In-situ ionic liquid-dispersive liquid-liquid microextraction method to determine endocrine disrupting phenols in seawaters and industrial effluents

We have evaluated an in-situ ionic liquid-dispersive liquid-liquid microextraction procedure for the determination of six endocrine disrupting phenols in seawaters and industrial effluents using HPLC. The optimized method requires 38???L of the water-soluble ionic liquid 1-butyl-3-methylimidazolium chloride, and 5?mL of seawater or industrial effluent. After appropriate work-up, a drop (~10???L) of an ionic liquid is formed that contains the analytes of interest. It is diluted with acetonitrile and injected into the HPLC system. This procedure is accomplished without heating or cooling the solutions. The method is characterized by (a) average relative recoveries of 90.2%, (b) enrichment factors ranging from 140 to 989, and (c) precisions (expressed as relative standard deviations) of less than 11% when using a spiking level of 10?ng?mL^?1. The limits of detection range from 0.8?ng?mL^?1 for 4-cumylphenol to 4.8?ng?mL^?1 for bisphenol-A.

Headspace-single drop microextraction (HS-SDME) in combination with high-performance liquid chromatography (HPLC) to evaluate the content of alkyl- and methoxy-phenolic compounds in biomass smoke

The content of ten phenolic compounds present in four different biomass smoke materials: rock rose (Cistus monpelienisis), prickly pear (Opuntia ficus indica), pine needles (Pinus canariensis), and almonds skin (Prunus dulcis), have been evaluated. The sampling method mainly consisted of a trap alkaline solution to solubilize the phenols, and was optimized by an experimental design. Average sampling efficiencies of 78.1% and an average precision value of 10.6% (as relative standard deviation, RSD), were obtained for the selected group of phenols. The trapped phenolates were further analyzed by a headspace-single drop microextraction (HS-SDME) procedure, in combination with high-performance liquid chromatography (HPLC) with UV detection. The optimum variables for the HS-SDME method were: 1-decanol as extractant solvent, 3.5 μL of microdrop volume, 2 mL of sample volume, a pH value of 2, saturation of NaCl, an extraction temperature of 60 °C, and an extraction time of 25 min. The optimized HS-SDME method presented detection limits ranging from 0.35 to 5.8 μg mL⁻¹, RSD values ranging from 0.7 to 7.4%, and an average relative recovery (RR) of 99.8% and an average standard deviation of 5.2. The average content of phenolic compounds in the biomass materials studied were 70, 161, 206 and 252 mg kg⁻¹ of biomass for prickly pear, almonds skin, rock rose, and pine needles, respectively. The main components of the smokes were vanillin, phenol and methoxyphenols, in all smoking materials studied.     

Multiparametric automated system for sulfate,nitrite and nitrate monitoring in drinking water and wastewater based on sequential injection analysis

An automated monitoring system for sulfate, nitrite and nitrate based on sequential injection analysis (SIA) was developed. For nitrite determination the modified Griess-Ilosvay method was used, whereas nitrate was previously reduced to nitrite using a cadmium column followed by nitrite determination. A turbidimetric method was carried out in order to determine sulfate. The results showed that the proposed SIA monitoring system constitutes an effective approach for nitrite, nitrate and sulfate determination since it is able to determine levels required by international agencies that regulate these parameters in water. Detection limits of 0.0207 mg N L^? 1, 0.0022 mg N L^? 1 and 3 mg SO₄^2? L^? 1 were obtained for nitrate, nitrite and sulfate, respectively. The developed method offers also typical characteristics of the multicommutated systems, as portability, low reagents consumption and the subsequently minimization of waste generation. The proposed system was successfully applied to drinking water and wastewater samples and validated with a certified river water sample (ION-96.3, LGC Standards).     

Pore-Scale Lattice Boltzmann Modeling and 4D X-ray Computed Microtomography Imaging of Fracture-Matrix Fluid Transfer

We present sequential X-ray computed microtomography (CMT) images of matrix drainage in a fractured, sintered glass-granule-pack. Sequential (4D) CMT imaging captured the capillary-dominated displacement of the oil-occupied matrix by the surfactant-brine-occupied fracture at the pore scale. The sintered glass-granule-pack was designed to have minimal pore space beyond the resolution of CMT imaging, ensuring that the pore space of the matrix connected to the fracture could be captured in its entirety. This provided an opportunity to validate the increasingly common lattice Boltzmann modeling technique against experimental images at the pore scale. Although the surfactant was found to alter the wettability of the originally weakly oil-wet glass to water-wet, the fracture-matrix fluid transfer is found to be a drainage process, showing minimal counter-current migration of the initial wetting phase (decane). The LB simulations were found to closely match experimental rates of fracture-matrix fluid transfer, and trends in the saturation profiles, but not the irreducible wetting-phase saturation behind the flooding front. The underestimation of the irreducible wetting phase saturation suggests that finer image and lattice resolutions than those reported here may be required for accurate prediction of some macroscale multiphase flow properties, at a sizable computational cost.     

