Three-Component,One-Pot Synthesis of Benzo[b][1,4]oxazines in Ionic Liquid 1-Butyl-3-methylimidazolium Bromide

Benzo[b][1,4]oxazines have been synthesized in good to excellent yields in the presence of the ionic liquid 1-butyl-3-methylimidazolium bromide [bmim]Br under relatively mild conditions without any added catalyst, The method offers the advantages of good yields and short reaction times, and the ionic liquid can be easily separated from the product and reused.     

Solvent‐Free Chemoselective Synthesis of 1,1‐Diacetates Catalyzed by Cu(NO3)2 · 3H2O

1,1‐Diacetates have been synthesized by the reaction of a variety of aldehydes with acetic anhydride in the presence of cupric nitrate as catalyst under solvent‐free conditions. Ketones were not converted to the corresponding diacetates under these conditions.     

Experimental Design Approach to Investigate the Effects of Operating Factors on the Surface Tension,Viscosity, and Stability of Heavy Crude Oil-in-Water Emulsions

In this article, the effects of various operating factors on the surface tension, viscosity, and stability of two heavy oil types in water emulsions for pipeline transportation are studied using the Taguchi experimental design approach. The surface tension of heavy crude oil-in-water emulsion is decreased by increasing the emulsifier concentration while the stability of emulsions is increased. The viscosity and stability are increased by an increase in oil content. An increase in the salinity and mixing speed leads to an increase in the stability of emulsion.     

Determination of carbaryl by flow injection with luminol chemiluminescence inhibition detection

A flow-injection procedure is described for the determination of carbaryl based on its inhibition effect on luminol-cobalt(II) chemiluminescence reaction in alkaline medium in the presence of hydrogen peroxide. The calibration data over the range 5.0?×?10^?7 to 20?×?10^?6?M give a correlation coefficient (r ²) of 0.9972 with relative standard deviations (RSD; n?=?4) in the range of 1.0–2.1% with a limit of detection (3?×?blank noise) of 2.37?×?10^?7?M for carbaryl. The sample throughput was 120?h^?1. The effects of some carbamates, anions, and cations were studied on luminol CL system for carbaryl determination. The proposed method has been applied to determine carbaryl in natural waters.     

Lewis Acid Mediated Vinyl‐Transfer Reaction of Alkynes to N‐Alkylimines by Using the N‐Alkyl Residue as a Sacrificial Hydrogen Donor

A variety of N‐alkyl‐α,α‐dichloroaldimines were vinylated by terminal acetylenes in the presence of Lewis acids such as In(OTf)₃ or BF₃ ? OEt₂ and hexafluoroisopropanol (HFIP) as an additive. The reaction proceeds at ambient temperature and leads to geometrically pure allylic β,β‐dichloroamines. This approach is complementary to previously reported transition‐metal‐catalyzed vinyl‐transfer methods, which are not applicable to aliphatic imines and are restricted to imines that contain an electron‐withdrawing nitrogen substituent. In the present approach, terminal alkynes were used as a source of the vinyl residue, and the N‐alkyl moiety of the imine acts as a sacrificial hydrogen donor. The additional advantage of this methodology is the fact that no external toxic or hazardous reducing agents or molecular hydrogen has to be used. This new methodology nicely combines a C(sp²)? C(sp) bond formation, hydride transfer, and an unusual cleavage of an unactivated C? N bond, thereby giving rise to functionalized primary allylic amines. A detailed experimental study supported by DFT calculations of the mechanism has been done.     

Polyvinylimidazole/sol–gel composite as a novel solid‐phase microextraction coating for the determination of halogenated benzenes from aqueous solutions

A polyvinylimidazole/sol–gel composite is proposed as a novel solid‐phase microextraction fiber to extract five halobenzenes from the headspace of aqueous solutions in combination with gas chromatography with mass spectrometry. The prepared fiber was characterized by scanning electron microscopy and Fourier transform infrared spectroscopy. The obtained results showed that porous polyvinylimidazole/sol–gel composite was chemically deposited on fused silica fiber. The effect of important extraction parameters including extraction temperature, extraction time, and salt content were investigated. The optimum conditions were as follows: extraction temperature 25°C, extraction time 20 min, and salt concentration 30 w/v%. Detection limits and relative standard deviations of the developed method for halogenated benzenes were below 0.1 pg/mL and 15%, respectively. Repeatability of the proposed method, explained by relative standard deviation, varied between 5.48 and 9.15% (n = 5). The limits of detection (S/N = 3) ranged between 0.01 and 0.10 ng/L using gas chromatography with mass spectrometry with selected ion monitoring mode. For real sample analysis, three types of water samples with different matrices (ground, surface, and tap water) were studied. The optimized procedure was applied to extraction and method validation of halogenated benzenes in spiked water samples.     

Aliphatic Amine Discrimination by Pentafluorophenyl Dibromo BODIPY

Two new fluorescent BODIPY dyes have been designed and synthesized. They dyes differ in their meso substituents, which have different electronic properties. Their selective reactivity towards an Ar‐S_N2 reaction has been explored as a potential basis for colorimetric and fluorescent discrimination of primary, secondary and tertiary aliphatic amines. This dual‐mode, instantaneous recognition event is unprecedented.     

Analysis of tamoxifen and its main metabolites in plasma samples of breast cancer survivor female athletes: Multivariate and chemometric optimization

A sensitive method based on liquid chromatography combined with a diode array detector was developed and validated to simultaneously determine tamoxifen, and its active metabolites N-desmethyltamoxifen, 4-hydroxytamoxifen, and endoxifen in human plasma samples. The green and sustainable vortex-assisted dispersive liquid-phase microextraction technique based on the natural hydrophobic deep eutectic solvent was used for the extraction and preconcentration of the analytes. Chemometrics and multivariate analysis were used to optimize the independent variables including the type and volume of deep eutectic solvent, extraction time, and ionic strength. Under optimal conditions, calibration curves were linear in a suitable range with the lower limits of quantification (0.8–10.0 μg/L), which covered the relevant concentrations of the analytes in plasma samples for a clinical study. Intra- and interday precision evaluated at three concentrations for the analytes were lower than 8.2 and 12.1%, respectively. Accuracy was in the range of 94.9–104.7%. The applicability of the developed method on human plasma samples illustrated the range 45.1–72.8, 98.4–128.3, 0.9–1.2, and 2.7–6.1 μg/L for tamoxifen, N-desmethyltamoxifen, 4-hydroxytamoxifen, and endoxifen, respectively. The validated method can be effective for the pharmacokinetics, pharmacodynamics, and therapeutic drug monitoring studies of tamoxifen and its main metabolites in biological fluids.     

Hydrogen Peroxide Detection Using Prussian Blue-modified 3D Pyrolytic Carbon Microelectrodes

A highly sensitive amperometric Prussian blue-based hydrogen peroxide sensor was developed using 3D pyrolytic carbon microelectrodes. A 3D printed multielectrode electrochemical cell enabled simultaneous highly reproducible Prussian blue modification on multiple carbon electrodes. The effect of oxygen plasma pre-treatment and deposition time on Prussian blue electrodeposition was studied. The amperometric response of 2D and 3D sensors to the addition of hydrogen peroxide in μM and sub-μM concentrations in phosphate buffer was investigated. A high sensitivity comparable to flow injection systems and a detection limit of 0.16 μM was demonstrated with 3D pyrolytic carbon microelectrodes at stirred batch condition