Nanoparticle Assisted Fabric Phase Sorptive Extraction for Azo Dye Determination in the Industrial Sewage.

Currently, one of the significant environmental problems is the presence of azo dye materials in water sources. In this study, for the first time, a fast and sensitive sample preparation approach using nanoparticle-assisted fabric phase sorptive extraction (NFPSE) followed by high-performance liquid chromatography was examined to remove some azo dyes such as methyl red and sunset yellow from aqueous solutions. Primarily, the significance of several parameters affecting NFPSE, such as fabric type, the kind of sorbent, the number of contacts with sol-gel and the time of contact, was investigated. In addition, experiments were performed to determine the effect of different adsorption parameters, such as sample volume, adsorption time, adsorbent value, desorption time, ionic strength and pH. It was found that the calibration curve was linear within two ranges of concentrations (0.05-0.1 and 0.5-15 ng/L for methyl red; 0.05-0.5 and 0.5-15 ng/L for sunset yellow) with correlation coefficients better than 0.9683. The limit of detection was 0.014 ng/L for methyl red and 0.015 ng/L for sunset yellow. Repeatability Relative Standard Deviation (RSD) with three replicated experiments was 1.5-10% for methyl red and 2.5-5.8% for sunset yellow. Relative recovery percentages of 88-96% for methyl red and 62-92% for sunset yellow were obtained in the samples. Moreover, the results have shown that acceptable accuracy, precision and linearity make the "fabric phase sorptive extraction" a proper method for the determination of dyes from industrial sewage samples.

A biosensor integrating the electrochemical and fluorescence strategies for detection of aflatoxin B1 based on a dual-functionalized platform.

BACKGROUND: Aflatoxin B1 (AFB1), is a potent hepatic carcinogen which causes cancer by inducing DNA changes in the liver cells. Variety of methods have been developed for detection of AFB1 which are based on single mode detection strategy. Fabrication of novel platform which are compatible for multimodal detection of AFB1 provide robust performance for reliable detection of AFB1. In this study, we aimed to develop a robust biosensing platform that combines electrochemical and fluorescence techniques for the sensitive and specific detection of Aflatoxin B1. RESULTS: The sensing platform includes the magnetic core-shell Fe3O4@AuNPs and zeolitic imidazolate framework-8 (ZIF-8). In electrochemical mode, the applied voltametric approach was used through functionalization of glassy carbon electrode and exhibited a linear range between 0.5 and 10000 pg mL-1 with LOD of 0.32 pg mL-1. Fluorescence analysis was based on the FRET on/off status of FAM-functionalized aptamer deposited on the same platform. The FAM emission recovered by the addition of AFB1 concentration in the range of 6-60 fg mL-1 with the LOD of 0.20 fg mL-1. The real sample analysis demonstrated satisfactory relative recoveries in the range of 92.81-105.32 % and 91.66-106.66 % using the electrochemical and fluorescence methods, respectively, and its reliability was confirmed by the HPLC technique. SIGNIFICANCE: The experimental results affirm that the proposed aptasensor serves as a sensitive, efficient, and precise platform for monitoring AFB1 in both electrochemical and fluorescence detection approaches. Proposed strategy showed efficient selectivity among different analytes and was reproducible. Furthermore, the applicability of biosensor was confirmed in food and biological samples.

Synthesis, characterization, and photocatalytic activities of green sol-gel ZnO nanoparticles using Abelmoschus esculentus and Salvia officinalis: A comparative study versus co-precipitation-synthesized nanoparticles.

