Dispersive micro-solid phase extraction (D-µSPE) of nickel on activated nanodiamonds@Bi2WO6 nanocomposite from water and food samples.

This study presents an original nano-sorbent using activated nanodiamonds@Bi2WO6 to separate and enrich nickel ions from water and food samples. FTIR, XRD, FE-SEM, FE-SEM-EDX, EDS-TEAM, TGA, and BET were used to characterize the nanocomposite. It has a large surface area, active functional groups, and better reactivity. Ni(II) ions were determined as Ni(II)-PADAP chelates using UV-VIS spectroscopy. The parameters were studied and optimized, including pH (6), eluent type and volume (1 mL), ligand quantity (10 µg), sorbent dosage (20 mg), and contact time (1 min). The method has a low limit of detection (LOD) of 1.6 µg L-1, a limit of quantification (LOQ) of 5.3 µg L-1, a relative standard deviation of 4.5%, and a preconcentration factor of 10. The method was validated by applying to certified reference materials (BCR estuarine water 505 and 1573a NIST). The method was successfully applied to tap waters, industrial waste waters, and vegetables.

Carboxylated nanodiamonds@CuAl2O4@TiO2 nanocomposite for the dispersive micro-solid phase extraction of nickel at trace levels from food samples.

Heavy metal pollution poses a significant health risk, necessitating regular environmental monitoring for public safety. Elevated nickel concentrations can disrupt ecosystems and impact human health. This study presents a nano-sorbent can be used for dispersive micro-solid phase extraction of nickel. The nano-sorbent was characterized using FT-IR, XRD, FESEM, BET, and BJH. It demonstrated remarkable efficiency due to its nanoscale properties, optimizing results in exceptional extraction performance with minimal interference from common ions. A flame atomic absorption spectrometer was utilized for all measurements. It has a low LOD (0.29 µg L-1) and RSDs% (7.3 % and 6 % intra-day and inter-day, respectively), minimal variation, and a precisely accurate correlation (0.997). It can be used on black tea, green tea, carrots, coffee beans, tuna fish, herring fish, tobacco, soil, natural water, and wastewater samples. The accuracy of the method was assessed by analyzing TMDA-64.3 fortified water and NIST 1573a tomato leaves certified reference materials.

Micro solid phase extraction of lead and cadmium using functionalized nanodiamonds@CuAl2O4@HKUST-1 nanocomposite for FAAS analysis in food and water samples.

This study focuses on the development and application of a novel nanocomposite (functionalized nanodiamonds@CuAl2O4@HKUST-1)-based µ-SPE method for the sensitive and selective extraction of Pb and Cd from food and water samples. The technique offers high sensitivity and selectivity, allowing accurate measurement of these metals at trace levels. The detection limit is 0.031 µg kg-1 for Cd and 0.052 µg kg-1 for Pb, with a relative standard deviation of 1.7 % for Cd and 4.8 % for Pb. The method was successfully applied to real samples and efficiently quantified Pb and Cd in food and natural water samples. The highest concentrations were found in red lentils (0.274 µg kg-1 Pb) and fresh mint (0.197 µg kg-1Cd), but still below recommended limits set by FAO/WHO (300 µg kg-1 for Pb and 200 µg kg-1 for Cd). It promises to ensure food safety, monitor environmental contamination, and informs regulatory decisions to protect public health.

Fe3O4-SiO2-MIL-53 (Fe) nanocomposite for magnetic dispersive micro-solid phase extraction of cadmium (II) at trace levels prior to HR-CS-FAAS detection.

A magnetic metal-organic framework Fe3O4-SiO2-MIL-53 (Fe) nanocomposite was synthesized for magnetic dispersion micro-solid phase extraction (M-d-µSPE) of cadmium in water, spice, chocolate, tea, and tobacco samples prior to the detection by flame atomic absorption spectrometry. Fe3O4-SiO2-MIL-53 (Fe) nanocomposite fabricated using the solvothermal technique was characterized using a field emission scanning electron microscope and X-ray diffraction. The extraction efficiency of the method was improved by optimizing the experimental factors. After optimization, the linearity range for Cd (II) was 4.3-500 µgL-1. The limits of detection and quantification were 1.3 and 4.3 µgL-1, respectively. The presented magnetic dispersion-micro solid phase extraction method was applied to Cd (II) analysis in food and some environmental samples.

