Determination of arsenic in scalp hair samples from exposed subjects using microwave-assisted digestion with and without enrichment based on cloud point extraction by electrothermal atomic absorption spectrometry

A simple and rapid cloud point extraction (CPE) procedure was applied for preconcentration of trace quantities of arsenic (As) in scalp hair samples. The samples were subjected to microwave-assisted digestion in a mixture of nitric acid and hydrogen peroxide (2 + 1, v/v) prior to preconcentration by CPE. The As in digested samples was complexed with ammonium pyrrolidine dithiocarbamate (APDC), and the resultant As-PDC complex was extracted by a nonionic surfactant, octylphenoxypolyethoxyethanol (Triton X-114). After centrifugation, the surfactant-rich phase was diluted with 0.1 M HNO3 in methanol and analyzed by electrothermal atomic absorption spectrometry. The experimental parameters, i.e., amount of APDC, concentration of Triton X-114, equilibrium temperature and time, were optimized. For validation of the proposed method, a certified reference material (CRM) of human hair (BCR 397) was used. No significant difference (P > 0.05) was observed between the experimental results and certified values of the CRM (paired t-test). The LOD and LOQ obtained under the optimal conditions were 0.025 and 0.083 microg/kg, respectively. The developed method was applied for the determination of As in scalp hair samples from male and female subjects of two villages of Khairpur Mir's, Pakistan.     

Development of extraction methods for speciation analysis of selenium in aqueous extracts of medicinal plants

Advanced extraction methods have been developed for direct speciation of dissolved inorganic and organic selenium (Se) species in aqueous extracts of medicinal plants (MPs). The inorganic species of Se (SeIV and SeVI) were separated from organic forms by adsorbing inorganic Se on alumina, while the organic Se was not retained. The retained inorganic Se species was eluted with 10 mL 0.2 M HCl. The total inorganic Se species was determined after prereduction of SeVI into SeIV with concentrated HCl. The SeIV in the eluent and total inorganic Se species were then complexed with diethyldithiocarbamate. The resultant complexes were entrapped in the nonionic surfactant Triton X-114. The total Se, organic Se, total inorganic Se, and SeIV species were determined by electrothermal atomic absorption spectrometry with a modifier. The SeVI concentration was obtained by subtracting SeIV from total inorganic Se contents. The main factors affecting the methodologies were investigated in detail. Under the optimized experimental conditions, the LOD for SeIV was 50 microg/L. Among dissolved inorganic and organic Se species in aqueous extracts of MPs, organic Se species were present in the range of 74-84%, SeIV 3.62-7.47%, and SeVI 12.4-18.57% of total Se contents.     

Novel Sensing Assembly Comprising Engineered Gold Dendrites and MWCNT‐AuNPs Nanohybrid for Acetaminophen Detection in Human Urine

A layered nanohybrid comprising of multi walled carbon nanotubes(MWCNT)‐gold nanoparticles (AuNPs) has been designed as a matrix for the development of Au dendritic nanostructures (AuDN) with enhanced catalytic activity. The developed sensor matrix was thoroughly characterized by scanning electron microscope (SEM), transmission electron microscope (TEM), and energy dispersive X‐ray spectroscopy (EDX). The developed sensor probe MWCNT‐AuNPs/AuDN over glassy carbon electrode (GCE) was used for the label free detection of acetaminophen (AP), a commonly used drug associated with hepatotoxicity when overdosed, as a model molecule. The final sensor probe was characterized by cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS), linear sweep voltammetry (LSV), and differential pulse voltammetry (DPV). The sensor shows excellent analytical performances with a linear dynamic range (LDR) of 100 to 7500 nM, and a low limit of detection (LOD) of 2.12 (±0.03) nM, which is better than recently reported AP sensors. The practical application / clinical possibilities of the final sensor were evaluated by real sample analysis in human urine by spike and recovery method, where the AP recoveries were found in between 92 % to 96 %. The sensor probe shows negligible response towards co‐existing interfering molecules like glucose, urea, uric acid and various amino acids, which are commonly found in real samples (p<0.001, n=3). The shelf life of the sensor probe was evaluated and found to be stable for 8 weeks. The fabricated sensor probe using MWCNT‐AuNPs/AuDN is easy to fabricate, simple, robust, and able to detect AP in urine with high recoveries shows its possibilities to be used in clinical settings.     

O-Tolyldithiocarbonate Complexes of Iron(II) and Iron(III)

Abstract

Reactions of O-tolyldithiocarbonate ligands, (o-, m-, and p-CH₃C₆H₄O)CS₂Na, with anhydrous FeCl₂ (1:2 molar ratio) and with FeCl₃ (1:1 and 1:3 molar ratio) yielded the complexes [{(CreO)CS₂}₂Fe] and [{(CreO)CS₂}_nFeCl_3–n] (Cre = o-, m-, and p-CH₃C₆H₄; n = 1 and 3), respectively. These complexes were reacted with nitrogen and phosphorus donor ligands in dichloromethane, which afforded the adducts corresponded to [{(CreO)CS₂}₂Fe.xL] and [(CreO)CS₂FeCl₂.xL] {x = 1, L = N₂C₁₂H₈; x = 2, L = NC₅H₅, P(C₆H₅)₃}. Elemental analyses and IR, UV-visible, and mass spectroscopic and magnetic studies indicated bidentate mode of bonding by dithiocarbonate ligands leading to sixcoordination around the iron atom as a consequence of Fe…Fe interaction in the complexes [{(CreO)CS₂}₂Fe] and [(CreO)CS₂FeCl₂]. The complexes exhibited antifungal activity. The fungicidal activity of the complexes has been tested by poisoned food technique using fungi Fusarium sp.