Background: The development of green chemistry methods involving plant-based nanoparticle synthesis presents an affordable and eco-friendly approach for wastewater treatment and color removal. This study aimed to synthesize ZnO nanoparticles using the sol-gel method with Salvia officinalis and Abelmoschus esculentus plants, examining their photocatalytic efficiency for organic dye removal. Methods: To compare the properties of ZnO nanoparticles, another type of ZnO-NPs was synthesized using the co-precipitation method. The characterization of synthesized nanoparticles was performed using thermogravimetric analysis (TGA-DTG), X-ray diffraction (XRD), Dynamic Light Scattering (DLS), Zeta potential (ZP), field emission scanning electron microscopy (FE-SEM), Energy Dispersive X-ray (EDX), Fourier transform infrared spectroscopy (FTIR), and UV-Vis spectrophotometry. Results: Based on XRD results, the average crystalline size of nanoparticles was calculated using the Debye-Scherer equation for synthesized nanoparticles using the S. officinalis at 22.99 nm and for the A. esculentus at 29.79 nm, and for the co-precipitation method at 18.83 nm. The FE-SEM images showed spherical ZnO nanoparticles. Photocatalytic properties of ZnO-NPs were investigated for remove of methylene blue organic dye in the presence of UV light. The pH 10 was identified as the best pH, which had the highest percentage of color degradation. All three types of nanoparticles were tested by up to 360 min to optimize the dyeing time. For A. esculentus, the highest percentage of color removal occurred in the first 90 min (41.0 %), for S. officinalis nanoparticles between 75 and 90 min (86.9 %), and for chemically synthesized nanoparticles between 30 and 45 min (100 %). Conclusions: In conclusion, the best MB dye degradation capacity belonged to co-precipitation ZnO nanoparticles followed by S. officinalis and A. esculentus nanoparticles.

Paper-based colorimetric detection of COVID-19 using aptasenor based on biomimetic peroxidase like activity of ChF/ZnO/CNT nano-hybrid.

Corona Virus Disease 2019 (COVID-19) as the infectious disease caused the pandemic disease around the world through infection by SARS-CoV-2 virus. The common diagnosis approach is Quantitative RT-PCR (qRT-PCR) which is time consuming and labor intensive. In the present study a novel colorimetric aptasensor was developed based on intrinsic catalytic activity of chitosan film embedded with ZnO/CNT (ChF/ZnO/CNT) on 3,3',5,5'-tetramethylbenzidine (TMB) substrate. The main nanocomposite platform was constructed and functionalized with specific COVID-19 aptamer. The construction subjected with TMB substrate and H2O2 in the presence of different concentration of COVID-19 virus. Separation of aptamer after binding with virus particles declined the nanozyme activity. Upon addition of virus concentration, the peroxidase like activity of developed platform and colorimetric signals of oxidized TMB decreased gradually. Under optimal conditions the nanozyme could detect the virus in the linear range of 1-500 pg mL and LOD of 0.05 pg mL. Also, a paper-based platform was used for set up the strategy on applicable device. The paper-based strategy showed a linear range between 50 and 500 pg mL with LOD of 8 pg mL. The applied paper based colorimetric strategy showed reliable results for sensitive and selective detection of COVID-19 virus with the cost-effective approach.

Dynamic removal of Pb(II) by live Dunaliella salina: a competitive uptake and isotherm model study.

The main aim of this study is modeling of a continuous biosorption system for the removal of Pb(II) ions in the aqueous conditions using live Dunaliella salina microalgae. The live microalgae can grow in saline water and opens new opportunities in varying the amount and properties of biosorbent. The effects of five parameters, including pH, optical density of algae as a factor indicating the adsorbent dosage, injection time, contact time, and initial concentration of Pb(II), were optimized by means of response surface methodology (RSM) based on the central composite design (CCD). Dunaliella salina algae showed maximum Pb(II) biosorption with 96% efficiency. For the selective Pb(II) uptake in the presence of Cd(II) and Ni(II), binary and ternary systems of ions were chosen. The mutual effect of each heavy metal ion in all systems on the total uptake percentage was also examined. The ion selectivity was investigated in the presence of diverse heavy metal ions, and the Pb(II) uptake percentage was determined to be 80%. Both Langmuir and Freundlich isotherm models were suitable for describing multicomponent binary and ternary systems depending on the presence of competitive ions in the mixture. Main functional groups and surface properties of the Dunaliella salina were identified by Fourier transform infrared spectroscopy, scanning electron microscopy, and energy dispersive spectrometry. Hence, effective heavy metal ion uptake, simple design, and cost-effective cultivation confirmed live Dunaliella salina as suitable microalgae for purifying contaminated water in an economic and safe manner.

A robust electrochemical sensing platform for the detection of erlotinib based on nitrogen-doped graphene quantum dots/copper nanoparticles-polyaniline-graphene oxide nanohybrid.