An electrochemical sensing platform with a molecularly imprinted polymer based on chitosan-stabilized metal@metal-organic frameworks for topotecan detection.

The present study aims to develop an electroanalytical method to determine one of the most significant antineoplastic agents, topotecan (TPT), using a novel and selective molecular imprinted polymer (MIP) method for the first time. The MIP was synthesized using the electropolymerization method using TPT as a template molecule and pyrrole (Pyr) as the functional monomer on a metal-organic framework decorated with chitosan-stabilized gold nanoparticles (Au-CH@MOF-5). The materials' morphological and physical characteristics were characterized using various physical techniques. The analytical characteristics of the obtained sensors were examined by cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS), and differential pulse voltammetry (DPV). After all characterizations and optimizing the experimental conditions, MIP-Au-CH@MOF-5 and NIP-Au-CH@MOF-5 were evaluated on the glassy carbon electrode (GCE). MIP-Au-CH@MOF-5/GCE indicated a wide linear response of 0.4-70.0 nM and a low detection limit (LOD) of 0.298 nM. The developed sensor also showed excellent recovery in human plasma and nasal samples with recoveries of 94.41-106.16 % and 95.1-107.0 %, respectively, confirming its potential for future on-site monitoring of TPT in real samples. This methodology offers a different approach to electroanalytical procedures using MIP methods. Moreover, the high sensitivity and selectivity of the developed sensor were illustrated by the ability to recognize TPT over potentially interfering agents. Hence, it can be speculated that the fabricated MIP-Au-CH@MOF-5/GCE may be utilized in a multitude of areas, including public health and food quality.

Application of magnetic solid-phase extraction for sensitive determination of anticancer drugs in urine by means of diamino benzidine tetrachlorohydrate modified magnetic nanoparticles.

BACKGROUND: The analysis of drug active molecules and residues in the treatment of cancer is important for the sustainability of human life and therapeutic effects. For this purpose, a new magnetic sorbent was developed to use in solid phase extraction prior to conventional high-performance liquid chromatography (HPLC) analysis of Paclitaxel (PAC) and Gemcitabine (GEM) molecules. METHODS: In this study, a separation and pre-concentration approach based on magnetic solid phase extraction (MSPE) was proposed for PAC and GEM by means of using a newly synthesized magnetic sorbent. After the MSPE procedure, an HPLC system with a diode array detector (DAD) was used to analyze trace amounts of PAC and GEM anticarcinogenic drugs in urine samples. Surface modification of magnetic Fe3O4 nanoparticles was carried out by diaminobenzidinetetrachloro hydrate (DABTC) for the first time and a useful sorbent was obtained for MSPE experiments. RESULTS: In the proposed method, PAC and GEM molecules were retained on the c in the presence of a pH 5.0 medium and desorbed to 300 µL of acetonitrile: methyl alcohol (1:1) eluent phase before HPLC-DAD analysis. Under the optimized conditions, the limit of detection (LOD) values for PAC and GEM were 1.38 and 1.44 ng mL-1 while the enhancement factor for PAC and GEM were 139.5 and 145.3, respectively. The relative standard deviations (RSD %) for PAC and GEM were below 3.50% in inter-day repeated experiments by means of model solutions containing 100 ng mL-1 drug active ingredients. CONCLUSIONS: Synthesis and characterization of DABTC-Fe3O4 nanoparticles were performed using suitable methodologies. Optimization of MSPE was done step by step. And finally, the developed method was successfully applied to urine samples with quantitative recoveries in the range of 99.0% and 105.0%.

Innovative molecularly imprinted electrochemical sensor for the nanomolar detection of Tenofovir as an anti-HIV drug.

