Determination of total extractable organofluorine (EOF) in food contact materials and target and non-target analysis of per- and polyfluoroalkyl substances using LC-MS/MS and LC-HRMS simultaneously coupled to ICP-MS.

Food contact materials (FCMs) from three countries were analysed for all extractable organofluorines (EOFs) from the materials and subsequently by target and non-target analysis for per- and polyfluoroalkyl substances (PFAS). The EOF varied by two orders of magnitude for FCM from UK and Saudi Arabia ranging between 2.14 and 483 ng cm-2 (0.2-48 ng g-1) showing that one quarter of all samples were above the Danish regulation for PFAS in FCM. Target PFAS showed high variability in composition and accounted for less than 1% of the EOF. Non-target PFAS screening using HPLC-ICP-MS and coupled simultaneously to HRMS showed the occurrence of organofluorines which were identified by neither LC-MS/MS nor LC-HRMS. This illustrates that the current target PFAS approaches fail to identify EOFs from FCM, which would be a problem with the new EU proposal to ban all PFAS.

Palladium and platinum complexes based on pyridine bases induced anticancer effectiveness via apoptosis protein signaling in cancer cells.

Palladium and platinum complexes, especially those that include cisplatin, can be useful chemotherapeutic drugs. Alternatives that have less adverse effects and require lower dosages of treatment could be provided by complexes containing pyridine bases. The complexes [Pd(SCN)2(4-Acpy)2] (1), [Pd(N3)2(4-Acpy)2] (2) [Pd(paOH)2].2Cl (3) and [Pt(SCN)2(paO)2] (4) were prepared by self-assembly method at ambient temperature; (4-Acpy = 4-acetylpyridine and paOH = pyridine-2-carbaldehyde-oxime). The structure of complexes 1-4 was confirmed using spectroscopic and X-ray crystallography methods. Complexes 1-4 have similar features in isomerism that include the trans coordination geometry of pyridine ligands with Pd or Pt ion. The 3D network structure of complexes 1-4 was constructed by an infinite number of discrete mononuclear molecules extending via H-bonds. The Pd and Pt complexes 1-4 with pyridine ligands were assessed on MCF-7, T47D breast cancer cells and HCT116 colon cancer cells. The study evaluated cell death through apoptosis and cell cycle phases in MCF-7 cells treated with palladium or platinum conjugated with pyridine base. Upon treatment of MCF-7 with these complexes, the expression of apoptotic signals (Bcl2, p53, Bax and c-Myc) and cell cycle signals (p16, CDK1A, CDK1B) were evaluated. Compared to other complexes and cisplatin, IC50 of complex 1 was lowest in MCF-7 cells and complex 2 in T47D cells. Complex 4 has the highest effectiveness on HCT116. The selective index (SI) of complexes 1-4 has a value of more than two for all cancer cell lines, indicating that the complexes were less toxic to normal cells when given the same dose. MCF-7 cells treated with complex 2 and platinum complex 4 exhibited the highest level of early apoptosis. p16 may be signal arrest cells in Sub G, which was observed in cells treated with palladium complexes that suppress excessive cell proliferation. High c-Myc expression of treated cells with four complexes 1-4 and cisplatin could induce p53. All complexes 1-4 elevated the expression of Bax and triggered by the tumor suppressor gene p53. p53 was downregulating the expression of Bcl2.

Effect of the magnetic core in alginate/gum composite on adsorption of divalent copper, cadmium, and lead ions in the aqueous system.

