Graphitic Carbon Nitride Nanoheterostructures as Novel Platforms for the Electrochemical Sensing of the Chemotherapeutic and Immunomodulator Agent MTX.

We report on the electrochemical determination of one the most effective and widely used chemotherapeutic, anti-inflammatory, and immunomodulator agents, methotrexate (MTX), using low-cost, green, and facile one-pot prepared graphitic carbon nitride (g-CN ) nanosheets. The g-CN nanosheets have been characterized utilizing Fourier transform infrared spectroscopy, X-ray diffraction(XRD), scanning electron microscopy(SEM), and density functional theory (DFT). In comparison to the bare carbon paste electrode (CPE), the g-CN -modified electrode showed a spectacular enhancement in the electrochemical oxidation and detection abilities of MTX. The proposed material exhibits very low limits of detection (12.45 nM) and quantification (41.5 nM), while possessing a wide linear range of 0.22-1.11 µM and 1.11-27.03 µM under optimized conditions at pH 7.0. Due to the ease of preparation of g-CN, it can be adopted for the cost-effective detection of MTX in industrial and clinical analyses.

Sensitive Determination of SARS-COV-2 and the Anti-hepatitis C Virus Agent Velpatasvir Enabled by Novel Metal-Organic Frameworks.

Herein, we report on the electrochemical determination of velpatasvir (VLP) as the main constituent of Epclusa, a SARS-COV-2 and anti-hepatitis C virus (HCV) agent, using a novel metal-organic framework (MOF). The NH2-MIL-53(Al) MOF was successfully modified with 5-bromo-salicylaldehyde to synthesize 5-BSA=N-MIL-53(Al) MOF. The synthesized MOF has been characterized using Fourier transform infrared spectroscopy, X-ray powder diffraction, scanning electron microscopy, cyclic voltammetry, square wave voltammetry, and electrochemical impedance spectroscopy. The modified MOF showed higher electrochemical activity and response than the bare NH2-MIL-53(Al) MOF. Compared to the bare carbon paste electrode (CPE), the 5-BSA=N-MIL-53(Al)/CPE platform was shown to enhance the electrochemical oxidation and detection of the anti-SARS-COV-2 and anti-HCV agent. Under optimized conditions, the 5-BSA=N-MIL-53(Al)/CPE platform showed a linear range of 1.11 × 10-6 to 1.11 × 10-7 and 1.11 × 10-7 to 25.97 × 10-6 M Britton-Robinson buffer (pH 7) with a detection limit and limit of quantification of 8.776 × 10-9 and 2.924 × 10-8 M, respectively. Repeatability, storage stability, and reproducibility in addition to selectivity studies and interference studies were conducted to illustrate the superiority of the electrode material. The study also included a highly accurate platform for the determination of VLP concentrations in both urine and plasma samples with reasonable recovery.

Detection of suspected carcinogen azo dyes in textiles using thermogravimetric analysis.

Textiles that are in direct contact with human skin are problematic due to the possibility of transferring the dyes or their aromatic amine metabolites through direct contact. 18 samples of women underwear panties of different colors and fabrics materials were examined for their content of azo dyes using thermogravimetric-gas chromatography-mass spectrometry (TGA-GCMS) technique. The nature of fabrics (cotton, nylon, and polyesters) was identified based on their unique thermogravimetric analyses (TGA) pattern. Aromatic amines produced from thermal degradation of the samples were identified using NIST mass spectra data base. Aniline was found in all samples regardless of their color or fabric composition. Black cotton textiles were characterized by the presence of diaminobenzene, red cotton sample showed the presence of 4-amino-3-nitrobenzene-1-sulfonic acid, blue cotton sample showed the presence of chlorobenzenediamine and chloroaniline, and purple cotton textiles showed the presence of 4-nitroaniline. All four purple nylon samples contained nitroaniline and biphenylamine, the three red nylon samples contained nitroaniline and methyldihydro-thiadiazole, the two pink samples showed the presence of chloro-2-(trifluoromethyl) anilinechloro- benzenediamine, the purple polyethylene sample show the presence of diphenyldiazene, and the brown polyester sample showed the presence of 2-amino-1,4-phenylene) dimethanol.[Formula: see text].

