Lead Fractionation Analysis in Lipstick Samples by Inductively Coupled Plasma-Mass Spectrometry

A new analytical approach based on fractionation was introduced for lead in lipstick samples. Different separation techniques including n-hexane, glycerol extraction, and activated carbon adsorption were used to characterize the lipid fraction, polar and aromatic components of the samples. Additionally, artificial saliva and food stimulant extractions were used for the risk assessment studies. Trace metal levels in fractions were determined by inductively coupled plasma-mass spectrometry. Method validation parameters in the total element determinations were defined in terms of detection limits, accuracy, and precision. The limits of detection and quantification were 0.02 and 0.07 mg kg^?1 for Pb; whereas the repeatability and reproducibility of the results based on percent relative standard deviation were 3.0% and 7.2% for lead, respectively.     

Identification of radiation‐induced radical structure in azocalix[4]arene: an EPR study

A macrocyclic azocalix[4]arene (1) based ester derivative was synthesized. The single crystals of azocalix[4]arene were produced by slow evaporation of concentrated ethyl acetate solutions. These single crystals were exposed to ⁶⁰Co gamma rays with a dose rate of 0.980 kGy h^‐1 for 48 and 72 h to produce a stable free radical. Electron paramagnetic resonance (EPR) measurements were performed in three mutually perpendicular planes of the single crystal in the magnetic field, in addition, temperature dependence of the EPR signal was studied between 120 K and 450 K. The spectra were found to be temperature and angular dependent. Analysis based on the spectra recorded showed that a free radical was formed by fission of a C–H bond. This radical is described as ^?C_aHC_bH₃ The averages of the principal values of the hyperfine parameters and g‐factor are: g = 2.0034, A_Ha = 1.28 mT, A_H1=H2 = 1.00 mT, and A_H3 = 0.49 mT. Copyright © 2013 John Wiley & Sons, Ltd.     

Synthesis and fluorescence sensing properties of novel pyrene-armed calix[4]arene derivatives

Fluorogenic tert-butylcalix[4]arenes bearing two pyrene pendant groups at the lower rim were synthesized. Based on ratiometric changes of monomer and excimer emissions, the pyrene amine derivative of calix[4]arene has been found to act as a selective sensor for Pb²⁺ and Cu²⁺ ions, respectively, due to a conformational change upon chelation of these ions.     

A Long Wavelength Excitable Fluorophore; Chloro Phenyl Imino Propenyl Aniline (CPIPA) for Selective Sensing of Hg (II)

In this study, a very sensitive and highly selective irreversible optical chemical sensor (optode) for mercury ions was described. The sensing scheme was based on the interaction of Hg (II) with a newly synthesized fluoroionophore; chloro phenyl imino propenyl aniline (CPIPA) in plasticized PVC membrane. The sensor membranes were tested for the determination of mercury ion in aqueous solutions by batch and flow-through methods. The optodes allow determination of Hg (II) in the working range of 1.0 × 10⁻⁹–1.0 × 10⁻⁵ M with a detection limit of 4.3 ppb. The sensor exhibited excellent selectivity for Hg (II) with respect to several common alkali, alkaline earth and transition metal ions. The association constant of the 1:1 complex formation for Hg (II) was found to be K_a = 1.86 × 10⁵ M⁻¹. The CPIPA exhibited high fluorescence quantum yield, long excitation and emission wavelength and high Stokes’ shift values in the solid matrix which makes it compatible with solid state optics.     

Vibrational spectroscopic studies and ab initio calculations of 5-methyl-2-(p-methylaminophenyl)benzoxazole

FT-IR spectra of 5-methyl-2-(p-methylaminophenyl)benzoxazole was recorded and analysed. The vibrational frequencies of the compound have been computed using the Hartree-Fock/6-31G* basis and compared with the experimental values.     

