Selenium analysis in water samples by dispersive liquid-liquid microextraction based on piazselenol formation and GC–ECD

The application of the recently introduced dispersive liquid–liquid microextraction (DLLME) for the separation and determination of an inorganic selenite [Se(IV)] derivative by means of a gas chromatography–electron-capture detection system has been studied. The selenium derivative was extracted with the DLLME technique using a mixture of ethanol (disperser solvent) and chlorobenzene (extraction solvent). The influences of the various analytical parameters on the derivatization reaction and microextraction procedure have been evaluated and optimized. Under the optimum conditions, an enrichment factor of 122 was obtained for only 5.00 mL of the water sample. The calibration graph was linear in the range of 0.015–10 μg L^?1 with a detection limit of 0.005 μg L^?1. The relative standard deviation for ten replicate measurements of 2 μg L^?1 of selenium was 4.1%. The method was applied to the determination of selenium in environmental surface water samples with satisfactory recovery.     

PhI(OTf)2 Does Not Exist (Yet)**

PhI(OTf)₂ has been used for the past 30 years as a strong I(III) oxidant for organic and inorganic transformations. It has been reported to be generated in situ from the reactions of either PhI(OAc)₂ or PhI=O with two equivalents of trimethylsilyl trifluoromethanesulfonate (TMS-OTf). In this report it is shown that neither of these reactions generate a solution with spectroscopic data consistent with PhI(OTf)₂, with supporting theoretical calculations, and thus this compound should not be invoked as the species acting as the oxidant for transformations that have been associated with its use.     

Multiple functions of microfluidic platforms: Characterization and applications in tissue engineering and diagnosis of cancer

Microfluidic system, or lab-on-a-chip, has grown explosively. This system has been used in research for the first time and then entered in the clinical section. Due to economic reasons, this technique has been used for screening of laboratory and clinical indices. The microfluidic system solves some difficulties accompanied by clinical and biological applications. In this review, the interpretation and analysis of some recent developments in microfluidic systems in biomedical applications with more emphasis on tissue engineering and cancer will be discussed. Moreover, we try to discuss the features and functions of microfluidic systems.     

Influence of bidentate phosphine ligands on the chemistry of [FeFe]-hydrogenase model: insight into molecular structures and electrochemical characteristics

Substitution of carbonyl ligands of the hydrogenase model complex [Fe₂(μ-SeCH₂CH(Me)CH₂Se-μ)(CO)₆] ( A ), by 1,1′-bis (diphenylphosphino)ferrocene (dppf), 1,2-bis (diphenylphosphino)benzene (dppbz) or 1,2-bis (diphenylphosphino)acetylene (dppac) is investigated. It is found that the reaction product depends on the diphosphine used. In the case of dppf, the product is an intramolecular bridged disubstituted complex [Fe₂{μ-SeCH₂CH(Me)CH₂Se-μ}(CO)₄{μ,κ¹,κ¹(P,P)-dppf}] ( 1 ), while the dppac-reaction produces an intermolecular bridged tetra-iron model [Fe₂{μ-SeCH₂CH(Me)CH₂Se-μ}(CO)₅]₂{μ,κ¹,κ¹(P,P)-dppac} ( 2 ). However, the dppbz-reaction gives [Fe₂{μ-SeCH₂CH(Me)CH₂Se-μ}(CO)₄{κ²(P,P)-dppbz}] ( 3 ) in which the dppbz ligand is bonded to one Fe atom in a chelated manner. The newly prepared complexes ( 1 – 3 ) have been characterized by elemental analysis, IR, ¹H-, ¹³C{H}-, ³¹P{H}-, ⁷⁷Se{H}-NMR spectroscopy and X-ray structure determination. The electrochemical behavior of 2 and 3 , in absence and presence of acid, is described by cyclic voltammetric measurements in CH₂Cl₂.     

Synthesis of Novel Triazole Incorporated Thiazolone Motifs Having Promising Antityrosinase Activity through Green Nanocatalyst CuI-Fe3O4@SiO2 (TMS-EDTA)

In the present work, novel 5-((1-benzyl-1,2,3-triazol-4-yl)methoxybenzylidene)-2-(arylamino)thiazol-4-one thiazolone incorporated triazole derivatives have been designed as tyrosinase inhibitors. The compounds were synthesized through click reaction in good yield. Moreover, the antityrosinas activity of the synthesized derivatives was evaluated. In the search for establishing a click copper-catalyzed azide/alkyne cycloaddition (CuAAC) reaction under strict conditions, in terms of a novel air-stable, a recyclable and efficient magnetic catalyst was planned for new triazole derivatives as a well-organized copper iodide supported on the functionalized Fe₃O₄@SiO₂ core-shell (CuI/Fe₃O₄@SiO₂(TMS-EDTA) nanoparticles). The engineered nanocatalyst synthesized for the first time and characterized by different methods, including FT-IR spectroscopy, XRD, FESEM, EDX, TEM, TGA, and BET analysis. The excellent catalytic performance in ethanol with high surface area (351.7 m²g⁻¹) and short reaction time for diverse functional groups (120–200 min), no use of toxic solvents, reusability of the catalyst, and using eco-friendly conditions are the advantageous of this work. Moreover,the nanocatalyst can be used at least five times without any significant decrease in the yield of the reaction. The thiazolidine-triazole derivatives 9a , 9c , 9e , and 9 g showed promising tyrosinase inhibitory activity with IC₅₀ values in the range of 5.90–9.81 μM. The compounds were found to be considerably more potent tyrosinase inhibitors than the reference inhibitor kojic acid (IC₅₀ = 18.36 μM).     