Tenofovir (TNF) is an antiviral medicine that is utilized to treat the human immunodeficiency virus (HIV). However, its level must be controlled in the human body and environment at the risk of causing kidney and liver problems. Therefore, determining TNF concentration in real samples with more advanced, inexpensive, and accurate sensing systems is essential. In this work, a novel electrochemical nanosensor for TNF determination based on molecularly imprinted polymer (MIP) on the screen-printed electrode modified with functionalized multi-walled carbon nanotubes, graphite carbon nitride, and platinum nanoparticles (MIP-Pt@g-C3N4/F-MWCNT/SPE) was constructed through the electro-polymerization approach. The molecularly imprinted polymers were prepared on the electrode surface with TNF as the template molecule and 2-aminophenol (2-AP) as the functional monomer. Moreover, factors that affect sensor response were optimized. Pt@g-C3N4/F-MWCNT nanocomposite had an excellent synergistic effect on MIP, allowing rapid and specific identification of the test substance. The results demonstrated that the electro-polymerization of 2-AP supplies large amounts of functional groups for the binding of the template molecules, which remarkably enhances the sensitivity and specific surface area of the MIP sensor. This surface enlargement increased the analyte accessibility to imprinted molecular cavities. Under optimum conditions, the oxidation peak current had a linear relationship with TNF concentration ranging from 0.005 to 0.69 µM with a low detection limit of 0.0030 µM (S/N = 3). The results demonstrated that the designed MIP sensor possesses acceptable sensitivity, repeatability, and reproducibility toward TNF determination. Moreover, the developed sensor was applied to biological and water samples to determine TNF, and satisfactory recovery results of 95.6-104.8% were obtained (RSD less than 10.0%). We confirm that combining as-synthesized nanocomposite Pt@g-C3N4/F-MWCNT with MIP improves the limitations of MIP-based nanosensors. The proposed electrode is also compatible with portable potentiostats, allowing on-site measurements and showing tremendous promise as a point-of-care (POC) diagnostic platform.

Sample Preparation Methods for Metal Containing Pesticides in Food and Environmental Samples.

Metal-containing pesticides are used in many areas for purposes such as harvest efficiency and keeping pests away from the vegetable environment. Metal-containing pesticides are in the form of dithiocarbamate complexes and are named differently according to the type of metal they contain and are used for different purposes. Since the presence of these pesticides even at residue level threatens human and environmental health, their determination at trace level is important. In this review, studies on the determination of metal-containing dithiocarbamate pesticides in different matrices are discussed. This review on the analysis of dithiocarbamate pesticides with different techniques will shed light on the studies to be carried out for the determination of these pesticides one by one in different matrices.

Vortex-assisted restricted access-based supramolecular solvent microextraction of trace Pb(II) ions with 4-(benzimidazolisonitrosoacetyl)biphenyl as a complexing agent before microsampling flame AAS analysis.

A new oxime compound, 4-(benzimidazolisonitrosoacetyl)biphenyl (BIBP) was synthesized and used as a complexing agent in this study to preconcentrate trace amounts of Pb(II) ions with vortex-assisted restricted access-based supramolecular solvent microextraction (RA/SUPRAS-LPME) method. The new complexing agent was characterized by a combination of elemental analyses, Proton Nuclear Magnetic Resonance (1H- NMR), Carbon-13 Nuclear Magnetic Resonance (13C NMR) and Fourier Transform Infrared spectroscopy (FT-IR) and techniques. Extraction of the complex which was formed at pH 8.0 was done by using a supramolecular solvent phase of tetrahydrofuran (THF) and 1-decanol. A microsampling flame atomic absorption spectrophotometer was used to measure the lead ion concentrations of the extract. The method optimized and the optimum experimental conditions were found as; pH = 8, amount of the ligand 2,25 mg, supramolecular solvent volume 50 µL, sample volume 20 mL and vortex time 3 min. The limit of detection (LOD), limit of quantification (LOQ) were calculated as 0.69 µg L-1 and 2.29 µg L-1, respectively. Linear range was found between 15.1 µg L-1 and 606 µg L-1. The developed method was applied to Pb(II) determination in real samples after evaluating the accuracy by using the TMDA-53.3 fortified environmental water sample as certified reference material.

Preconcentrations of Cu (II) and Mn (II) by magnetic solid-phase extraction on Bacillus cereus loaded γ-Fe2O3 nanomaterials.

