Application of a novel deep eutectic solvent modified carbon nanotube for pipette-tip micro solid phase extraction of 6-mercaptopurine.

BACKGROUND: 6-mercaptopurine (6-MP) is a chemotherapy drug mainly used to treat leukemia. It is a persistent organic pollutant and can remain in the environment for a long period of time. The presence of 6-MP in the environment poses a number of hazards and needs to be assessed to monitor its potential risk to human health and the environment. However, due to its trace amount in complicated matrices, a clean-up and preconcentration step before its determination is compulsory. RESULTS: As a highly efficient adsorbent for the extrication of 6-mercaptopurine (6-MP), a novel carbon nanotube doped with camphor: decanoic acid deep eutectic solvent was synthesized and applied as a packing material for the pipette-tip micro solid phase extraction sorbent of 6-MP from tap, wastewater and seawater samples before its spectrophotometric determination. Characteristics and structure of this adsorbent was fully investigated. Factors affecting extraction, including type and volume of the eluent, ionic strength and pH of the sample solution, amount of adsorbent, and number of extraction and elution cycles were optimized using one-factor-at-a-time and response surface methodologies. The method was found to be linear in the range of 1 to 1000 µg/L with a limit of detection and quantification of 0.2 and 0.7 µg/L, respectively. Reproducibility as relative standard deviation was better than 4.6%. CONCLUSION: Application of deep eutectic solvent modified carbon nanotube indicated suitable microextraction results and good potential for rapid extraction of trace amounts of 6-MP from different aqueous samples. The amount of sample required for the analysis was less than 10 mL and only 1.5 mg of the adsorbent was used. The total analysis time, including extraction was less than 15 min and the adsorbent could be used for at least 10 times, without significantly losing its adsorption ability. Compared to using unmodified usual carbon nanotubes, deep eutectic solvent doped carbon nanotubes showed 19.8% higher extraction ability.

Application of a magnetically separable Zr-MOF for fast extraction of palladium before its spectrophotometric detection.

In this research, a novel magnetic zirconium-based metal-organic framework (Fe3O4@SiO2@MIP-202, MMOF), was fabricated, fully characterized, and applied for the batch-mode solid phase extraction of trace amounts of Pd2+ ions from water and wastewater samples before its spectrophotometric detection. Pd2+ ions were desorbed from MMOF by nitric acid and were complexed by treating with KI solution to have a maximum absorbance at 410 nm. The synthesized MMOF composite showed a very large surface area (65 m2.g- 1), good magnetization (1.7 emu.g- 1) and a large pore volume (0.059 cm3.g- 1) with adsorption capacity of 194.5 mg of Pd2+ ions/g of the adsorbent. This nanosorbent boasts chemo-mechanical stability, high adsorption capacity due to its vast active sites, and facile recovery facilitated by its magnetic properties. Parameters affecting the extraction efficiency of the method were optimized as pH of the sample 7.4, volume of the sample 25 mL, 15 mg adsorbent, 1 mL of 0.1 M HNO3 eluent, with 10 and 15 min as the extraction and desorption times, respectively. The calibration curve was found to be linear across the 10.0-1500.0 µg.L- 1 range with a limit of detection of 1.05 µg.L- 1. The obtained extraction efficiency and enrichment were 98% and 245, respectively. The total analysis time was less than 30 min. This MMOF has never been used for the extraction of Pd2+ ions before.

A Comprehensive Review on Shilajit: What We Know about Its Chemical Composition.