Real-time NMR characterization of structure and dynamics in a transiently populated protein folding intermediate

Recent advances in NMR spectroscopy and the availability of high magnetic field strengths now offer the possibility to record real-time 3D NMR spectra of short-lived protein states, e.g., states that become transiently populated during protein folding. Here we present a strategy for obtaining sequential NMR assignments as well as atom-resolved information on structural and dynamic features within a folding intermediate of the amyloidogenic protein β2-microglobulin that has a half-lifetime of only 20 min.     

The simplex dispersion ordering and its application to the evaluation of human corneal endothelia

A multivariate dispersion ordering based on random simplices is proposed in this paper. Given a R^d-valued random vector, we consider two random simplices determined by the convex hulls of two independent random samples of sizes d+1 of the vector. By means of the stochastic comparison of the Hausdorff distances between such simplices, a multivariate dispersion ordering is introduced. Main properties of the new ordering are studied. Relationships with other dispersion orderings are considered, placing emphasis on the univariate version. Some statistical tests for the new order are proposed. An application of such ordering to the clinical evaluation of human corneal endothelia is provided. Different analyses are included using an image database of human corneal endothelia.     

NbCl5 Promoted the Efficient Synthesis of Phthalein Derivatives: Optical Characterization and Solvatochromic Effect

Organic dyes derived from phthaleins have a large number of industrial applications and can be synthesized using a Lewis acid by Friedel–Crafts acylation, followed by an addition reaction to the carbonyl compound. This work aims to investigate the use of NbCl₅ as a catalyst for the acylation reaction. The behavior of the phthalein derivatives in several solvents and when subjected to different pH conditions was studied. These compounds showed a color‐changing effect depending on the pH and solvent, making them useful for applications as indicators. The phthaleins change their conformations depending on the condition of the medium. Photophysical studies of these compounds were carried out through their UV–Vis absorption spectra. Here, we show the umbrella‐like conformation change of phthalein derivatives that depend on the solvent and the pH of the medium.     

First measurements with the neutron decay spectrometer a SPECT

The neutron decay spectrometera SPECT has been built to perform a precise measurement of the proton spectrum shape in the decay of free neutrons. Such a measurement allows a determination of the neutrino electron angular-correlation coefficienta . The present best experiments have an uncertainty of Δa/a = 5% and since the seventies there is no substantial improvement. Witha SPECT, we aim for an uncertainty which is lower by more than an order of magnitude, thus enabling us to perform several precise tests of the Standard Model. In our first beam time at the particle physics beam MEPHISTO at the Forschungsneutronenquelle Heinz Maier-Leibnitz, we studied the properties of the spectrometer. The most serious problem turned out to be the situation- and time-dependent behavior of the background. From the data sets from this beam time in which a background problem was not obvious, we could extract a value ofa = - 0.1151±0.0040^stat , but we could not quantify the background uncertainty. We show ways to deal with the background and other problems for future beam times.     

Polymorphism incidence in commercial tablets of mebendazole: a vibrational spectroscopy investigation

Mebendazole is a broad spectrum anthelminthic drug, which is widely used in large scale deworming programmes. This active pharmaceutical ingredient exhibits three crystal forms, namely, polymorphs A, B, and C. Therapeutic trials suggested that the most stable form, polymorph A, is inactive. However, the dissolution test normally used as a quality control tool is not able to discriminate among the polymorphs of mebendazole. In this work, the ability of the vibrational spectroscopic techniques (mid and nearinfrared absorption and Raman scattering) for the identification of the crystal form of this compound is evaluated. On the basis of these observations, this methodology is applied to determine the polymorphs of MBZ used in the formulation of the commercial tablets available in the Brazilian and German markets. Copyright © 2008 John Wiley & Sons, Ltd.