For the simultaneous preconcentrations of Cu(II) and Mn(II), a novel preconcentration technique was developed and described. Bacillus cereus loaded magnetic É£-Fe2O3 nanoparticles were prepared and used as support materials on solid-phase extraction procedure. Important experimental parameters were investigated in details and pH 6.0, 3 mL min-1 of flow rate, 5 mL of 1 mol L-1 of HCl as eluent, 200 mg of biomass, and 200 mg of magnetic É£-Fe2O3 nanoparticles as support material was found as the best conditions. The preconcentrations factor were found to be 80 for Cu (II) and Mn(II). It was confirmed by the results that SPE columns could be used in 32 cycles. The LOD values calculated for Cu (II) and Mn (II) were 0.09 and 0.08 ng mL-1, respectively. The RSD values found were less than 3.4%. The extraction recoveries were achieved as higher than 98%. The biosorption capacities of Cu (II), and Mn (II) were 26.0 mg g-1, 30.3 mg g-1 respectively. The approach devised for analyzing analyte concentrations in food samples proved to be successful.

Advanced Methodologies for Trace Elements in Edible Oil Samples: A Review.

Advanced methodologies were applied for the detection of some elements at trace levels in edible oils. Trace elements play a role in oil stability, quality of edible oils and fats. In the present study, problems were addressed related to simple, cheap, less time consuming and suitable pretreatment advanced methods for suitable sample introduction and calibrations as well as the strategies and techniques are discussed. The present review is aimed to discuss the significance of simplifying sample treatments are offered for trace elements in oils. The period covered by this review is last twenty years. However, the various applications of advanced methodologies including extraction and microextraction. The scope of spectrometric techniques used for the analysis of trace elements in edible oils was discussed by new instrumental development trends.

Dual-response electrochemical electrode for sensitive monitoring of topotecan and mitomycin as anticancer drugs in real samples.

This research paper employed an innovative electrochemical electrode to simultaneously determine topotecan (TPT) and mitomycin (MMC) as anticancer agents. For this purpose, a novel nanocomposite was synthesized using a hydrothermal procedure. The nanocomposites were characterized using FTIR, STEM, FESEM, mapping analysis, EDX, and XRD methods. The novelty of this work is the successful synthesis of Fe3O4 decorated on the surface of CuCo2S4 (Fe3O4@CuCo2S4) nanocomposites showed two separate anodic peaks at 0.8 V for TPT and 1.0 V for MMC with potential separation of 0.2 V. This was enough for the simultaneous electrochemical determination of topotecan and mitomycin on a glassy carbon electrode (GCE), simultaneously. At optimized conditions, the developed electrode exhibited linear responses with TPT and MMC concentration in the ranges of 0.01-0.89 and 0.89-8.95 µM for topotecan and 0.1-19.53 µM for mitomycin. The detection limits were observed as 6.94 nM and 80.00 nM for topotecan and mitomycin, respectively. The fabricated Fe3O4@CuCo2S4/GCE showed high sensitivity, long-term stability, and repeatability towards the sensing of TPT and MMC simultaneously and can be utilized in real samples. The obtained results confirmed that the fabricated Fe3O4@CuCo2S4/GCE nanocomposites can be utilize in the simultaneous electrochemical determination of topotecan and mitomycin in real samples.

New Trend in the Extraction of Pesticides from the Environmental and Food Samples Applying Microextraction Based Green Chemistry Scenario: A Review.

This review focused on the green microextraction methods used for the extraction of pesticides from the environmental and food samples. Microextraction techniques have been explored and applied in various fields of analytical chemistry since its beginning, as evinced by the numerous reviews published. The success of any technique in science and technology is measured by the simplicity, environmentally friendly, and its applications; and the microextraction technique is highly successive. Deliberations were attentive to studies where efforts have been made to validate the methods through the inter-laboratory comparison study to assess the analytical performance of microextraction techniques against conventional methods. Succinctly, developed microextraction methods are shown to impart significant benefits over conventional techniques. Provided that the analytical community continues to put forward attention and resources into the growth and validation of the microextraction technique, a promising future for microextraction is forecasted.

Switchable-hydrophilicity solvent liquid-liquid microextraction prior to magnetic nanoparticle-based dispersive solid-phase microextraction for spectrophotometric determination of erythrosine in food and other samples.