Erlotinib is a potent and highly specific tyrosine kinase inhibitor with the hindering effects on the growth of cancer cells. An electrochemical sensor with the great sensitivity and selectivity was fabricated for determining erlotinib by using a graphite rod electrode modified by the nitrogen-doped graphene quantum dots (N-GQDs) and a ternary nanohybrid comprising copper nanoparticles, polyaniline, along with graphene oxide (N-GQDs/CuNPs-PANI@GO) for the first time. The establishment of PANI and CuNPs was done simultaneously on the GO surface by thein situoxidative polymerization method. The morphological characteristics and elemental structure of the synthesized nanoparticles were examined by some microscopy techniques and x-ray energy/diffraction methods. The fabricated sensor represented the electrocatalytic activity towards erlotinib with a linear detection range from 1.0 nM to 35.0µM, a detection limit of 0.712 nM, and a sensitivity of 1.3604µAµM-1. Moreover, the N-GQDs/CuNPs-PANI@GO sensor showed acceptable stability up to 30 d (94.82%), reproducibility (RSD values of 3.19% intraday and 3.52% interday), and repeatability (RSD value of 3.65%) as a novel and powerful electrochemical sensor. It was successfully applied to monitor erlotinib in the drug-injected aqueous solution, serum, and urine samples that proved the capability of the sensor for the erlotinib monitoring in the biological samples.

Multi-template molecularly imprinted polymer hybrid nanoparticles for selective analysis of nonsteroidal anti-inflammatory drugs and analgesics in biological and pharmaceutical samples.

The multi-template molecularly imprinted polymers reinforced with hybrid oxide nanoparticles were developed for the selective separation and determination of the trace level of naproxen (NPX), methocarbamol (MTH), and omeprazole (OMZ) simultaneously from biological and pharmaceutical samples. The polymers were constructed by magnetic core@shell molecularly imprinted polymer nanocomposite (Fe3O4/ZnO/CuO/MWCNT@MIP). An electrochemical sensor has been fabricated for this purpose. Fe3O4/ZnO/CuO/MWCNT nanocomposite was introduced to improve the electron transport capability and increase the sensor surface area, as well as enhance the electronic conductivity. The triple-template MIP-coated layer provides simultaneous selective identification of three analytes by using [Fe (CN)6]3-/4-as the redox probe. Electrochemical behavior of MTH, NPX, and OMZ on the modified electrode (Fe3O4/ZnO/CuO/MWCNT@MIP) by various techniques such as cyclic voltammetry, differential pulse voltammetry, and chronoamperometry was examined. The morphology of the modified and unmodified carbon paste electrodes was performed by scanning electron microscopy (SEM) and X-ray diffraction analysis (XRD). The average crystal size for fabricated nanoparticles obtained by calculating the X-ray diffraction technique was 17 nm in the Scherer method. The particle size which was determined by SEM was 48 nm. Some electrochemical parameters such as the diffusion coefficient and electron transfer coefficient were determined. The effect of many variables such as the pH and scan rate was also investigated. Under optimal conditions, the sensor is designed in the linear range 5.0 nM-100 µM and 5.0 nM-100 µM and 1.0 nM-130 µM with a detection limit of 1.5 nM, 1.0 nM, and 0.7 nM for measurement OMZ, NPX, and MTH, respectively. The relative standard deviation (RSD) of the five measurements was 1.21%, 2.23%, and 2.56% for NPX, MTH, and OMZ. Finally, the designed sensor was successfully used for simultaneous detection of target analytes in the real samples; tablets, water samples, and biological samples.

Determination of Phthalate Esters in Cosmetics and Baby Care Products by a Biosorbent Based on Lawsone Capped Chitosan and Followed by Liquid Chromatography.

This research presents a green synthetic pathway for the preparation of a new biosorbent and eco-friendly extraction process of three phthalate esters: dimethyl phthalate, di-butyl phthalate and benzyl butyl phthalate, from cosmetics and baby care products. Dispersive solid-phase extraction was used based on a new core-shell biomass/sorbent; chitosan-loaded lawsone. The proposed method provides fortunate trapping of phthalate esters in a one-step extraction. Under the optimized extraction conditions, the current work was presented low detection limits (0.03-0.15 ng. g-1), limits of quantification (0.1-0.5 ng·g-1) and reasonable linearity (0.1-10 000 ng. g-1). The applicability of the method was estimated by recovery experiments at different spiking levels (n = 5) for phthalate esters in the real samples.