Effect of exposure to light emitted diode (LED) lights on essential oil composition of sweet mint plants.

Sweet mint plants (Mentha spicata) were separately exposed to blue, red and green light emitted diodes (LED) lights and natural sunlight as a control. Leaves were analyzed periodically for their essential oil composition using head space GCMS analysis. Control experiments showed that the main essential oil components were carvone (80%), limonene (17%) and other minor terpenes (3%). Exposed plants to green and red lights showed that their headspace essential oils were similar to that of the control plants. However, blue LED lights caused complete disappearance of carvone and limonene, which were never recovered. Disappearance of carvone and limonene were associated with the appearance of new chemicals at concentrations of 65 and 21% that were identified as carvone oxide and eucalyptol, respectively.

Caenorhabditis elegans as a model to study the impact of exposure to light emitting diode (LED) domestic lighting.

This study aimed to investigate the biological impact of exposure on domestic light emitting diodes (LED) lighting using the free-living nematode Caenorhabditis elegans as a model. Nematodes were separately exposed to white LED light covering the range of 380-750 nm, blue light at 450 nm and black light at 380-420 nm for one life cycle (egg to adult) with dark exposure as the control. Each light range induced stress to the nematode C. elegans such as reducing the number of the hatched eggs and/or delayed the maturation of the hatched eggs to the adult stage. In addition, it lowered or prevented the ability of adults to lay eggs and impaired the locomotion in the exposed worms. The observed type of biological stress was also associated with the production of reactive oxygen species (ROS) as compared to nematodes grown in the dark. It is concluded that the blue light component of white LED light may cause health problems, and further investigation is required to test commercial brands of white LEDs that emit different amounts of blue light.

Exposure of women to trace elements through the skin by direct contact with underwear clothing.

Heavy metals pose a potential danger to human health when present in textile materials. In the present study, inductive coupled plasma mass spectrometry (ICPMS) was used to determine the concentrations and the identity of extractable inorganic elements from different brands of women undergarments. A total of 120 samples consisting of 63 cottons, 44 nylons and 13 polyesters manufactured in 14 different countries having different colors were analyzed for their extractable metals contents. Elements analyzed were Ag, Al, As, Ba, Be, Bi, Ca, Cd, Co, Cr, Cu, Fe, Hg, K, Li, Mg, Mn, Na, Ni, Pb, Sb, Se, Sr, Ti, V and Zn. Cotton undergarments were rich in Al, Fe and Zn, nylon undergarments had high levels of Cr, Cu and Al, while polyester fabrics contained higher levels of Ni and Fe compared to cotton or nylon. With respect to manufacturing countries, China, Egypt and India showed the highest concentrations of metals in all fabrics. With respect to the color, black garments were characteristic by high concentration of Fe, blue colors with Cu, brown garments with Fe and Cu, green garments with Cu and Fe, pink garments with Al, purple garments with Al and Cu and red garments with Cr, Zn and Al. The consumer should be made aware of the potential dangers of these metals in their clothing.

Fatty acids composition of Caenorhabditis elegans using accurate mass GCMS-QTOF.

The free living nematode Caenorhabditis elegans is a proven model organism for lipid metabolism research. Total lipids of C. elegans were extracted using chloroform and methanol in 2:1 ratio (v/v). Fatty acids composition of the extracted total lipids was converted to their corresponding fatty acids methyl esters (FAMEs) and analyzed by gas chromatography/accurate mass quadrupole time of flight mass spectrometry using both electron ionization and chemical ionization techniques. Twenty-eight fatty acids consisting of 12 to 22 carbon atoms were identified, 65% of them were unsaturated. Fatty acids containing 12 to17 carbons were mostly saturated with stearic acid (18:0) as the major constituent. Several branched-chain fatty acids were identified. Methyl-14-methylhexadecanoate (iso- 17:0) was the major identified branched fatty acid. This is the first report to detect the intact molecular parent ions of the identified fatty acids in C. elegans using chemical ionization compared to electron ionization which produced fragmentations of the FAMEs.

Simultaneous Determination of Metformin, Glipizide, Repaglinide, and Glimepiride or Metformin and Pioglitazone by a Validated LC Method: Application in the Presence of Metformin Impurity (1-Cyanoguanidine).