Shilajit, a natural material known for thousands of years, is primarily famous because it was the main constituent used for the mummification of bodies by dynastic Egyptians. However, for millennia, it has also been an important drug and supplement in traditional and modern medicine. A full search of Shilajit in the literature, reveals that its chemical composition is not known with certainty. That's due to the fact that surprisingly, no comprehensive chemical analysis has ever been performed to find all the chemicals and species present in it. Moreover, its source is not known; some believe that it is formed from dead plant residues or animal excrements, and some others believe it is a mineral secreted from rocks gradually. In this review article, it is tried to gather chemical property information available regarding this soft, mysterious black material to clarify what it is composed of and what formulation commercial supplements and drugs based on Shilajit may have. While there are many differences in the chemical compositions of Shilajit from various regions, it has been discovered that more than 80% of weight of Shilajit is mainly composed of humic substances and almost 20% of its weight consists of calcium, potassium, and magnesium. It also contains amino acids (mainly glycine) and proteins, fatty acids, bioactive compounds such as caffeic acid and gallic acid, and heavy metals including chromium, selenium, and cobalt.

Microplastics removal from aqueous environment by metal organic frameworks.

This paper provides an overview of recent research performed on the applications of metal-organic frameworks (MOFs) for microplastics (MPs) removal from aqueous environments. MPs pollution has become a major environmental concern due to its negative impacts on aquatic ecosystems and human health. Therefore, developing effective and sustainable methods for removing them from aqueous environments is crucial. In recent years, MOFs have emerged as a promising solution for this purpose due to their unique properties such as high surface area, renewability, chemical stability, and versatility. Moreover, their specific properties such as their pore size and chemical composition can be tailored to enhance their efficiency in removing MPs. It has been shown that MOFs can effectively adsorb MPs from aqueous media in the range of 70-99.9%. Besides some high price concerns, the main drawback of using MOFs is their powder form which can pose challenges due to their instability. This can be addressed by supporting MOFs on other substrates such as aerogels or foams. Meanwhile, there is a need for more research to investigate the long-term stability of MOFs in aqueous environments and developing efficient regeneration methods for their repeated use.

Deep Eutectic Solvent Stir Bar Sorptive Extraction: A Rapid Microextraction Technique for the Determination of Vitamin D3 by Spectrophotometry.

In this paper, a new microextraction method, named deep eutectic solvent stir bar sorptive extraction (DES-SBSE), is described that utilizes a hydrophobic DES (hDES) as a coating for SBSE. As a model, vitamin D3 was extracted efficiently by this technique from different real samples before its spectrophotometric determination. A conventional magnet was encapsulated inside a glass bar (1.0 cm × 2 mm) and coated by the hDES consisting of tetrabutylammonium chloride and heptadecanoic acid (mole ratio 1:2). Parameters affecting microextraction were studied and optimized by one-variable-at-a-time, central composite design, and Box-Behnken design methods. Under the optimum conditions, the detection limit of 0.08 µg L-1 could be reached. The linear range of the method was between 0.5 and 1000.0 µg L-1 for the analyte. Precision for intraday repeatability and interday reproducibility of the method was better than 3.1 and 4.2, respectively. A single stir bar could be used for at least 50 successive extractions and the batch-to-batch reproducibility of SB coated with hDES was 4.5%.

Microplastics in atmospheric dust samples of Sistan: sources and distribution.

In this work, the amount and physical and chemical characteristics of airborne microplastics (MPs) pollution in dust samples in Sistan, located in the eastern part of Iran, is reported. Sampling stations were selected according to the wind direction and population density. MPs were collected by a static dust sampler and analyzed by optical microscopy and FT-IR spectroscopy. Results showed that the distribution frequency of MPs in residential and non-residential areas was 6 to 11 pieces per 100 g (pcs/100 g) with an average abundance of 9.8 pcs/100 g. Fragmented MPs were approximately consisted 64% of total MPs and their sizes were in the range of 0.9-3.8 mm. Polyethylene (49%), polystyrene (21%) and polyester (18%) were the main MPs presented in the dust samples. It was observed that population density and wind direction were the most important parameters affecting MPs pollution in dust. Supplementary Information: The online version contains supplementary material available at 10.1007/s40201-022-00833-y.

Magnetic Covalent Organic Frameworks-Fundamentals and Applications in Analytical Chemistry.