A combination of switchable-hydrophilicity liquid-liquid microextraction prior to magnetic nanoparticle-based dispersive solid-phase microextraction is proposed for the determination of erythrosine using UV/Vis spectrophotometry at 520 nm. Under optimum conditions (i.e., 1.0 mL octylamine as the extraction solvent, 1.5 mL of 10.0 M sodium hydroxide as the phase separation trigger, pH 4.0, 750 µL of acetone as the eluent, 10.0 mg of Fe3O4@XAD-16 as the adsorbent, and 15.0 mL of the sample solution), the method showed a superior analytical performance with limits of detection less than 25.9 ng mL-1, limits of quantitation less than 86.3 ng mL-1 and linear dynamic ranges ranging between 86.3 and 1000 ng mL-1. Percentage relative standard deviations were less than 4.1 and 7.2% for intra-day and inter-day, respectively. The method was successfully applied for the extraction and determination of erythrosine in food samples and other consumer products with recoveries in the range of 94.6-103.9% and within extraction time of 7.8 min per sample.

Development of Armillae mellea immobilized nanodiamond for the preconcentrations of Cr(III), Hg(II) and Zn(II).

In this study, we present an environmental friend and easy procedure for simultaneous preconcentration of Cr(III), Hg(II) and Zn(II) by solid-phase extraction before their determination by inductively coupled plasma optical emission spectrometry. Armillae mellea immobilized nanodiamond was used as sorbent. During the study, critical parameters influencing the extraction performance were investigated in detail. The best parameters were found as pH 5.0, 2.0 mL min-1 of flow rate, 200 mg of Armillae mellea, 300 mL of sample volume. LOD values were found as 0.025, 0.13 and 0.038 ng mL-1, respectively for Cr(III), Hg(II) and Zn(II). By applying the developed procedure, sensitivities of ICP-OES were improved for 60 fold for Cr(III), Hg(II) and Zn(II). Their concentrations in different food samples were measured after microwave digestion and solid-phase extraction.

The Determination of Toxic Metals in some Traditional Cosmetic Products and Health Risk Assessment.

In present study, the levels of some toxic elements in 19 different home-made cosmetic products (spray hair dye, henna, tattoo, eyeliner, eye mascara, smear, lip moisturizer, and lipstick) were analyzed by inductively coupled plasma mass spectrometric (ICP-MS) after microwave digestion. The ICP-MS results were verified by the analyzing certificated reference material (EnviroMAT Drinking Water, High).The detection limit (LOD) was set from 0.1 to 0.2 and the quantification limit (LOQ) from 0.2 to 0.8 µg L-1 and the recoveries estimated from 99% to 109%. The relative standard deviation (RSD) (%) for elements was determined in the range of 0.9 and 2.1%. Although various concentrations of arsenic (As),cadmium (Cd), cobalt (Co), chromium (Cr), cupper (Cu), and nickel (Ni) were determined in some samples, lead (Pb) concentration was found in all the samples. Data obtained were compared with the permissible limit of cosmetic products by the WHO. The concentration of Pb in smear samples was higher than the permitted limit created by the WHO, and Ni concentration in the some samples exceeds the limit set by the WHO. The rank order of toxic elements based on THQ index was Cr > Pb > Ni. The potential non-carcinogenic was considerably lower than the safe risk limits (THQ > 1).

Nano-clay as a solid phase microextractor of copper, cadmium and lead for ultra-trace quantification by ICP-MS.

Heavy metal microextraction and determination in daily used water is accurately achieved by applying nano-clay as an extractor. The conditions for adsorption/elution of Cu(ii), Cd(ii) and Pb(ii) were investigated by adjusting the pH of samples, sample volume and the type of eluent. The nano-clay showed superior efficiency for microextraction of Cu(ii), Cd(ii) and Pb(ii) at pH 2 using 2 mL of nitric acid (1 M) as the eluent. The microextraction procedure showed high recovery% by changing the sample volume from 15 mL to 70 mL. The preconcentration factor was found to be 37.5. The LOD and LOQ were 1.8, 1.3, and 1.9 µg L-1 and 5.3, 3.9, and 5.7 µg L-1 for Cu(ii), Cd(ii) and Pb(ii) respectively. The addition/recovery from different water samples showed recovery% in the range 88-105 which confirms the efficiency and the accuracy of the developed solid phase microextraction using nano-clay for enrichment of Cu(ii), Cd(ii) and Pb(ii).