A rapid, simple, and precise RPLC method was developed for the simultaneous determination of the widely used oral antidiabetic, metformin hydrochloride (MTF), with some commonly coadministered oral antidiabetics from different pharmacological classes-glipizide (GPZ), pioglitazone hydrochloride (PGZ), glimepiride (GLM), and repaglinide (RPG)-in bulk, laboratory-prepared mixtures and pharmaceutical formulations in the presence of metformin-reported impurity [1-cyanoguanidine (CNG)]. Chromatographic separation was achieved using isocratic elution mode with a mobile phase of acetonitrile: 0.02 M potassium dihydrogen phosphate (pH 3.17; 50-50, v/v) flowing through a CN Phenomenex column (Phenosphere Next, 250 × 4.6 mm, 5 µm) at a rate of 1.5 mL/min at ambient temperature. UV detection was carried out at 220 nm. The method was validated according to International Conference on Harmonization guidelines. Linearity, accuracy, and precision were satisfactory for concentration ranges: 0.175-350 µg/mL for MTF, 0.0525-105 µg/mL for GPZ, 0.125-250 µg/mL for PGZ, and 0.05-100 µg/mL for GLM and RPG. Correlation coefficients were >0.99 for all analytes. LOQs were 0.009 µg/mL for MTF, 0.009 µg/mL for GPZ, 0.04 µg/mL for GLM, 0.124 µg/mL for PGZ, and 0.044 µg/mL for RPG. The developed method is specific, accurate, and suitable for the QC and routine analysis of the cited drugs in their pharmaceutical products.

Detection of azo dyes and aromatic amines in women undergarment.

Women are exposed to several chemical additives including azo dyes that exist in textile materials, which are a potential health hazard for consumers. Our objective was to analyze suspected carcinogenic azo dyes and their degradation aromatic amines in women underwear panties using a fast and simple method for quantification. Here, we evaluated 120 different samples of women underwear for their potential release of aromatic amines to the skin. Seventy-four samples yielded low level mixtures of aromatic amines; however eighteen samples were found to produce greater than 200 mg/kg (ppm) of aromatic amines. Azo dyes in these 18 samples were extracted from the fabrics and analyzed by reverse phase thin layer chromatography in tandem with atmospheric pressure chemical ionization mass spectrometry. Eleven azo dyes were identified based on their mass spectral data and the chemical structure of the aromatic amine produced from these samples. We demonstrate that planar chromatography and mass spectrometry can be really helpful in confirming the identity of the azo dyes, offering highly relevant molecular information of the responsible compounds in the fabrics. With the growing concern about the consumer goods, analysis of aromatic amines in garments has become a highly important issue.

The role of various amino acids in enzymatic browning process in potato tubers, and identifying the browning products.

The effects of five structurally variant amino acids, glycine, valine, methionine, phenylalanine and cysteine were examined as inhibitors and/or stimulators of fresh-cut potato browning. The first four amino acids showed conflict effects; high concentrations (⩾ 100mM for glycine and ⩾ 1.0M for the other three amino acids) induced potato browning while lower concentrations reduced the browning process. Alternatively, increasing cysteine concentration consistently reduced the browning process due to reaction with quinone to give colorless adduct. In PPO assay, high concentrations (⩾ 1.11 mM) of the four amino acids developed more color than that of control samples. Visible spectra indicated a continuous condensation of quinone and glycine to give colored adducts absorbed at 610-630 nm which were separated and identified by LC-ESI-MS as catechol-diglycine adduct that undergoes polymerization with other glycine molecules to form peptide side chains. In lower concentrations, the less concentration the less developed color was observed.

Accurate Mass GC/LC-Quadrupole Time of Flight Mass Spectrometry Analysis of Fatty Acids and Triacylglycerols of Spicy Fruits from the Apiaceae Family.