Magnetic covalent organic frameworks are new emerging materials which, besides many other applications, have found unique applications in analytical chemistry as separating media and adsorbents. They have outstanding features such as special morphology, chemical and thermal stability, high adsorption capacity, good magnetic response, high specific surface area, uniform pore size distribution, strong π-π interactions with analytes and high reusability that makes reported studies on their properties and applications increased in the recent years. After discussing the methods of synthesis of MCOFs with different geometries that cause their special physic-chemical properties, this review focuses on their high potential which has been exhibited in various applications in extraction and pre-concentration of different analytes such as organic compounds, heavy metal ions and biological samples. The article also highlights the applications of magnetic covalent organic frameworks in other chemical analysis such as adsorbent and being used in sensors.

Application of gas flow headspace liquid phase micro extraction coupled with gas chromatography-mass spectrometry for determination of 4-methylimidazole in food samples employing experimental design optimization.

BACKGROUND: 4-Methylimidazole (4-MeI) or 4-methyl-1H-imidazole, a slightly yellowish solid with molecular formula C4H6N2, is a heterocyclic compound which supposedly does not exist as a natural product and is formed when carbohydrates are heating with ammonium compounds. This compound is used in pharmaceuticals, agriculture and photography chemicals, dyes and pigments, and rubber manufacturing. In the present study, a simple and efficient sample preparation method designated gas flow headspace liquid phase microextraction (GF-HS-SDME) was employed for the extraction and preconcentration of 4-methylimidazole (4-MeI) from food and beverage samples, before its determination by gas chromatography-mass spectrometry. RESULT: To investigate the optimal conditions for the extraction process in GF-HS-SDME method, factors affecting extraction, including selection of extraction solvent, vial volume, extraction solvent ratio, position of extracting solvent, drop volume, sample volume, stirring speed, temperature, extraction time, sample pH, ionic strength of the sample solution and gas flow rate were optimized by utilizing both one-variable-at-a-time method and Plackett-Burman design. The investigation of protocol was carried out by using a standard solution containing 100.0 µg L-1 of 4-MeI in deionized water. CONCLUSION: In this study, a simple and green analytical method based on GF-HS-SDME was proposed for the extraction and preconcentration of 4-MeI from foodstuffs, followed by GC-MS determination. The main advantage of this method is its high preconcentration factor and fastness due to the application of an inert gas stream during microextraction.

Synthesis, characterization and application of a zirconium-based MOF-808 functionalized with isonicotinic acid for fast and efficient solid phase extraction of uranium(VI) from wastewater prior to its spectrophotometric determination.

BACKGROUND: A zirconium-based metal-organic framework (Zr-MOF), named MOF-808, was synthesized and fully characterized by solvo-thermal method and functionalized by isonicotinic acid and employed as an efficient adsorbent for selective extraction and preconcentration of uranyl ions from water and waste water samples in a batch solid phase extraction. RESULTS: Parameters affecting extraction such as volume and pH of the sample solution, the amount of sorbent, type and volume of eluting solvent, and adsorption and desorption times were investigated and optimized. Under the optimized conditions, high extraction efficiency was observed with a limit of detection of 0.9 µg L- 1 for uranyl ions and relative standard deviations were found to be better than 2.1% in the range of 0.07-1000 µg L- 1. CONCLUSIONS: These results indicated that the above procedure is fast, inexpensive, effective, reliable, applicable and organic solvent-free and showed the highly performance and stability of the Zr-MOF in SPE based analytical techniques.

Determination of profenofos in seawater and foodstuff samples after its molecularly imprinted polymer pipette-tip micro solid phase extraction optimized by response surface methodology.