The change of composition of an adsorbent material has been widely used as a method to increase its adsorption capacity, particularly concerning adsorbents made of polysaccharides. Introducing magnetic adsorbents into contaminated water treatment systems is a highly promising strategy, as it promotes the metal ions removal from water. Considering this, gum Arabic (GA) was associated with alginate (Alg), when magnetite nanoparticles were present or absent, to produce beads that were utilised to take up Cu(II), Cd(II), and Pb(II) from aqueous solution. After a complete characterisation (for which Fourier transform infrared spectroscopy, thermogravimetric analysis, scanning electron microscopy, and swelling were used), the adsorption properties were established using batch and column tests. The magnetic beads (MAlg/GA) demonstrated improved adsorption in comparison with the beads made without magnetite (Alg/GA) under the same conditions. In normal adsorption conditions (pH 6.0, 25 °C, 2.5 g L-1 of adsorbent dosage), the highest uptake capacities recorded for the MAlg/GA beads were: for Cu(II), 1.33 mmol g-1; Cd(II), 1.59 mmol g-1; and for Pb(II), 1.43 mmol g-1. The pseudo-second-order kinetics and Langmuir isotherm models provided good fits for the adsorption of these metals. Overall, ion exchange and physical forces led to the uptake of these metals by both Alg/GA and MAlg/GA; moreover, the functional groups on the beads played crucial roles as binding sites. Additionally, it was observed that flow rates of >2 mL min-1 did not produce noticeable changes in uptake levels over the same flow period. It was found that the efficient eluting agent was HNO3 (0.2 M). In some cases, the metals were not removed fully from the used beads during the first five cycles of regeneration and reuse. The results of this investigation show that these beads are efficient adsorbents for the removal of metal ions from spiked well water samples.

Synthesis, Crystal Structure, DFT, and Anticancer Activity of Some Imine-Type Compounds via Routine Schiff Base Reaction: An Example of Unexpected Cyclization to Oxazine Derivative.

The synthesis, characterization, and anticancer properties of three imine-type compounds 1-3 and an unexpected oxazine derivative 4 are presented. The reaction of p-dimethylaminobenzaldehyde or m-nitrobenzaldehyde with hydroxylamine hydrochloride afforded the corresponding oximes 1-2 in good yields. Additionally, the treatment of benzil with 4-aminoantipyrine or o-aminophenol was investigated. Routinely, the Schiff base (4E)-4-(2-oxo-1,2-diphenylethylideneamino)-1,2-dihydro-1,5-dimethyl-2-phenylpyrazol-3-one 3 was obtained in the case of 4-aminoantipyrine. Unexpectedly, the reaction of benzil with o-aminophenol proceeded with cyclization to produce the 2,3-diphenyl-2H-benzo[b][1,4]oxazin-2-ol 4. The structures of compounds 3 and 4 were unambiguously determined by single crystal X-ray diffraction. Hirshfeld analysis of molecular packing revealed the importance of the O…H (11.1%), N…H (3.4%), C…H (29.4%), and C…C (1.6) interactions in the crystal stability of 3. In the case of 4, the O…H (8.8%), N…H (5.7%), and C…H (30.3%) interactions are the most important. DFT calculations predicted that both compounds have a polar nature, and 3 (3.4489 Debye) has higher polarity than 4 (2.1554 Debye). Different reactivity descriptors were calculated for both systems based on the HOMO and LUMO energies. The NMR chemical shifts were calculated and were found well correlated with the experimental data. HepG2 growth was suppressed by the four compounds more than MCF-7. The IC50 values of 1 against HepG2 and MCF-7 cell lines were the lowest, and it is considered the most promising candidate as an anticancer agent.

A Novel, Simple, and Reliable Spectrophotometric Determination of Total Hexavalent Chromium by Complexation with a New Reagent of Thiazole Linked to 2H-Chromen-2-One.

Hexavalent chromium is a known environmental contaminant and carcinogen. In the current work, a simple, rapid, and reliable direct spectrophotometric method was used for the determination of total Cr (VI) in environmental samples. Acid-base equilibria and ionization constant (pKa) of the new reagent 3-(2-(2-(4-(trifluoromethyl)benzylidene)hydrazineyl) thiazol-4-yl)-2H-chromen-2-one (thiazole linked to 2H-chromen-2-one, TFZ) were investigated. The value of pKa for the reagent was found to be 7.6 which was initially reported. The reaction of the TFZ ligand with Cr (VI) was optimized to produce a highly absorbent complex at 370 nm and pH 7.0 within 1 min. With a correlation coefficient of 0.9994, the linear concentration range ranges from 2 to 20,000 ng·mL-1. The detection limit and quantification limit were 0.73 and 2.43 ng·mL-1, respectively. The method has high precision with relative standard deviations less than 1.0 and high accuracy with recovery of 100 ± 2%. A large excess of cations and anions did not interfere with the determination of Cr (VI). The proposed method was successfully applied to the determination of Cr (VI) in cement samples. The current method could be useful for the routine analysis of Cr (VI) in environmental labs.

Potential Anticancer Activity of Juniperus procera and Molecular Docking Models of Active Proteins in Cancer Cells.