A new magnetized thermophilic bacteria to preconcentrate uranium and thorium from environmental samples through magnetic solid-phase extraction.

A magnetic solid-phase extraction (MSPE) method was developed for simultaneous preconcentrations of U(VI) and Th(IV) before their measurements by inductively coupled plasma optical emission spectrometry (ICP-OES). The main idea of this biotechnological application depends on the use of bacteria, thermophilic Bacillus cereus SO-14, as a solid-phase biosorbent. It was immobilized to γ-Fe2O3 magnetic nanoparticles and used for MSPE. Characterization of the biosorbent was performed using the scanning electron microscope (SEM), the energy dispersive X-ray (EDX) and Fourier transform infrared (FT-IR) spectroscopy. Also, the the best conditions of experimental parameters were examined, and the reliability of the method developed was verified by applying the certified reference materials. Limit of detections (LODs) of the U(VI) and Th(IV) was calculated as 0.008 and 0.013 ng mL-1 respectively. Relative standard deviations (RSDs) were found to be 1.6 and 2.4 %, respectively, for U(VI) and Th(IV). R2 was also calculated as 0.9991. Preconcentration factors were achieved as 100 for both elements. It should be highlighted that LODs were critically improved and the sensitivity of ICP-OES was enhanced.

A magnetized fungal solid-phase extractor for the preconcentrations of uranium(VI) and thorium(IV) before their quantitation by ICP-OES.

The fungus Bovista plumbea immobilized on γ-Fe2O3 nanoparticles is shown to be a novel sorbent for magnetic solid-phase extractions of U(VI) and Th(IV). The biosorbent was characterized by FT-IR, SEM, and EDX. The effects of pH value, flow rate and volume of sample, amounts of biomass and support material, eluent type, foreign ions and repeated use of the sorbent on extraction efficiency were investigated. The sorption capacities are 41 and 44 mg g-1, respectively, for U(VI) and Th(IV). The results indicated that B. plumbea immobilized onto γ-Fe2O3 nanoparticles can be utilized as a novel material for the preconcentrations of U(VI) and Th(IV) in certified materials and in spiked tap, river and lake waters. Graphical abstract Schematic presentation of a method for preconcentrations of Th(IV) and U(VI) ions using γ-Fe2O3 nanoparticles loaded with the fungus Bovista plumbea.

Trace elements in blood samples of smoker and nonsmoker active pulmonary tuberculosis patients from Jamshoro, Pakistan.

Pulmonary tuberculosis (PTB) is a serious public threat throughout the world. PTB and smoking have a strong correlation. Malnutrition, poverty, addiction, overcrowding, illiteracy, unemployment, and poor hygienic conditions are the collective aspects for the disease progress. Pakistan is the fifth among 22 high tuberculosis (TB) burden countries and the fourth regarding multidrug-resistant tuberculosis (MDR-TB). The aim of study was to determine the concentration of essential and toxic elements from blood samples of smoker and nonsmoker PTB patients by inductively coupled plasma mass spectrometry (ICP-MS) followed by microwave acid digestion and compared with control subjects (n = 30). Eighty PTB patients were selected from different hospitals with age ranging 20-70 years. It was interpreted that the mean age among males and females was found to be 35.6 ± 1.4 and 33.5 ± 1.2, respectively, and the male patients were highly affected in contrast to females. Essential elements such as Mn, Fe, Zn, and Se were statistically found to be lower while Ca, Co, and Cu were found to be higher compared to the control group (p = 0.00). However, toxic elements like Al, Cr, Ni, As, Cd, and Pb were statistically elevated in smokers than nonsmokers. Further research is needed to understand the degree of the impact of essential trace elements on treatment outcome (follow-up) followed by balanced healthy nutritional supplementation along with medical therapy, consequently improving the pulmonary tuberculosis outcome and survival as well.