The triacylglycerol (TAG) structure and the regio-stereospecific distribution of fatty acids (FA) of seed oils from most of the Apiaceae family are not well documented. The TAG structure ultimately determines the final physical properties of the oils and the position of FAs in the TAG molecule affects the digestion; absorption and metabolism; and physical and technological properties of TAGs. Fixed oils from the fruits of dill (Anethum graveolens), caraway (Carum carvi), cumin (Cuminum cyminum), coriander (Coriandrum sativum), anise (Pimpinella anisum), carrot (Daucus carota), celery (Apium graveolens), fennel (Foeniculum vulgare), and Khella (Ammi visnaga), all from the Apiaceae family, were extracted at room temperature in chloroform/methanol (2:1 v/v) using percolators. Crude lipids were fractionated by solid phase extraction to separate neutral triacylglycerols (TAGs) from other lipids components. Neutral TAGs were subjected to transesterification process to convert them to their corresponding fatty acids methyl esters (FAMES) using 1% boron trifluoride (BF3) in methanol. FAMES were analyzed by gas chromatography-quadrupole time of flight (GC-QTOF) mass spectrometry. Triglycerides were analyzed using high performance liquid chromatography-quadrupole time of flight (LC-QTOF) mass spectrometry. Petroselinic acid was the major fatty acid in all samples ranging from 57% of the total fatty acids in caraway up to 82% in fennel. All samples contained palmitic (16:0), palmitoleic (C16:1n-9), stearic (C18:0), petroselinic (C18:1n-12), linoleic (C18:2n-6), linolinic (18:3n-3), and arachidic (C20:0) acids. TAG were analyzed using LC-QTOF for accurate mass identification and mass spectrometry/mass spectrometry (MS/MS) techniques for regiospesific elucidation of the identified TAGs. Five major TAGs were detected in all samples but with different relative concentrations in all of the tested samples. Several other TAGs were detected as minor components and were present in some samples and absence in the others. Regiospecific analysis showed a non-random fatty acids distribution. Petroselinic acid was predominantly located at the sn-1 and sn-3 positions.

Determination of polycyclic aromatic hydrocarbons in dry tea.

Twenty-eight different tea samples sold in the United States were evaluated using high-performance liquid chromatography (HPLC) with fluorescence detection (FLD) for their contamination with polycyclic aromatic hydrocarbons (PAHs). Many PAHs exhibit carcinogenic, mutagenic, and teratogenic properties and have been related to several kinds of cancer in man and experimental animals. The presence of PAHs in environmental samples such as water, sediments, and particulate air has been extensively studied, but food samples have received little attention. Eighteen PAHs congeners were analyzed, with percentage recovery higher than 85%. Contamination expressed as the sum of the 18 analyzed PAHs was between 101 and 1337 µg/kg on dry mass and the average contents in all of the 28 examined samples was 300 µg/kg on dry mass. Seven of the congeners were found in all samples with wide ranges of concentrations as follows: fluorene (7-48 µg/kg), anthracene (1-31 µg/kg), pyrene (1-970 µg/kg), benzo(a)anthracene (1-18 µg/kg) chrysene (17-365 µg/kg), benzo(a)pyrene (1-29 µg/kg), and indeno(1,2,3-cd)pyrene (4-119 µg/kg). The two most toxic congeners benzo(a)pyrene and dibenzo(a,h)anthracene were found at high concentrations only in Earl Grey Twinnings, Earl Grey Harney& Sons Fine Teas, and Chai Ultra Spice Black Tea Twinnings. Six PAH congeners are considered as suspected carcinogens (U.S.EPA), formed the basis of the estimation of the toxic equivalent (TEQ), Chai Ultra-Spice Black Tea Twinnings had the highest TEQ (110.9) followed by two grey tea samples, Earl Grey Harney & Sons Fine Tea (57.7) and Earl Grey Twinnings (54.5). Decaffeinated grey teas had the lowest TEQs, decaffeinated Earl Grey Bigelow (9.4) and Green Tea Honey Lemon Decaffeinated Lipton (9.6).

Browning inhibition mechanisms by cysteine, ascorbic acid and citric acid, and identifying PPO-catechol-cysteine reaction products.