Ratiometric sensing of CO2 in ionic liquid modified ethyl cellulose matrix

In this study emission-based ratiometric response of ion pair form of 1-hydroxy-3,6,8-pyrenetrisulfonate (HPTS) to gaseous CO(2) has been evaluated in ionic liquid (IL) containing ethyl cellulose (EC) matrix. The ionic liquid: 1-ethyl-3-methylimidazolium tetrafluoroborate (EMIMBF(4)); provided longer storage time and highly stable microenvironment for the HPTS molecule due to the buffering effect. The utilization of ionic liquid in ethyl cellulose matrix resulted with superior spectral characteristics. The excitation spectra of HPTS exhibited an atypical isoemmissive point in modified EC matrix at 418 nm which allows ratiometric processing of the signal intensities. EMIMBF(4)-doped sensor films exhibited enhanced linear working range between 0 and 100% pCO(2). The signal changes were fully reversible and the shelf life of the EMIMBF(4)-doped films was extended from 15 to 95 days.     

Synthesis of two new p-tert-butylcalix[4]arene β-ketoimin derivatives for extraction of dichromate anion

In this study the selective derivatization of p-tert-butylcalix[4]arene was carried out and two new p-tert-butylcalix[4]arene β-ketoimin, 5,11,17,23-tetra-tert-butyl-25,27-bis-3-methyl-[(β-ketoimine)-ethoxy]-26,28-dihydroxycalix[4]arene (4), and 5,11,17,23-tetra-tert-butyl-25,27-bis-3-chloro-[(β-ketoimine)-ethoxy]-26,28-dihydroxycalix[4]arene (5) have been synthesized. In the synthesis, the lower rim of p-tert-butylcalix[4]arene was modified in order to acquire binding site for the recognition of dichromate anion. It was observed that these ionophores 4 and 5 showed high affinity towards dichromate anion. The protonated Schiff-base forms of the receptors were effective for transferring the HCr₂O₇ ^? anion from aqueous phase to a dichloromethane phase.     

IR, Raman and SERS spectra of 2-phenoxymethylbenzothiazole

The FT-IR and FT-Raman spectra of 2-phenoxymethylbenzothiazole were recorded and analyzed. The surface enhanced Raman scattering (SERS) spectrum was recorded in a silver colloid. The vibrational wavenumbers of the compound have been computed using the Hartree–Fock/6-31G* basis and compared with the experimental values. The appearance of the Ag–O stretching mode at 237 cm⁻¹ in the SERS spectrum along with theoretically calculated atomic charge density, leads us to suggest that the molecule is adsorbed through the oxygen atom with the molecular plane tilted on the colloidal silver surface. The direction of charge transfer contribution to SERS has been discussed from the frontier orbital theory.     

An empirical study on the benefit of split loads with the pickup and delivery problem

Splitting loads such that the delivery of certain loads is completed in multiple trips rather than one trip has been shown to have benefit for both the classic Vehicle Routing Problem (VRP) and the Pickup and Delivery Problem (PDP). However, the magnitude of the benefit may be affected by various problem characteristics. In this paper, we characterize those real world environments in which split loads are most likely to be beneficial. Based on practitioner interest, we determine how the benefit is affected by the mean load size and variance, number of origins relative to the number of destinations, the percentage of origin–destination pairs with a load requiring service, and the clustering of origin and destination locations. We find that the magnitude of benefit is greatest for load sizes just over one half vehicle capacity as these loads can not be combined without splitting, while they are the easiest to combine on a vehicle with splitting; increases as the number of loads sharing an origin or destination increases because there are more potential load combinations to split at each stop; and increases as the average distance from an origin to a destination increases because splitting loads reduces the trips from origins to destinations.     

Biomimetic mineralization of hydroxyapatite crystals on the copolymers of vinylphosphonic acid and 4-vinilyimidazole

In the present work, copolymers of vinylphosphonic acid and 4-vinilyimidazole (poly(4-VIm-co-VPA)) were found to be substrates favoring the precipitation of nanohydroxyapatite (HAP) crystals from stable supersaturated solutions at pH 7.4 and 37 degrees C. Deposition kinetics were studied by the constant composition technique. The rates of crystallization both on HAP seed crystals as reference and on the copolymer in powder form were investigated at constant supersaturation conditions. The rates of HAP crystal growth on the polymeric substrate were found to depend on the amount of seed material and on the phosphate content of the copolymer.