Medicinal plants provide a wide range of active compounds that can be exploited to create novel medicines with minimal side effects. The current study aimed to identify the anticancer properties of Juniperus procera (J. procera) leaves. Here, we demonstrate that J. procera leaves' methanolic extract suppresses cancer cells in colon (HCT116), liver (HepG2), breast (MCF-7), and erythroid (JK-1) cell lines. By applying GC/MS, we were able to determine the components of the J. procera extract that might contribute to cytotoxicity. Molecular docking modules were created that used active components against cyclin-dependent kinase 5 (Cdk5) in colon cancer, aromatase cytochrome P450 in the breast cancer receptor protein, the -N terminal domain in the erythroid cancer receptor of the erythroid spectrin, and topoisomerase in liver cancer. The results demonstrate that, out of the 12 bioactive compounds generated by GC/MS analysis, the active ingredient 2-imino-6-nitro-2H-1-benzopyran-3-carbothiamide proved to be the best-docked chemical with the chosen proteins impacted by DNA conformational changes, cell membrane integrity, and proliferation in molecular docking studies. Notably, we uncovered the capacity of J. procera to induce apoptosis and inhibit cell growth in the HCT116 cell line. Collectively, our data propose that J. procera leaves' methanolic extract has an anticancer role with the potential to guide future mechanistic studies.

Magnetic solid phase extraction as a nonchromatographic method for the quantification of ultratrace inorganic arsenic in rice by inductively coupled plasma-optical emission spectrometry (ICP OES).

An alternative analytical method was developed for the quantification of inorganic arsenic (iAs) in rice by ICP OES. Iron nanoparticles modified with an organophosphorus compound were used as the solid phase for MSPE of iAs from the plant matrix. The MSPE procedure was performed using 4 mL of a buffer solution with pH 4.0, 20 mg of the nanomaterial, and a 15-min extraction time. The total As (tAs) by ICP OES was also quantified using the same MSPE procedure after solubilization of the samples by a block digester. The accuracy of tAs and iAs quantification was verified using CRM NIST 1568b (97 % and 101 % recovery, respectively). The precision (RSD < 15 %) and LOD and LOQ (1.08 and 3.70 µg kg-1, respectively) of the proposed method were satisfactory. The rice samples had tAs contents between 0.090 and 0.295 mg kg-1 and iAs mass fractions between 0.055 and 0.109 mg kg-1.

Methylene blue removal from aqueous solutions using a biochar/gellan gum hydrogel composite: Effect of agitation mode on sorption kinetics.

Hydrogel membranes are prepared by casting a mixture of gellan gum (associated with PVA) and biochar produced from a local Egyptian plant. The mesoporous material is characterized by a specific surface area close to 134 m2 g-1, a residue of 28 % (at 800 °C), and a pHPZC close to 6.43. After grinding, the material is tested for Methylene Blue sorption at pH 10.5: sorption capacity reaches 1.70 mmol MB g-1 (synergistic effect of the precursors). The sorption isotherms are fitted by both Langmuir and Sips eqs. MB sorption increases with temperature: the sorption is endothermic (∆H°: 12.9 kJ mol-1), with positive entropy (∆S°: 125 J mol-1 K-1). Uptake kinetics are controlled by agitation speed (optimum ≈200 rpm) and resistance to intraparticle diffusion. The profiles are strongly affected by the mode of agitation: the equilibrium time (≈180 min) is reduced to 20-30 min under sonication (especially at frequency: 80 kHz). The mode of agitation controls the best fitting equation: pseudo-first order rate agitation for mechanical agitation contrary to pseudo-second order rate under sonication. The sorption of MB is poorly affected by ionic strength (loss <6 % in 45 g L-1 NaCl solution). Desorption (faster than sorption) is completely achieved using 0.7 M HCl solution. At the sixth recycling, the loss in sorption is close to 5 % (≈ decrease in desorption efficiency). The process is successfully applied for the treatment of MB-spiked industrial solution: the color index decreases by >97 % with a sorbent dose close to 1 g L-1; a higher dose is required for maximum reduction of the COD (60 % at 3 g L-1).

EOF and target PFAS analysis in surface waters affected by sewage treatment effluents in Berlin, Germany.

