDs of the methods were below 6% throughout all experiments. All absorbance measurements were performed at 506 nm. Validations of the methods were performed comparatively with determination of the Allura Red contents of some foodstuff, pharmaceutical, and energy drink samples. Allura Red concentrations in investigated solid and liquid samples ranged from 298 to 501 µg/g and 53.8 to 508 µg/mL, respectively. Satisfactory results were obtained from the real samples analysis. Allura Red contents of samples were determined to be highly similar using the two extraction methods. Comparisons of the methods were performed by analysis of Allura Red contents of the real samples. In addition to analytical parameters, adsorption isotherm studies were performed for the two kinds of Amberlite resins. It was observed that developed methods fit the linear form of the Freundlich adsorption isotherm model. All of the experimental results suggested that the developed SPE procedures are suitable for separation, preconcentration, and determination of Allura Red in solid and liquid matrixes.

Evaluation of trace heavy metal levels of some fish species sold at retail in Kayseri, Turkey.

Cd, Ni, Cr, Zn, Cu and Pb concentrations of muscle tissue of 61 fish samples belonging to six fish species (Sparus auratus, Pomatomus saltatrix, Sarda sarda, Engraulis encrasicholus, Sander lucioperca, Scomber scombrus) retailed in Kayseri, Turkey were determined by flame atomic absorption spectrometry after wet digestion. Cd concentrations of at least 31 fish samples (50.8%) and Pb concentrations of at least six fish samples (9.8%) exceeded the corresponding Turkish permissible limit of 0.05 and 0.2 mg kg(-1) respectively whereas Zn concentrations of 11 fish samples (18%) exceeded the Turkish Food Codex limits of 50 mg kg(-1) for Zn. Cu concentrations of all fish species analyzed (100%) were below the corresponding Turkish legislations of 20 mg kg(-1). No limits were established concerning Ni and Cr concentrations in fish by the Turkish governmental authorities.

Ligandless cloud point extraction of Cr(III), Pb(II), Cu(II), Ni(II), Bi(III), and Cd(II) ions in environmental samples with Tween 80 and flame atomic absorption spectrometric determination.

A cloud point extraction (CPE) procedure has been developed for the determination trace amounts of Cr(III), Pb(II), Cu(II), Ni(II), Bi(III), and Cd(II) ions by using flame atomic absorption spectrometry. The proposed cloud point extraction method was based on cloud point extraction of analyte metal ions without ligand using Tween 80 as surfactant. The surfactant-rich phase was dissolved with 1.0 mL 1.0 mol L(-1) HNO(3) in methanol to decrease the viscosity. The analytical parameters were investigated such as pH, surfactant concentration, incubation temperature, and sample volume, etc. Accuracy of method was checked analysis by reference material and spiked samples. Developed method was applied to several matrices such as water, food and pharmaceutical samples. The detection limits of proposed method were calculated 2.8, 7.2, 0.4, 1.1, 0.8 and 1.7 microg L(-1) for Cr(III), Pb(II), Cu(II), Ni(II), Bi(III), and Cd(II), respectively.

Coprecipitation of Ni(2+), Cd(2+) and Pb(2+) for preconcentration in environmental samples prior to flame atomic absorption spectrometric determinations.

A coprecipitation procedure has been presented prior to flame atomic absorption spectrometric determination of nickel, cadmium and lead ions in environmental samples. Analyte ions were coprecipitated by using copper hydroxide precipitate. The influences of some analytical parameters like amounts of copper, sample volume, etc., on the recoveries of the analytes were investigated. The interference of other ions was negligible. Under the optimized conditions, the detection limits (3 sigma, n=15) of lead(II), nickel(II) and cadmium(II) were 7.0, 3.0 and 2.0 microg/L, respectively. The proposed method has been successfully applied for the determination of traces of Ni, Cd and Pb in environmental samples like tap water.

A novel solid phase extraction procedure on Amberlite XAD-1180 for speciation of Cr(III), Cr(VI) and total chromium in environmental and pharmaceutical samples.

Due to the toxicity of chromium, species depend on their chemical properties and bioavailabilities, speciation of chromium is very important in environmental samples. A speciation procedure for chromium(III), chromium(VI) and total chromium in environmental samples is presented in this work, prior to flame atomic absorption spectrometric determination of chromium. The procedure is based on the adsorption of Cr(III)-diphenylcarbazone complex on Amberlite XAD-1180 resin. After oxidation of Cr(III), the developed solid phase extraction system was applied to determinate the total chromium. Cr(III) was calculated as the difference between the total Cr content and the Cr(VI) content. The analytical conditions for the quantitative recoveries of Cr(VI) on Amberlite XAD-1180 resin were investigated. The effects of some alkaline, earth alkaline, metal ions and also some anions were also examined. Preconcentration factor was found to be 75. The detection limits (LOD) based on three times sigma of the blank (N: 21) for Cr(VI) and total chromium were 7.7 and 8.6 microg/L, respectively. Satisfactory results for the analysis of total chromium in the stream sediment (GBW7310) certified reference material for the validation of the presented method was obtained. The procedure was applied to food, water and pharmaceutical samples successfully.

Trace metal levels and some chemical parameters in herby cheese collected from south eastern Anatolia-Turkey.

Due to the consumption of the herby cheese in south eastern Anatolia-Turkey is at high ratio, chemical parameters such as dry matter, pH, acidity, aCl, protein, fat and trace metal contents in 50 different herby cheeses produced at this region have been determined in the presented study. The content of lead, copper, cobalt, nickel, chromium, cadmium, and iron have been analyzed by flame atomic absorption spectrometer in air/acetylene flame after combination ash digestion method and wet digestion method. The mean concentration of lead, copper, cobalt, nickel, chromium and cadmium in our samples are higher than literature values except iron.