BACKGROUND: In this research, a molecularly imprinted polymer (MIP) was synthesized and employed as a sorbent for pipette-tip micro solid phase extraction of profenofos insecticide in seawater, rice, and fish samples. The instrument employed for quantitation was spectrophotometry. RESULTS: Various factors affecting the microextraction protocol, including type and volume of the elution solvent, weight of MIP, pH and volume of sample solution, and number of cycles of loading and desorption were considered and optimized using one-factor-at-a-time, central composite design and Box-Behnken design. Factors optimized at: pH 4.0, amount of sorbent 2.5 mg, volume of methanol:acetic (9:1) acid as eluent 250 µL, both the number of extraction and elution cycles 5, and volume of sample 8.0 mL. At optimized conditions, an enrichment factor of 31 was achieved and the linearity range of the method was between 1.0 and 1000.0 µg/L. A good detection limit of 0.33 µg/L with a reproducibility better than 5.6% (as RSD) was observed. CONCLUSION: The technique showed good analytical features for determination of profenofos in seawater, rice, and fish samples. Simplicity of operation of spectrophotometry and lack of using expensive HPLC grade solvents are other points of strengths of this method. The total analysis time was about 10 min, which is far less than techniques such as HPLC. Comparison between optimization with central composite design and Box-Behnken design showed better performance of the former.

Chromium-based metal organic framework for pipette tip micro-solid phase extraction: an effective approach for determination of methyl and propyl parabens in wastewater and shampoo samples.

BACKGROUND: A chromium-based metal organic framework was synthesized and employed as an efficient sorbent for pipette tip micro-solid phase extraction and preconcentration of parabens from wastewater and shampoo samples up to sub-ppb level before their spectrophotometric analysis. RESULTS: Factors affecting preconcentration including volume and type of solvent, amount of sorbent, number of extraction, and volume and pH of samples were optimized employing one-variable-at-a-time and response surface methodology. Obtained analytical characteristics of the method proves its usefulness for analysis of real samples. Linear range of the method for parabens was 1.0-200.0 µg/L. Detection limit of the protocol was 0.24 µg/L for propyl paraben and 0.25 µg/L for methyl paraben. Reproducibility of the protocol defined as % RSD was better than 5.78%. Synthesized adsorbent can be re-used for at least 20 extractions. CONCLUSION: The method showed a good detection limit and precision for determination of methyl- and propyl-paraben in wastewater and shampoo samples.

Preconcentration and Analytical Methods for Determination of Methyl Tert-Butyl Ether and Other Fuel Oxygenates and Their Degradation Products in Environment: A Review.

Fuel oxygenates (FOs) are mainly ethers or alcohols which are added to gasoline either to boost the octane number or to make the fuel burning process more "cleaner" with increasing the oxygen content, or to obtain a combination of both effects. FOs are water soluble with high mobility in the environment which presence even at very low concentrations lower the quality of water making it unsafe or unpleasant due to their objectionable taste and/or odor. Thus, their determination at trace in environmental samples is of high importance because of their sparingly biodegradability and their biological hazards. Instruments such as gas chromatography, Fourier transform infrared spectroscopy and ion mobility spectrometry are mainly used for the determination of FOs. However, the main challenge for determination of such oxygenates relates to proper sample preparation. Dilute or complex samples often demand a specific treatment to ensure effective enrichment of FOs before their detection. The main techniques used for this purpose are purge and trap, membrane extraction, and solid phase microextraction. This review presents a comprehensive evaluation of extraction/preconcentration techniques and analytical methods for determination of FOs in environmental samples. Advantages and disadvantages of each method are discussed in details along with critical evaluation of currently available methods.

Nanoparticle coatings for stir bar sorptive extraction, synthesis, characterization and application.

During the last ten years, number of articles published on synthesis and applications of nano-particles (NPs) have been increased by a factor of 40. One of the most interesting applications of NPs is their using as high capacity, robust and highly selective coatings for stir bar sorption extraction (SBSE). Utilizing NPs greatly promoted applications of SBSE and has gained importance on green sample preparation. In this article, all available literature on nano-coatings as media for microextraction by stir bar is reviewed. This includes non-functionalized NPs (mostly, metallic/metallic oxide and graphene based), functionalized coatings, and decorated coatings (both mono- and multifunctional). Various applications, advantages and disadvantages of each nano-coated prepared stir bar are discussed in detail along with critical evaluation of currently available methods.

Fabrication of a Smartphone-Based Spectrophotometer and Its Application in Monitoring Concentrations of Organic Dyes.