Plant Extract and Herbal Products as Potential Source of Sorbent for Analytical Purpose: An Experimental Study of Morphine and Codeine Determination Using HPLC and LC-MSMS.

Solid-phase microextraction (SPME) is an analytical method for microextraction of analytes, in which the analytes bind to the sorbent on the surface of the SPME fiber. Many types of chemical agents are used as sorbent; however, many of these sorbents cause secondary contamination or are not cost-effective. Here, aqueous extract of Ferula gummosa was evaluated as potential source of sorbent for simultaneous microextraction of morphine and codeine. For this purpose, multiwalled carbon nanotubes were carboxylated with H2SO4/HNO3 (3:1) and then functionalized with aqueous extract of F. gummosa. Functionalization was confirmed by Fourier transform infrared and Raman spectroscopy measurements as well as scanning electron microscopy analysis. Porous polypropylene hollow fibers were filled with the functionalized carbon nanotubes (CNTs) and used for analyte extraction in urine sample at 40°C and pH 6 for 2 min. Reversed-phase high-performance liquid chromatography (RP-HPLC) and liquid chromatography-tandem mass spectrometry (LC-MS/MS) analysis showed that the fiber could preconcentrate 1 ng/mL of morphine and 0.75 ng/mL codeine in urine sample and was successfully used for 30 times with no significant loss in the extraction efficiency. Limit of detection (LOD) and limit of quantification (LOQ) for morphine were 1 and 3.3 ng/mL, respectively. LOD and LOQ for codeine were determined 0.75 and 2.47 ng/mL, respectively. Recovery of the fiber was 80% and 93% for morphine and codeine, respectively. SPME fiber using extract of F. gummosa plant was used for the detection of a small amount of morphine in urine sample. Therefore, plants can be considered as abundant and cheap sources of sorbent for various analytical purposes.

Graphene oxide/ layered double hydroxides@ sulfonated polyaniline: A sorbent for ultrasonic assisted dispersive solid phase extraction of phthalates in distilled herbal beverages.

In this study, the ultrasonic-assisted dispersive solid phase extraction (UA-d-SPE) method coupled to gas chromatography-mass spectrometry (GC-MS) was applied for the analysis of phthalate esters in drinking water and distilled herbal beverages (Rosa, Mentha, Cichorium). A new nanocomposite based on layered double hydroxide supported on graphene oxide was synthesized and modified by sulfonated polyaniline via a simple one-pot in-situ polymerization method. The structure and morphology of the nanocomposite was confirmed by means of complementary techniques: Fourier transform infrared spectroscopy, X-ray diffraction, scanning electron microscopy, energy dispersive X-ray spectroscopy, and transmission electron microscopy. The effects of key parameters including adsorbent mass, type and amount of back extraction solvent, extraction and desorption time, pH of the solution and ionic strength were optimized and good precision and sensitivity were achieved. Under the optimum conditions, the limits of detection were between 0.06-0.3 ng mL-1 in aqueous solutions. The hybrid nanomaterial exhibited good adsorption ability toward phthalates in drinking water and distilled herbal beverages. The relative standard deviations (RSD%) for beverage samples varied from 0.1% to 9.9% (n = 3). The relative recoveries varied from 54.5% to 112.6%.

Migration of dihydroxyalkylamines from polypropylene coffee capsules to Tenax® and coffee by salt-assisted liquid-liquid extraction and liquid chromatography-mass spectrometry.

Migration of N,N-Bis(2-hydroxyethyl) alkyl(C8-C18)amines from five different polypropylene capsules to Tenax® and coffee powder have been studied. A single step extraction-cleanup procedure using salting out liquid-liquid extraction (SALLE) method followed by ultra-high performance liquid chromatography-tandem mass spectrometry (UHPLC-MS/MS) was applied. The critical parameters on the SALLE procedure such as extracting solvent, extracting volume, sample pH, salt and its concentration were optimized. The recovery values were in the range of 87.5%-106.5%. The %RSD were lower than 3.7%. The limit of detection was improved from 2.3 ng/g in Tenax® to 0.8 ng/g in coffee. The results indicated that the analyzed compounds have the potential to migrate from the polypropylene capsule containers to the coffee. In most of the cases, the migrated values were higher in Tenax® than in coffee in a range between 1.8 and 61%. One sample did not comply with the specific migration limit established by the European Commission.