Per- and polyfluoroalkyl substances (PFAS) are emerging organic pollutants and can occur in surface and groundwater. To identify the degree of pollution in surface water with PFAS, often targeted HPLC-ESI-MS/MS has been employed in which commonly 30-40 compounds are analyzed. However, other PFAS and organofluorines remain undetected. We sampled surface water of the river Spree and the Teltow Canal in Berlin, Germany, which are affected by the effluent discharge of wastewater treatment plants. Here, we employed high-resolution continuum source graphite furnace molecular absorption spectrometry (HR-CS-GFMAS) for measuring extractable organofluorines (EOF) and compared in a mass balance approach the total fluorine to the identified and quantified PFAS from the targeted analysis. The analysis highlights that the EOF are in the range expected for an urban river system (Winchell et al. in Sci Total Environ 774, 2021). However, downstream of an effluent discharge, the EOF increased by one order of magnitude, e.g., 40.3 to 574 ng F L-1, along the Teltow Canal. From our target analytes, mostly short-chained perfluorinated carboxylic acids and sulfonates occur in the water, which however makes up less than 10% of the EOF. The increase in EOF in the Teltow Canal correlates well with the increase of perfluorohexanoic acid (PFHxA), indicating that PFHxA is characteristic for the discharged EOF but not responsible for the increase. Hence, it points to PFHxA precursor discharge. The study highlights that EOF screening using HR-CS-GFMAS is necessary to identify the full scale of pollution with regard to PFAS and other organofluorines such as pharmaceutical compounds from the effluent of WWTPs.

A photoluminescence sensor for in-situ monitoring of the dopamine neurotransmitters released from PC12 cells.

Constructing simple, stable, fast, and sensitive neurotransmitter-based sensors is a promising tool to diagnose neurological diseases. Dopamine (DA), "a catecholamine neurotransmitter" is important in transmitting nerve impulses. Therefore, great attention is taken to monitor DA concentrations received. The challenge in developing a DA-based sensor is to enhance its stability and sensitivity. Thus, we have used o-phthalaldehyde (OPA)/2-mercapto ethanol (2ME)/mesoporous silica instated of 2ME in solution. Here we have successfully developed a fluorescence DA neurotransmitters sensor. The sensor was used for detecting a wide range of concentrations of DA (5 nM to 5 µM). Effects of pH (4.3-11.4) and temperatures (25-70 °C) on the sensor efficiency were investigated. The detection limit was 1.35 × 10-11 mol/dm3, which is lower than the normal DA level in the central nervous system. The results indicated that using OPA/2ME/MSNPs has long-time stability over a year of its preparation. Moreover, the developed sensor showed high specificity towards DA in the presence of different interferences such as ascorbic acid or another catecholamine neurotransmitter such as γ-aminobutyric acid. Finally, the fabricated biosensor was used to monitor the DA neurotransmitter released from PC12 cells. Hence, it was successfully developed a simple and stable probe for accurate photoluminescence detection of DA neurotransmitters.

Biosorption kinetics of cerium(III) and cobalt(II) from liquid wastes using individual bacterial species isolated from low-level liquid radioactive wastes.

The existence of toxic heavy metals in the aquatic environment has emphasized a considerable exigency to develop several multifunctional biosorbents for their removal. Herein, three individual bacterial species of Cellulosimicrobium cellulans, Bacillus coagulans, and Microbacterium testaceum were successfully isolated from low-level liquid radioactive wastes. Their loading capacities towards cerium and cobalt metal ions were inclusivity inspected under variable operational parameters of pH, primary pollutant concentration, interaction time, temperature, stirring speed, and biosorbent dosage. By analyzing the influence of solution pH, concentration, temperature, biosorbent mass, and agitation speed on the biosorption kinetics, the biosorption process confirms pseudo-second-order kinetic, intraparticle diffusion, and Elovich equation. Remarkably, the isolated Microbacterium testaceum exhibited high loading capacities reaching 68.1 mg g-1, and 49.6 mg g-1 towards Ce(III), and Co(II) ions, respectively, at the initial concentration of 2.8 mM, pH 4.5, and 25 °C. Overall, the isolated bacterial species can potentially be offered up as a promising scavenger for Ce(III) and Co(II) from liquid waste effluents.

Synergistic effect of Cu-nanoparticles and ß-cyclodextrin functionalized reduced graphene oxide nanocomposite on the adsorptive remediation of tetracycline antibiotics.