In this study, an in-house constructed paper-based spectrophotometer is presented and demonstrated for detecting three organic dyes, namely, methylene blue, malachite green, and rhodamine B, and monitoring the efficiency of their removal from a wastewater sample with Sistan sand as a costless adsorbent. The compact design and light weight of this simple spectrophotometer delivered portability, with materials costing less than a dollar. Spectral analysis of the captured images was performed using free downloadable software from the Google Play store. The main experimental parameters affecting the efficiency of dye adsorption including pH, sorbent dosage, initial dye concentration, and contact time were investigated and optimized using the Taguchi design experimental method. Validation experiments were performed using a standard commercial bench-top spectrophotometer, and results were compared in terms of analytical performance, speed, and cost of analysis. The smartphone-based spectrometer was able to measure accurately, as confirmed using the commercial spectrometer, with enhanced sensitivity for methylene blue and rhodamine B. The combination of the high spectral accuracy of the paper-based spectrophotometer, together with sand as a readily accessible sorbent, enabled us to develop a powerful yet simple approach and tool for the removal and monitoring of dyes within wastewater samples, which is potentially available to everybody who owns a smartphone.

Sputtered silicon solid phase microextraction fibers with a polydimethylsiloxane stationary phase with negligible carry-over and phase bleed.

We report the preparation of high performance, sputtered, polydimethylsiloxane (PDMS)-coated solid phase microextraction (SPME) fibers that show negligible carry-over and phase bleed. This process involves sputtering silicon onto silica fibers and functionalizing the resulting porous nanostructures with ultrathin films of vapor-deposited PDMS. Different thicknesses of silicon (0.25, 0.8, and 1.8 µm) and PDMS (8, 16, and 36 nm) were produced and their extraction efficiencies evaluated. The deposition of PDMS was confirmed by time-of-fight secondary ion mass spectrometry (ToF-SIMS), X-ray photoelectron spectroscopy (XPS), spectroscopic ellipsometry (SE), and contact angle goniometry on model, planar silicon substrates. These fibers were investigated using direct immersion SPME coupled with gas chromatography-mass spectrometry (GC-MS) analysis of a series of polycyclic aromatic hydrocarbons (PAHs), which are carcinogenic pollutants. The 1.8 µm thick silicon coating with 16 nm of PDMS (Si (1.8 µm)/PDMS (16 nm)) produced the best response among the combinations tested. Conditions for the extraction of PAHs with this fiber were optimized and its extraction performance was compared to that of a commercial 7 µm PDMS fiber. The linearity (1-110 µgL-1), repeatability (RSD%, n = 3) (17% ave.), and minimum detection limits (0.6-1.5 µgL-1) of the sputtered fibers were determined and found to be superior to the commercial 7 µm PDMS fiber in many respects. Carry-over and phase bleed from commercial PDMS-based SPME fibers are two of their major drawbacks, which decrease their lifetimes and usefulness. Minimal carry-over and phase bleed were observed for our sputtered PDMS-coated fibers. In particular, our fiber only shows 12% of the phase bleed of the comparable commercial fiber. In addition, it shows no carry-over for analytes with retention times greater than pyrene, and only 5% of the carry-over of the other analytes. Our fibers could be used for at least 300 injections without any significant loss of performance.

PCN-222 metal-organic framework: a selective and highly efficient sorbent for the extraction of aspartame from gum, juice, and diet soft drink before its spectrophotometric determination.