Innovative method for analysis of safranal under static and dynamic conditions through combination of HS-SPME-GC technique with mathematical modelling.

INTRODUCTION: Saffron (Crocus sativus L.) is a well-known spice which is used as the colourant and flavouring agent in food products. Safranal could act as an indicator for saffron grading, authentication and adulteration, as well as for quality evaluation of saffron flavoured products; since it is the main odourant and the most aroma-active compound of saffron. OBJECTIVES: Firstly, determination of the optimum static conditions for safranal extraction through headspace solid-phase micro-extraction combined with gas chromatography (HS-SPME-GC) technique. Secondly, safranal measurement in different saffron flavoured products under the optimised static conditions. Thirdly, elucidation of the method efficiency for safranal measurement under non-equilibrium conditions for a saffron drink sample. METHODS: Different equilibrium times, pH and salt concentrations were applied on aqueous solutions of safranal. Accordingly, the optimised static conditions were determined for safranal extraction through HS-SPME-GC approach using polydimethylsiloxane (PDMS) fibre. RESULTS: Under static conditions, a linear response was obtained for standard curve within the safranal concentration range of 0.08-30 ppm, with R2 = 0.9999. The limits of detection and quantification were 0.04 and 0.08 ppm, respectively. Despite the fact that safranal peak area was an efficient parameter for quantifications under static conditions; its poor reproducibility was proved under dynamic conditions for the saffron drink sample. This observation necessitated application of kinetic studies on real food samples. CONCLUSIONS: Safranal extraction was successfully performed from aqueous matrices through HS-SPME-GC, under static conditions. Mathematical modelling resulted in kinetic parameters that improved the efficiency of safranal measurement under dynamic conditions, using PDMS fibre.

Adsorptive removal of endocrine disrupting compounds from aqueous solutions using magnetic multi-wall carbon nanotubes modified with chitosan biopolymer based on response surface methodology: Functionalization, kinetics, and isotherms studies.

Recently, the presence of endocrine disrupting compounds in the environment has emerged as a global and ubiquitous problem. In this study, a novel synthesis of magnetically carbon nanotube modified with biological polymeric was successfully prepared. The effect of different parameters on the Bisphenol A (BPA) adsorption was studied. A prediction model for BPA adsorption was extended based on the Central Composite Design. Also, the prepared biopolymeric nanotubes were characterized by FT-IR, XRD, TEM, FE-SEM. The surface morphology of nanocomposite was observed, increased carbon nano tube size, and the levels after surface deposition were completely covered by chitosan proteins. The results of our experiments showed that optimum adsorption conditions was achieved at t = 76 min, BPA concentration 6.5 mg/L, adsorbent dosage 1 g/L and pH = 6.2.The data obtained in this study followed the Langmuir isotherm model and the pseudo-second order model. The maximum monolayer adsorption capacity of nanocomposite for BPA was 46.2 mg/g at 20 °C. This study showed that the adsorption of BPA onto nanocomposite was spontaneous and thermodynamically desirable.

The high levels of heavy metal accumulation in cultivated rice from the Tajan river basin: Health and ecological risk assessment.

Consumption of food crops contaminated with heavy metals (HMs) is a significant risk factor for human health and safety. We evaluated the health risks of HMs in contaminated food crops irrigated with surface water. Results showed there is a substantial buildup of HMs in rice, collected from the Tajan river basin, Iran. The transfer factor (TF) value for toxic elements Cd (3.6-12.4) and Pb (4.9-23.6) were significantly high and exceeded the permissible limits for crops set by WHO. The principal component analysis was used to analyze the relevance of different metals and identify the primary sources. The results showed that two factors dominated the metals variability (94.10% of total variance) that Cr, Fe, Cd, and Pb were dominated by PC1 whereas another factor charged Zn and Cu. The average total hazard quotient (THQ) values for Pb, Fe, Cr, and Cd were 13.8, 7.7, 5.5, and 1.5, respectively, that suggest a considerable risk to the health of regular rice consumers. The high hazard index (HI) value (29.2) demonstrated that the exposure concentration was very high compared to the effective threshold, and it may have potentially harmful implications for human health. To sum up, these results proved that rice from this basin could be a serious dietary source of Pb and Cd exposure to the consumer population.

Determination of adhesive acrylates in recycled polyethylene terephthalate by fabric phase sorptive extraction coupled to ultra performance liquid chromatography - mass spectrometry.