The titled compounds were examined as PPO inhibitors and antibrowning agents; their various mechanisms were investigated and discussed. All compounds reduced significantly both the browning process and PPO activity. Browning index gave strong correlation with PPO activity (r(2) = 0.96, n = 19) indicating that the browning process is mainly enzymatic. Ascorbic acid could reduce the formed quinone instantly to the original substrate (catechol) at high concentration (>1.5 %) while at lower concentrations acted as competitive inhibitor (KI = 0.256 ± 0.067 mM). Cysteine, at higher concentrations (≥1.0 %), reacted with the resulted quinone to give a colorless products while at the low concentrations, cysteine worked as competitive inhibitor (KI = 1.113 ± 0.176 mM). Citric acid acted only as PPO non-competitive inhibitor with KI = 2.074 ± 0.363 mM. The products of PPO-catechole-cysteine reaction could be separation and identification by LC-ESI-MS. Results indicated that the product of the enzymatic oxidation of catechol, quinone, undergoes two successive nucleophilic attacks by cysteine thiol group. Cysteine was condensed with the resulted mono and dithiocatechols to form peptide side chains.

Evaluation of the essential oil of Foeniculum vulgare Mill (fennel) fruits extracted by three different extraction methods by GC/MS.

BACKGROUND: Hydrodistillation (HD) and steam-distillation, or solvent extraction methods of essential oils have some disadvantages like thermal decomposition of extracts, its contamination with solvent or solvent residues and the pollution of residual vegetal material with solvent which can be also an environmental problem. Thus, new green techniques, such as supercritical fluid extraction and microwave assisted techniques, are potential solutions to overcome these disadvantages. MATERIALS AND METHODS: The aim of this study was to evaluate the essential oil of Foeniculum vulgare subsp. Piperitum fruits extracted by three different extraction methods viz. Supercritical fluid extraction (SFE) using CO2, microwave-assisted extraction (MAE) and hydro-distillation (HD) using gas chromatography-mass spectrometry (GC/MS). RESULTS: The results revealed that both MAE and SFE enhanced the extraction efficiency of the interested components. MAE gave the highest yield of oil as well as higher percentage of Fenchone (28%), whereas SFE gave the highest percentage of anethol (72%). CONCLUSION: Microwave-assisted extraction (MAE) and supercritical fluid extraction (SFE) not only enhanced the essential oil extraction but also saved time, reduced the solvents use and produced, ecologically, green technologies.

Charcoal burning as a source of polyaromatic hydrocarbons in waterpipe smoking.

Polyaromatic hydrocarbons (PAH) content from seven commercial waterpipe charcoals were determined during the smoking process to estimate how much PAHs would not be trapped by the water trap and could reach the lungs of the smokers. Naphthalene, 2-methylnaphthalene, acenaphthylene, acenaphthene, phenanthrene and fluoranthene were the most abundant PAH compounds produced during smoking. Naphthalene was the highest in all of the smoke contents and levels of 5 to 405 µg/15 minutes could be inhaled by the smoker. The amounts of PAHs produced during the smoking events in absence of tobacco varied greatly among different brands of charcoal. The amount and composition of the emitted PAH were not related to the amount and composition of the original chemicals in the charcoal prior to burning. Our findings suggest that public health agencies should regulate smoked charcoal products alongside tobacco.

Nematicidal activity of terpenoids.

Thirty four phytoterpenoids were evaluated for their nematicidal effect using the model nematode Caenorhabditis elegans. Nematicidal activities of the tested compounds at concentrations of 50 µg/mL showed wide variation in their effects ranging from no effect, weak, moderate and strong effects. Terpenoids exerting 50% or higher mortality at 50 µg/mL were further tested at five different concentrations to calculate the concentration that will kill 50% of the nematode population (LC(50)). Among the most effective terpenoids were carvacrol, thymol, nerolidol, α-terpinene, geraniol, citronellol, farnesol, limonene, pseudoionone and eugenol in a descending order. These compounds exhibited a dose-dependent effect. The results suggest that the selected monoterpenoids and essential oils with a high concentration of these compounds mayprovide potential natural nematicides and merit further study as botanical nematicides for the control of both plant and animal parasitic nematodes. In general, oxygenated terpenoids and phenolic terpenoids exhibited higher nematicidal activity than hydrocarbons terpenoids.

Lipophilic Constituents of Rumex vesicarius L. and Rumex dentatus L.