In this paper, we describe synthesis and application of an iron porphyrinc metal-organic framework PCN-222(Fe) for solid phase extraction of aspartame, an artificial non-saccharine sweetener, from gum, juice and diet soft drink samples prior to its determination by spectrophotometry. The mesoporous MOF was synthesized solvo-thermally and characterized by Fourier transform-infrared spectroscopy, powder X-ray diffraction, scanning electron microscopy, and Brunauer-Emmett-Teller techniques. To obtain the best extraction efficiency of aspartame, significant affecting parameters such as pH of sample solution, amount of the sorbent, type and volume of eluting solvent, and adsorption and desorption times were investigated and optimized. Under optimum conditions, the calibration graph for aspartame was linear in the range of 0.1 to 100.0 mg.L-1 and relative standard deviation of aspartame was 1.7% (n = 7). Limit of detection of method calculated as 0.019 mg.L-1 and the enrichment factor of 350 folds was obtained. Adsorption capacity of synthesized sorbent was found to be 356 mg.g-1. Hierarchical porosity, the eight terminal-OH groups of the Zr6 node, and hydrogen bonding possibly play vital role for selective adsorption of aspartame. The optimized method was successfully applied to the determination of aspartame in real samples with reasonable recoveries (> 98%).

Simultaneous Removal of Heavy Metals from Wastewater Using Modified Sodium Montmorillonite Nanoclay.

Sodium montmorillonite nanoclay particles were modified by 3-aminopropyltrimetoxysilane using a physical vapor deposition method and applied for the simultaneous removal of Cd, Zn, Pb and Ni heavy metals from wastewater samples. Experiments were performed in both batch and column systems. Several parameters that influence the removal efficiency, such as the pH, contact time, amount of adsorbent, interfering ions, flow rate of sample passage and eluent solvent, were evaluated and optimized. The results showed that the adsorption isotherms obeyed Langmuir isotherms for all heavy metals. Also, interfering ions did not influenced the removal efficiency. Finally, modified nanoclay successfully could remove all heavy metals from real wastewater samples to near completeness.

Application of a smartphone based spectrophotometer for rapid in-field determination of nitrite and chlorine in environmental water samples.

In this paper, a low cost and portable smartphone-based spectrophotometer with the purpose of measuring trace levels of two important anions, chlorine and nitrite ions in water samples, is introduced. This home-made spectrophotometer is made of Plexiglas, equipped with two LEDs as a light source, and a piece of DVD is acted as light dispersing element. Battery of smartphone was used as its power supply and spectral analysis was performed by a free software downloadable from Google Playstore. By using this lightweight spectrophotometer, various environmental samples were analyzed for their NO2- and Cl2 content in field. Good detection limits of 5.00 × 10-2 mg L-1 and 8.60 × 10-3 mg L-1 were obtained for chlorine and nitrite, respectively. The linear range for chlorine was 1.00-4.00 mg L-1 and this range for nitrite was 0.05-1.20 mg L-1. Reproducibility as relative standard deviation for both chlorine and nitrite was better than 8.75%. In order to investigate validity of data, results were compared to standard methods of measuring chlorine and nitrite, using both spectrophotometry and commercial kits which showed no difference between results obtained. This very simple to use and inexpensive device can be used many times, so can be considered as a low-cost alternative to the detection device of commercial kits.

Separation and determination of ciprofloxacin in seawater, human blood plasma and tablet samples using molecularly imprinted polymer pipette-tip solid phase extraction and its optimization by response surface methodology.

By synthesizing a molecular imprinted polymer as an efficient adsorbent, ciprofloxacin was micro-extracted from seawater, human blood plasma and tablet samples by pipette-tip micro solid phase extraction and determined spectrophotometrically. Response surface methodology was applied with central composite design to build a model based on factors affecting on microextraction of ciprofloxacin; including volume of eluent solvent, number of extraction cycles, number of elution cycles, and pH of sample. Other factors that affect extraction efficiency, such as type of eluent solvent, volume of sample, type, and amount of salt were optimized with one-variable-at-a-time method. Under optimum extraction condition, pH of sample solution was 7.0, volume of eluent solvent (methanol) was 200 µL, volume of sample solution was 10 mL, and the number of extraction and elution cycles was five and seven, respectively, amount of Na2 SO4 (as salt) and MIP (as sorbent) were optimized at 150 and 2 mg, respectively. The linear range of the suggested method under optimum extraction factors was 5-150 µg/L with a limit of detection of 1.50 µg/L for the analyte. Reproducibility of the method (as relative standard deviation) was better than 7%.