Mg-catalyzed one-pot preparation of benzimidazoles and spirooxindoles by an immobilized chlorophyll b on magnetic nanoparticles

Chlorophyll b was extracted from Heliotropium europaeum plant, then immobilized on magnetic nanoparticles (Fe₃O₄@SiO₂@Chl-Mg) and found as an efficient and green catalyst for the preparation of a variety of benzimidazoles and spirooxindoles in mild conditions. The catalyst was fully characterized by Fourier-transform infrared (FTIR), ultraviolet–visible (UV–vis) spectroscopy, X-ray diffraction (XRD), energy-dispersive X-ray spectroscopy (EDX), thermogravimetric (TGA), vibrating sample magnetometer (VSM), transmission electron microscopy (TEM), and dynamic light scattering (DLS) analyses. To prove the catalytic influence of Mg over the reactions, the catalytic activity of the demetalated chlorophyll b as well as some other control experiments was investigated. High to excellent yields were achieved for all entries, whether benzimidazole or spirooxindole derivatives at short reaction times. The catalyst could be recovered and reused for several consecutive runs by a simple external magnetic field without any considerable reactivity loss. The properties of the recovered catalyst were investigated by various analyses. Finally, the reasonable mechanisms were proposed for the reactions based on the literature.     

Novel marine-based gold nanocatalyst in solvent-free synthesis of polyhydroquinoline derivatives: Green and sustainable protocol

We report an ecofriendly synthetic approach for the fabrication of biogenic gold nanoparticles (AuNPs) using electron-rich sea cucumber extract as a bio-reductant and stabilizing agent in reducing gold cations into AuNPs at the optimal conditions. The produced AuNPs are spherical in shape with an average particle size of 11 ± 1.5 nm in transmission electron microscopy (TEM) and exhibited a crystal structure of face-centered cubic in X-ray diffraction (XRD) analyses. Our results indicated that bioinspired AuNPs demonstrate superior catalytic activity in the safe and facile one-pot synthesis of polyhydroquinoline derivatives under solvent-free reaction conditions. This green route encompasses multiple benefits including highly recyclable bioinspired catalyst (5 cycles), short reaction times, convenient workout, high to excellent product yields (82%–97%), and nonhazardous conditions.     

Extraction of methyl xanthines and their UHPLC–DAD determination in consumable beverages used in Eastern province of Saudi Arabia

Coffee and tea are the most widely consumed beverages worldwide. However, the consumer may be unaware of the exact amount of methyl xanthine (MX, i.e. caffeine [C], theobromine [TB] and theophylline [TH]) consumed, as most of the products do not list the proper amounts. This may lead to serious risks including cardiovascular, kidney and stimulant effects. The aim of the study was to determine the MX amount in ready-to-use beverages (coffee and tea) collected from various outlets in the city of Al-Khobar, Saudi Arabia. Forty different samples of espresso, black coffee and red tea were collected. A fast, reliable and efficient UHPLC–DAD method was developed and validated for MX determination. Total lipids were extracted and fractionated in order to determine glycolipids, phospholipids and neutral lipids. The r² value for the method was 0.980–0.988 in a linearity range of 0.5–200 ppm. The range for MX (C [0.02–2.39 mg/ml], TB [0.00–0.10 mg/ml] and TH [0.00–0.004 mg/ml]) and total lipids was 1–5 g. The amount of glycolipids (3.1 g) was higher among the lipid fractions followed by phospholipids (1.8 g) and neutral lipids (0.25 g). In general, espresso beverages (20–30 ml) contained high amounts of MX whereas black coffee beverages contained high amount of lipids. Most of the beverages expressed C, TB, TH, lipids or their fractions; however, the product with high amounts of MX and lipids at the same time was espresso (brands Chemistry and Wogard). Although the MX and lipid levels in these beverages well below the allowed limits, care must still be taken, especially when using the beverages with high serving volumes (200–250 ml) or coffee prepared via the filter method i.e. black coffee, using a high temperature for a longer time.     

TEAD–YAP Interaction Inhibitors and MDM2 Binders from DNA-Encoded Indole-Focused Ugi Peptidomimetics

DNA-encoded combinatorial synthesis provides efficient and dense coverage of chemical space around privileged molecular structures. The indole side chain of tryptophan plays a prominent role in key, or “hot spot”, regions of protein–protein interactions. A DNA-encoded combinatorial peptoid library was designed based on the Ugi four-component reaction by employing tryptophan-mimetic indole side chains to probe the surface of target proteins. Several peptoids were synthesized on a chemically stable hexathymidine adapter oligonucleotide “hexT”, encoded by DNA sequences, and substituted by azide-alkyne cycloaddition to yield a library of 8112 molecules. Selection experiments for the tumor-relevant proteins MDM2 and TEAD4 yielded MDM2 binders and a novel class of TEAD-YAP interaction inhibitors that perturbed the expression of a gene under the control of these Hippo pathway effectors.