Heavy metal contents of the karasu creek sediments, Nigde, Turkey.

Heavy metal contamination in sediments of the Karasu spring was investigated in the presented study. In this respect, sediment samples were collected from contaminant sites along the spring starting from the spring water manifestation site, base of the Akkaya dam to the dam exit site. Heavy metal concentrations were determined by X-ray Fluorescence Spectrometer. Cobalt, copper, arsenic, tin, nickel, zinc, cadmium, lead, aluminum, iron, titan, chromium and manganese contents of the Karasu creek sediments are found as 18.30-69.00, 12.40-595.0 5.50-345.3, 5.80-15.1, 10.9-64.1, 28.90-103,300, 4.1-356.2, 7.70-37,840, 13,460-109,400, 11,740-62,900, 22.18-59.04, 41.70-369 and 12.09-3,480 mg/kg, respectively. Results indicate the presence of a contamination in the Karasu creek. All the metal concentrations were found to be exceeding their acceptable limit values. Eutrophication is developed in the Karasu creek and the Akkaya dam. It is thought that heavy metal accumulation in the creek is originated from discharge from mine quarries, industrial and domestic wastes. Protection zones should be defined and all necessary measures must be taken along the Karasu creek.

SP70-alpha-benzoin oxime chelating resin for preconcentration-separation of Pb(II), Cd(II), Co(II) and Cr(III) in environmental samples.

In the presented work, alpha-benzoin oxime immobilized SP70 chelating resin was synthesized for separation and preconcentration of Pb(II), Cd(II), Co(II) and Cr(III). The optimization procedure for analytical parameters including pH, eluent type, flow rate, etc. was examined in order to gain quantitative recoveries of analyte ions. The effects of foreign ions on the recoveries of studied metal ions were also investigated. The detection limits (3sigma) were found to be 16.0, 4.2, 1.3, 2.4microgL(-1) for Pb, Cd, Co and Cr, respectively. The preconcentration factor was 75 for Pb, 100 for Cd, Co and Cr. The optimized method was validated with certified reference materials and successfully applied to the waters, crops and pharmaceutical samples with good results (recoveries greater than 95%, R.S.D. lower than 10%).

Speciation of Cr(III) and Cr(VI) in environmental samples by solid phase extraction on Ambersorb 563 resin.

A simple and sensitive method for the speciation, separation and preconcentration of Cr(VI) and Cr(III) in natural water, soil and sediment samples was developed. Cr(VI) has been separated from Cr(III) and preconcentrated as Cr(III)-diphenylcarbazone complex by using Ambersorb 563 resin and determined by spectrophotometric method at 540 nm. Effect of analytical parameters such as sulfuric acid concentration, ligand volume, type of elution solution, sample volume, amount of resin and foreign ions were investigated. The presented procedure was successfully applied for the chromium speciation in various environmental samples with successfully results.

Factorial design in the optimization of preconcentration procedure for lead determination by FAAS.

The present paper proposes a preconcentration procedure for lead determination using flame atomic absorption spectrometry (FAAS). It is based on lead(II) ions extraction as brilliant cresyl blue (BCB) complex and its sorption onto Diaion HP-2MG, a methacrylic ester copolymer. The optimization step was carried out using factorial design and the variables studied were pH, shaking time and reagent concentration. In the established experimental conditions, lead can be determinate with a limit of detection of 3.7mugL(-1) lead (N = 20) and a relative standard deviation of 7% for a lead concentration of 100mugL(-1). The accuracy was confirmed by analysis of a certified reference material, the stream sediment furnished by National Research Centre for Certified Reference Materials (NRCCRM), China (GBW 07310). Effect of other ions in the procedure proposed was also studied. The method was applied for lead determination in real samples of water, tea, soil and dust. Tests of addition/recovery in the experiments for lead determination in water samples revealed that the proposed procedure could be applied satisfactorily for analysis of these samples.

Aluminium determination in environmental samples by graphite furnace atomic absorption spectrometry after solid phase extraction on Amberlite XAD-1180/pyrocatechol violet chelating resin.

A chelating resin, pyrocatechol violet (PV) immobilised on an Amberlite XAD-1180 support, was prepared and its use for the atomic absorption spectrometric determination of aluminium was investigated. The XAD-1180-PV resin was characterised by infrared spectrometry and thermal gravimetric analysis. The optimum pH value for quantitative sorption is 8-9, and desorption can be achieved by using 5.0-10.0ml of 2M HCl. The effects of diverse ions on the sorption and recovery of aluminium have been studied. The capacity of sorbent was 6.45+/-0.59mgg(-1) Al XAD-1180-PV. Recoveries for aluminium from water samples were in the range 95-105%. The accuracy of procedure was confirmed by aluminium determination in certified reference materials. The method developed was applied with varying results to the analysis of natural water, haemodialysis fluids and microwave digested red wine samples from Tokat City.

Comparison of sample preparation procedures for the determination of trace heavy metals in house dust, tobacco and tea samples by atomic absorption spectrometry.

The effect of wet ashing, dry ashing and microwave procedure for the determination of trace metal levels was investigated in house dust, tobacco and tea samples by atomic absorption spectrometry. The study of sample preparation procedures showed that the microwave method was the best. The recovery of trace metals was very good and precision and accuracy were compatible with standard reference material. The relative standard deviations for all measured metal concentrations were lower than 10%. The digestions of HNO3/H2SO4/HClO4 (4: 1: 1) mixture for house dust, HNO3/H2SO4/H2O2 (2: 2: 2) mixture for tea and HNO3/H2O2 (4: 2) mixture for tobacco were very efficient.