Pollution by tetracyclines antibiotics has a great potential risk on human and animal health even at trace levels. Copper nanoparticles immobilized-ß-cyclodextrin functionalized reduced graphene oxide (Cu/ß-CD/rGO) were successfully prepared as an efficient extractor of tetracycline (TC), oxytetracycline (OTC) and doxycycline (DC) antibiotics from different environmental water samples. Tetracyclines (TCs) are strongly deposited in the matrix of Cu/ß-CD/rGO nanocomposite via surface complexation with the Cu-nanoparticles besides the formation of inclusion complexes with ß-cyclodextrin and π-π interaction of reduced graphene oxide. The novel nanocomposite was characterized by HRSEM, TEM, TGA, FT-IR, XPS, and XRD. The optimization of variables such as the pH, contact time, ionic strength and TC concentration were successfully analyzed. The maximum adsorption capacity (qm) of Cu/ß-CD/rGO calculated from the Langmuir isotherm was 403.2 mg.g-1 for TC, 476.2 mg.g-1 for OTC and 434.8 mg.g-1 for DC at 298 K. The removal efficiency was decreased by 3.7% after five adsorption-desorption cycles. The Cu/ß-CD/rGO nanocomposite was applied for removing TCs from tap water and the Nile River water samples. The novel nanocomposite demonstrated fast and highly efficient removing performance for different TCs with low levels and large sample volume.

The use of microwave-induced plasma optical emission spectrometry for fluorine determination and its application to tea infusions.

This study presents a novel method for fluorine quantification determination by microwave-induced plasma optical emission spectrometry (MIP-OES). Due to the low temperature of this plasma, atomic emission of fluorine could not be measured, instead CaF molecular emissions were measured by using a calcium solution mixed in the spray chamber with the sample using a T-piece. Several wavelengths were studied to find the best signal to noise ratio for fluorine determination and 530.45 nm was chosen. The limit of detection for the determination of fluorine via CaF using MIP-OES was 1.1 mg L-1. A linear response was observed over two orders of magnitude (R2 = 0.998). The developed method was applied to ten tea infusion samples from the UK and Saudi Arabia. The results were not significantly different (paired Student's t-test, p = 0.97) to the results obtained using the reference method, high-resolution continuum source graphite furnace molecular absorption spectrometry (HR-GF MAS). The total fluorine in the tea infusions varied between 2.7 and 7.8 mg L-1; all of which were above the WHO recommended level of fluoride (0.8-1.5 mg L-1) in drinking water. This method can potentially be used for total fluorine determination and might be useful for fluorine speciation analysis when coupled with HPLC.

The use of high resolution graphite furnace molecular absorption spectrometry (HR -MAS) for total fluorine determination in extractable organofluorines (EOF).

The determination of total fluorine content using high-resolution graphite furnace continuum source molecular absorption spectrometry (HR- MAS) has been employed in a variety of samples for over 10 years. However, most of the samples analysed by HR- MAS are rich in fluoride, with negligible levels of organic fluorinated species. With an increase in concern surrounding per- and polyfluoroalkyl substances (PFASs), new methods to measure total fluorine of organofluorine using different techniques have been developed. However, no studies focused on PFASs behaviour in HR-MAS have been performed. As these compounds encompass a wide range of different structures, boiling points, decomposition temperatures and matrix interactions, a loss of accuracy can occur when an aqueous external calibration is performed using only one compound. To overcome this issue, an investigation into permanent modifiers for the graphite furnace was performed. After optimisation similar sensitivity for different PFCA was achieved when 400 µg of W was used as a permanent modifier together with an optimised temperature program. The relative deviation between the different PFCA standard slopes relative to the PFOA slope was lower than 15%. The instrumental limit of detection and quantification (LOD and LOQ, respectively) of total fluorine as total PFCA was 0.1 mg L-1 and 0.3 mg L-1, respectively, while the method LOD and LOQ (using solid phase extraction) was 0.3 µg L-1 and 1.0 µg L-1, respectively. The developed method gave satisfactory recoveries for the spiked PFCA into seawater, river water and effluent using PFOA calibration standards. The optimised method is useful for measuring extractable organofluorines (EOF) when only ionic PFASs such as PFCA are expected. When other organofluorines are expected, the results using HR GF-MAS should be taken with caution.