Rumex dentatus L. and Rumex vesicarius L., of the family Polygonaceae, are edible herbs growing wild in Egypt. Their lipoid constituents were examined by both liquid chromatography/mass spectrometry (LC/MS) and by gas chromatography/mass spectrometry (GC/MS). Their essential oil compositions consisted mainly of thujene, limonene, fenchon, estragole, and anethole but at largely different concentration. Fatty acid compositions were similar among the two species and consisting of palmitic, oleic, linoleic and linolenic acids, with R. vesicarius containing much higher level of omega-3-fatty acids. Both of the crude lipid extracts of the two species showed strong antioxidant activity as a radical quenching agent against 2,2-diphenyl-1-picrylhydrazyl (DPPH) systems. Antioxidant activities were mostly associated with the polar lipid fractions. High performance thin layer chromatography (HPTLC), both in the normal and reversed phase,as well as liquid chromatography/mass spectrometry (LC/MS) in the positive and negative electrospray ionization (ESI), showed unique chemical profile for each species that can be useful for species identification and quality control of herbal drug formulations. R. vesicarius was characterized by abundances of flavonoids and R. dentatus was abundant in anthraquinones and chromones.

Free Radical Scavenging and Antioxidant Activities of Silymarin Components.

Silymarin is an over the counter food supplement that is sold as a liver enhancement and liver protection preparation. It is a major constituent of the seeds of Silybum marianum which is composed of a mixture of seven major components and several minor compounds. The seven major components: taxifolin, silychristin, silydianin, silybin A, silybin B, iso-silybin A and iso-silybin B were isolated and purified from the crude mixture of silymarin using preparative high performance liquid chromatography to determine which were the most effective for liver protection. Free radical scavenging, hydroxyl radical antioxidant capacity, oxygen radical antioxidant capacity, trolox-equivalent antioxidant capacity and total antioxidant capacity antioxidant activities were determined for each of the individual purified components as well as the crude silymarin mixture. Taxifolin was the most effective component for scavenging free radicals in the DPPH assay with an EC50 of 32 µM far more effective than all other components which showed EC50 ranging from 115 to 855 µM. Taxifolin was also found to be the most effective antioxidant in the oxygen radical antioxidant capacity (ORAC) assay with a trolox equivalent of 2.43 and the second most effective in the hydroxyl radical antioxidant capacity (HORAC) assay with a gallic acid equivalent of 0.57. Other antioxidants assays did not show significant differences between samples.

Comprehensive assessment of antioxidant activity of essential oils.

UNLABELLED: Essential oils have been studied for their unique ability to act as antioxidants. Antioxidant activities of 423 essential oils of 48 different botanical families were evaluated for their antioxidant activities as free radical scavenging agents using the 1,1-diphenyl-2-picrylhydrazyl method. Seventy-three oils showed 50% or more inhibition at a concentration of 1.25 mg/mL. The 73 most active oil samples were further evaluated for their scavenging activities using series of dilutions to estimate their EC(50) . The EC(50) of the 73 most active oils ranged from 4 to 2000 µg/mL. Oils having an EC(50) of less than 300 µg/mL (20 selected samples) were subjected to ß-carotene bleaching antioxidant activity test and more detailed analysis including thin layer chromatography, gas chromatography/mass spectrometry, high performance liquid chromatography and bioautography. Essential oils of the botanical families Lamiaceae and Myrtaceae were the most effective antioxidants. Thymol and carvacrol were the major constituents in most of the essential oils of the family Lamiaceae and eugenol was the major terpene in all of the essential oils of the family Myrtaceae. PRACTICAL APPLICATIONS: Supplementation of food with spices containing essential oils may counteract and retard the process of oxidative damage, lipid oxidation and elevate antioxidant activity of the final product.

Hair as a marker for pesticides exposure.

Rats were orally treated with mixtures of chlorinated pesticides. Hair was collected and analyzed for pesticide residues over a period of up to four weeks. Quantitative and qualitative analysis of the recovered pesticides in hair were determined using gas chromatography with electron capture detector. Results suggest that hair can be used as a biomarker for the monitoring of organochlorinated pesticide residues at low parts per billion levels. Chlorinated pesticides were also detected in human hair of environmentally exposed and occupationally exposed individuals, which indicates that hair can be used for monitoring pesticides exposure.