Supplemental materials are available for this article. Go to the publisher's online edition of Phosphorus, Sulfur, and Silicon and the Related Elements for the following free supplemental resource: Antifungal Activity.     

Protic ionic liquid-based gel polymer electrolyte: structural and ion transport studies and its application in proton battery

Proton-conducting free standing gel polymer electrolyte (GPE) films containing protic ionic liquid, 1-butyl-3-methylimidazolium hydrogen sulphate, immobilized in blend of poly(vinylidenefluoride-co-hexafluoropropylene) and poly(vinylpyrrolidone) have been prepared by solution-cast technique. Films have been characterized by Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), scanning electron microscope (SEM), differential scanning calorimetry (DSC), complex impedance spectroscopy, and cyclic voltammetry. Ionic conductivity of the semicrystalline and porous GPE films has been obtained as ~3.9?×?10^?3 S cm^?1 at room temperature. Protonic nature of conduction in the films has been established by performing cyclic voltammetry and complex impedance spectroscopy on the cells having both blocking (stainless steel) and both reversible electrodes (Zn + ZnSO₄.7H₂O). The electrochemical stability window of the films has been found as ~3.8 V. The highest conducting film has been used as a separator and proton conductor to fabricate a proton battery of configuration Zn + ZnSO₄.7H₂O |GPE film| PbO₂ + V₂O₅. The battery shows an open circuit voltage of ~1.62 V. Energy density of the cell has been obtained as 35.2 W h kg^?1 for low current drain. Rechargeability of the cell has been tested for ten cycles. The maximum discharge capacity of the cell has been obtained as ~2.50 mA h g^?1 during the first discharge cycle.     

Rh(II) acetate catalyzed cyclopropanation of styrenes with enaldiazo esters: diastereoselective synthesis of enal-cyclopropanes

An efficient Rh(II) acetate catalyzed highly diastereoselective cyclopropanation of styrenes with enaldiazo esters has been developed (up to >95:5 dr and 62–82% yield). The reaction is proposed to involve diacceptor electrophilic rhodium enalcarbenoids and constitutes the first direct synthesis of enal-cyclopropanes with an all carbon γ-quaternary stereocenter.     

Simplified design of low-loss and flat dispersion photonic crystal waveguide on SOI

A low-loss and flat dispersion line-defect photonic crystal waveguide is proposed with a simplified waveguide-design on silicon-on-insulator (SOI) based on hexagonal lattice of 2D photonic crystals. A propagation loss of 3.6 dB/mm and flat dispersion over a large wavelength band is reported with an easy-to-implement design without disturbing the periodicity (keeping lattice constant and hole diameter fixed) in the line-defect photonic crystals. The combined effect of photonic crystals (in-plane periodicity) and the vertical layers on SOI results in efficient waveguiding and dispersion characteristics.     

Essential oil–cyclodextrin complexes: an updated review

Cyclodextrins, degradation product of carbohydrates, have been extensively exploited by food, pharmaceutical and cosmetic industry by virtue of their ease of availability and their ability to entrap guest moieties. Various cyclodextrin derivatives have been granted generally recognized as safe (GRAS) status by several countries. The most noteworthy characteristic of cyclodextrins is their ability to form inclusion complexes with variety of molecules, imparting protection and enabling solubility, bioavailability and safety enhancement of challenging bioactives. In the last few decades, investigations have revealed anti-microbial, anti-inflammatory, insecticidal, analgesic and sedative properties of essential oils. However, their poor solubility, volatility and sensitivity to environmental factors pose challenge for the formulation scientists. Inclusion complexes of essential oils with cyclodextrins have proved a useful strategy to circumvent these challenges. The success of this approach for essential oils is examplified by the commercial garlic oil/β-cyclodextrin products, available under the trade names Xund, Tegra, Allidex and Garlessence. Here, we present an in-depth account of essential oil loaded cyclodextrin inclusion complexes.     

Cyanuric chloride catalyzed mild protocol for synthesis of biologically active dihydro/spiro quinazolinones and quinazolinone-glycoconjugates

We have developed an efficient cyanuric chloride (2,4,6-trichloro-1,3,5-triazine, TCT) catalyzed approach for the synthesis of 2,3-dihydroquinazolin-4(1H)-one (3a-3x), 2-spiroquinazolinone (5, 7), and glycoconjugates of 2,3-dihydroquinazolin-4(1H)-one (10a, 10b) derivatives. The reaction allows rapid cyclization (8-20 min) with 10 mol % cyanuric chloride to give skeletal complexity in good to excellent yield. We believe that this novel procedure may open the door for the easy generation of new and bioactive quinazolinones.