This article presents fabric phase sorptive extraction (FPSE) as a simple and effective pre-concentration method for the enrichment of acrylate compounds in different food simulants and subsequent analysis of the extracts by ultra-high-performance liquid chromatography with mass spectrometric detection (UPLC-MS). Acrylate compounds come from acrylic adhesives used commonly for sticking the paper labels on polyethylene terephthalate (PET) bottles and therefore, they may exist in recycled polyethylene terephthalate (rPET). Four acrylates were studied: ethylene glycol dimethacrylate (EGDM), pentaerythritol triacrylate (PETA), triethylene glycol diacrylate (TEGDA) and trimethylolpropane triacrylate (TMPTA). Five different types of FPSE media coated with different sol-gel sorbents were studied and finally sol-gel polyethylene glycol- polypropylene glycol-polyethylene glycol triblock copolymer (PEG-PPG-PEG) coated FPSE media was chosen for its satisfactory results. The optimal conditions affecting the extraction efficiency of compounds were determined in three different food simulants. Statistical evaluation of this method reveals good linearity and precision. Under the optimized conditions, the method provided limits of detection of the compounds in the range of (0.1-1.9 ng g-1, 0.1-1.2 ng g-1, 0.2-2.3 ng g-1) in EtOH 10%, HAc 3% and EtOH 20% and the enrichment factor values (EFs) after applying N2 were in the range of 11.1-25.0, 13.8-26.3, 8.3-21.9, in simulants A, B and C respectively. The optimized method was applied successfully to analyze thirteen types of recycled PET samples. Acrylates were found in some of the samples at ng g-1 levels.

Targeted imaging of breast cancer cells using two different kinds of aptamers -functionalized nanoparticles.

Breast cancer which is the most commonly diagnosed cancer among women; have been known as a serious threat for health and life around the world. So development of an approach for early-stage diagnosis of breast cancer is vital. In this study, we designed a double aptamer-nanoparticle conjugates-based (DANP) complex for specific detection and visualization of MCF-7 cells using Mucin 1 (MUC 1) aptamer-conjugated gold nanoparticles (MUC1 apt - GNPs) and adenosine triphosphate (ATP) aptamer-conjugated CdTe quantum dots (ATP apt-QDs). The ATP apt-QDs was attached onto MUC1 apt - GNPs surface through Van der Waals forces and electrostatic interactions between ATP aptamer and GNPs leading to the formation of DANP complex. Atomic force microscopy asserted DANP complex formation. The imaging process was based on the recognition of MUC1 protein on the surface of MCF-7 cells by MUC1 aptamer and specific internalization of DANP complex into target cells (MCF-7). Existence of abundant amounts of ATP in lysosome led to release of ATP apt-QDs from the MUC1 apt-GNPs surface resulting in strong fluorescence emission. The flow cytometry analysis and fluorescence microscopy confirmed significant internalization of DANP complex into MCF-7 cells (target) in comparison with CHO cells (non-target). Based on the obtained results, the DANP complex possesses high potency for efficient detection and monitoring of breast cancer cells (MCF-7).

Binding of safranal to whey proteins in aqueous solution: Combination of headspace solid-phase microextraction/gas chromatography with multi spectroscopic techniques and docking studies.

The objective of this work was to study molecular binding of safranal to whey proteins by taking advantage of headspace solid-phase microextraction combined with gas chromatography (HS-SPME/GC), fluorescence and circular dichroism (CD) spectroscopies, and docking studies. The results of HS-SPME/GC indicated that bovine serum albumin (BSA) had the highest affinity toward safranal, with binding constant of 3.196 × 103 M-1. Also, binding strength was reduced in the order of α-lactalbumin (α-Lact), whey protein isolate (WPI), and ß-lactoglobulin (ß-Lg). Although there was a good agreement between results of HS-SPME/GC and fluorescence spectroscopy regarding the safranal binding site on whey proteins, the order of their binding affinity toward safranal was not consistent for both techniques. According to docking studies, conformational alterations in secondary and tertiary structures of whey proteins induced by safranal association resulted from hydrophobic interactions and hydrogen bonds.

Potential application of amino acids in analytical toxicology.

