Smart dual imprinted Origami 3D-ePAD for selective and simultaneous analysis of vanillylmandelic acid and 5-hydroxyindole-3-acetic acid carcinoid cancer biomarkers using graphene quantum dots coated with dual molecularly imprinted polymers.

Measuring the levels of the biomarkers vanillylmandelic acid (VMA) and 5-Hydroxyindole-3-acetic acid (5-HIAA) is a valuable tool for clinical diagnosis not only of neuroblastoma or carcinoid syndrome, but also of essential hypertension, depression, migraine, and Tourette's syndrome. Herein, we explore using graphene quantum dots (GQDs) coated with molecularly imprinted polymer (MIP) as novel dual-imprinted sensors for selective and simultaneous determination of VMA and 5-HIAA in urine and plasma samples. The dual-MIP was successfully coated on the GQDs core via co-polymerization of (3-aminopropyl) triethoxysilane (APTES) and tetraethyl orthosilicate (TEOS), acting as functional and cross-linking monomers, respectively. In addition, we successfully created the dual imprinted VMA and 5-HIAA shell on the GQDs' core via a one-pot synthesis. We fabricated a facile and ready-to-use Origami three-dimensional electrochemical paper-based analytical device (Origami 3D-ePAD) for simultaneous determination of VMA and 5-HIAA using a GQDs@dual-MIP modified graphene electrode (GQDs@dual-MIP/SPGE). The Origami 3D-ePAD was designed to form a voltammetric cell on a three-layer foldable sheet with several advantages. For example, they were quickly assembled and enhanced the device's physical durability with the hydrophobic backup sheet. The developed dual imprinted Origami 3D-ePAD leads to substantially enhanced sensitivity and selectivity to electrochemical signal amplification generated from increasing the electrode-specific surface area, electrocatalytic activity, and the large numbers of dual imprinted sites for VMA and 5-HIAA detection. The synthetic recognition sites are highly selective for 5-HIAA and VMA molecules with an imprinting factor of 8.46 and 7.10, respectively. Quantitative analysis relying on square wave voltammetry reveals excellent linear dynamic ranges of around 0.001-25 µM, with detection limits of 0.023 nM for 5-HIAA and 0.047 nM for VMA (3Sb, n = 3). The Origami 3D-ePAD provides high accuracy and precision (i.e., recovery values of 5-HIAA ranged from 82.98 to 98.40 %, and VMA ranged from 83.28 to 104.39 %), and RSD less than 4.37 %) in urine and plasma samples without any evidence of interference. Hence, it is well suited as a facile and ready-to-use disposable device for point-of-care testing. It is straightforward, cost-effective, reproducible, and stable. Furthermore, it allows for rapid analysis (analysis time ∼20s) useful in medical diagnosis and other relevant fields.

A method to assess glyphosate, glufosinate and aminomethylphosphonic acid in soil and earthworms.

A new sensitive and selective analytical methodology to quantify glyphosate (GLY), aminomethylphosphonic acid (AMPA), and glufosinate (GLU) in both soil and earthworms (Allolobophora chlorotica) was developed. The extraction and purification methods were optimized. The samples were extracted with various aqueous solutions (HNO3, H2O, KOH and borate buffer) and derivatized with 9-Fluorenylmethyl chloroformate (FMOCCl). To optimize the extraction step, a method to remove the excess FMOCCl was applied based on liquid-liquid extraction with diethyl ether. The purification of derivatized extracts was carried out using XLB solid phase extraction (SPE) cartridges before internal standard quantification by liquid chromatography coupled to tandem mass spectrometry (LC/MS/MS). The elution step was optimized to obtain the best recoveries possible, which was with acidic methanol (1% formic acid) (67% for GLY, 70% for GLU and 65% for AMPA). The extraction and purification method followed by analysis of the two herbicides and AMPA in soils using LC/MS/MS determined limit of quantification (LOQ) values of 0.030 µg g - 1 for GLY, 0.025 µg g - 1 for AMPA and 0.020 µg g - 1 for GLU . For earthworms, LOQ were 0.23 µg g - 1 for GLY, 0.20 µg g - 1 for AMPA and 0.12 µg g - 1 for GLU. . The developed method was applied to determine these compounds in natural soils and earthworms.

The use of Pinus nigra as a biomonitor of pesticides and polycyclic aromatic hydrocarbons in Lebanon.

Among the various species of vegetation, conifers play an important role as a biomonitor of air pollution. The current study presents the determination of pesticides and polycyclic aromatic hydrocarbons in 15 conifer samples collected in August 2018 (summer season) from different regions in north Lebanon (Tripoli, Koura, Bcharre, and Akkar). Pollutants were extracted based on QuEChERS-SPME followed by liquid and gas chromatography-tandem mass spectrometry. Results showed that the samples collected from Bcharre region had the lowest concentration in both pesticides and polycyclic aromatic hydrocarbons with a total concentration of 50 and 66 ng g-1, while the samples collected from the regions widely known by their agriculture (Akkar, Tripoli, and Koura areas) were the most polluted with concentrations of 231 and 422 ng g-1, 192 and 370 ng g-1, and 127 and 98 ng g-1 for pesticides and polycyclic aromatic hydrocarbons respectively. This study revealed that conifers are suggested to be efficient biomonitors of contamination levels in the air.

Synthesis of aromatic functionalized cage-rearranged silsesquioxanes (T8, T10, and T12) via nucleophilic substitution reactions.

Organic-inorganic hybrid nano-building blocks of aromatic nitro-, aldehyde-, and bromo-functionalized polyhedral oligomeric silsesquioxanes were easily prepared through nucleophilic substitutions, starting from the reactions between octakis(3-chloropropyl)octasilsesquioxane and phenoxide derivatives. These phenoxide anions not only supply the substitution functions to a silsesquioxane cage, but can also induce a cage-rearrangement leading to the formation of octa-, deca-, and dodecahedral silsesquioxane cages.

Synthesis and isolation of methacrylate- and acrylate-functionalized polyhedral oligomeric silsesquioxanes (T8, T10, and T12) and characterization of the relationship between their chemical structures and physical properties.

Novel organic-inorganic hybrid nanobuilding blocks of methacrylate- and acrylate-functionalized polyhedral oligomeric silsesquioxanes were easily prepared via nucleophilic substitution on octakis(3-chloropropyl)octasilsesquioxane, using sodium methacrylate and sodium acrylate, respectively. From a practical standpoint, these cage-rearranged silsesquioxanes (T8, T10, and T12) could be readily isolated in their pure form with conventional silica gel column chromatography. Octakis(3-propyl methacrylate)octasilsesquioxane (T8) is a colorless, crystalline solid with a melting point of 66.7-67.2 °C, while other cage products are colorless viscous liquids at room temperature. Moreover, we report that the chemical structure/physical property relationship of silsesquioxane cages not only is dependent on the symmetry of the inorganic silsesquioxane core at a given temperature but also is dictated by the organic substituent mobility. Structures of the products were confirmed by (1)H, (13)C, and (29)Si NMR spectroscopy and high resolution electrospray ionization mass spectrometry analysis.