The ability of extraction and preconcentration of small quantities of substances from biological samples is important in analytical sciences, particularly forensic medicine. In the present study, we evaluated the binding potential of amino acids to produce a new solid phase microextraction fiber based on carbon nanotube (CNTs) for extraction and preconcentration of small amount of morphine in urine sample. Raw CNTs were first carboxylated and then functionalized with 3 amino acids including glutamate, arginine, and cysteine. Functionalization was confirmed by FTIR analysis, Raman spectroscopy and SEM imaging. The functionalized CNTs were coated on polypropylene hollow fiber and used for preconcentration. The results of HPLC analysis in isocratic elution mode using acetonitrile-sodium acetate (10:90, v/v; pH 4; 0.01 M) as the mobile phase showed that amino acids are able to adsorb morphine and the prepared fiber could preconcentrate a very low concentration of morphine (0.25 ppb) in urine matrix. In addition, the fiber was successfully used for up to 30 times with no significant loss in the extraction efficiency. Lowest limit of detection (LOD) and limit of quantitation (LOQ) was 0.07 and 0.25, respectively. Also, the lowest and best recovery of the fiber was 87.8% and 139% at LOQ, which belonged to glutamate and arginine, respectively. The fibers based on amino acids can be used for the detection of a small amount of morphine in biological samples, which are not detectable by conventional methods. Simple mechanism of these fibers in preconcentrating morphine makes them a novel candidate for detection of other opiates and drugs of abuses in crime scene investigations and postmortem examinations several days after exposure.

Molecular modeling and experimental study of a new peptide-based microextraction fiber for preconcentrating morphine in urine samples.

Antimicrobial peptides (AMPs) are best known for their bactericidal properties; however, due to their unique and flexible structures, they have also been proposed as potential selective sorbents for specific molecules. In the present study, we aimed to design and produce a new peptide-based microextraction fiber for preconcentrating morphine in urine samples. The binding of morphine to the peptide was first evaluated by computational simulation using the Molecular Operating Environment (MOE) 2015.10 software. A similar study was then performed using DS BIOVIA Materials Studio 2017 v17.1.0.48, which confirmed the results of the simulation carried out with MOE. Afterwards, those results were also confirmed by experimental research. In the experimental evaluation, carbon nanotubes (CNTs) were initially carboxylated with H2SO4/HNO3 (3:1) and then functionalized with the peptide. FTIR analysis, Raman measurements, and SEM imaging were used to confirm that CNT functionalization was successful as well as to check the nanostructure of the fiber. To evaluate the functionality of the fiber, it was inserted into a microtube containing a urine sample that included morphine and then sonicated for 5 min at 40 °C. Afterwards, the fiber was washed with methanol 20% (H2O/methanol) and the resulting sample was analyzed by HPLC. This procedure was repeated for different concentrations of morphine in the urine sample. The computational and experimental results showed that a morphine concentration as low as 0.25 ppb in urine could be adsorbed and detected using the peptide fiber. Therefore, given its semi-selective binding affinity for morphine, this peptide-based fiber can be considered a new approach to the detection of small amounts of morphine in biological samples.

Carbon nanotube/polyurethane modified hollow fiber-pencil graphite electrode for in situ concentration and electrochemical quantification of anticancer drugs Capecitabine and Erlotinib.

A sensitive electrochemical sensor has been designed for in situ preconcentration and determination of anticancer drugs Capecitabine (CPT) and Erlotinib hydrochloride (ETHC) based on a pencil graphite electrode modified with multivalued carbon nanotube-polyurethane (MWCNT-PUFIX) nanocomposite that was supported with a piece of polypropylene hollow fiber (HF-PGE). The electrochemical behavior of CPT and ETHC on the MWCNT-PUFIX/HF-PGE modified electrode was investigated by differential pulse voltammetry (DPV) techniques and the obtained results confirmed its efficiency for sensing of CPT and ETHC. The synthesized nanocomposite was characterized by infrared spectroscopy and scanning electron microscope. After optimization of some effective parameters on the method efficiency including pH, nanocomposite amount, the type of organic solvent, scan rate and the effect of some additives, the mentioned sensor presented suitable results for determination of CPT and ETHC with the linear ranges from 7.70 to 142.00 µM and 0.11 to 23.50 µM and detection limits of 0.11 and 0.02 µM, respectively. Also, the fabricated sensor has shown good performance in analysis of CPT and ETHC in biological samples.