Determination of non-ionic polyethoxylated surfactants in wastewater and river water by mixed hemimicelle extraction and liquid chromatography-ion trap mass spectrometry

The capability of hemimicelles-based solid phase extraction (SPE)/liquid chromatography/atmospheric pressure chemical ionisation in positive mode, ion trap mass spectrometry (LC/(APCl+-IT)-MS) for the concentration, separation and quantitation of non-ionic surfactants has been investigated. Concentration was based on the formation of mixed aggregates of analytes [alkylphenol ethoxylates (APE, octyl and nonyl) and alkyl ethoxylates (AE, C12-C16)] with the anionic surfactant sodium dodecyl sulphate (SDS) that is adsorbed on alumina. Parameters affecting SPE were investigated on the basis that hemimicelles are dynamic entities in equilibrium with the aqueous phase. The performance of ion trap mass spectrometry for MS and MS/MS quantitation of non-ionic homologues was assessed. Recoveries of analytes from wastewater influent and effluent and river water samples ranged between 91 and 98% and were found independent on the length of the alkyl chain under the optimised conditions. Anionic surfactants did not interfere to the levels found in environmental samples. The detection limits ranged between 14 and 111 ng/l for wastewater influent, 10 and 40 for wastewater effluent and 4 and 35 for river water, after concentration of 250, 500 and 750 ml of sample, respectively. The approach was applied to the determination of AE and APE in influent and effluent samples from four wastewater treatment plants and four river samples. The concentrations of individual non-ionic surfactants found ranged between 0.3 and 373 microg/l.     

Conformational dependence of pyranoid rings 1,2-cis-fused to dioxolane rings on the configuration of the dioxolane rings in acetylated derivati

X-Ray and ¹H N.M.R. studies on pyranoid rings 1,2-$\text{cis}$-fused to dioxolane rings in acetylated $\text{D}$-gluco- and $\text{D}$--galactopyranose derivatives demonstrate that the configuration of the dioxolane ring influences the conformation of the pyranoid ring in the $\text{D}$-gluco but not in the $\text{D}$-galactopyranose series. The crystal structure of 3,4,6-tri-$\text{O}$-acetyl-1,2-$\text{O}$-(R)--(l-cyano-ethylidene)-α-$\text{D}$-glucopyranose ($\text{1}$) and 3,4,6-tri-$\text{O}$-acetyl-1,2-$\text{O}$-($\text{R}$)-(1-cyano-ethylidene)-α-$\text{D}$-galactopyranose ($\text{2}$)have been determined by X-ray analysis. Lattice parameters for $\text{1}$ are a=20.6021 (11), b=8.0438 (2), c=5.5541 (1) Å and β= 95.588 (3)° for a cell with P21 symmetry. These parameters for $\text{2}$ are a=20.3361 (7), b=10.0907 (2), c=18.9115 (5) Å, β =112.399 (2)°, C2, with two crystallographycally independent molecules. The conformation of the pyranoid ring in both compounds can be described as flattened ⁴C₁ and that of the dioxolane ring as distorted E₁. The importance of the torsion angles for describing problems of configuration is remarked and the use of relative configurational angles is stressed. The ¹H N.M.R. spectra of $\text{1}$ and $\text{2}$ and 3,4,6-tri-$\text{O}$-acetyl-1,2-O-(S)- and (R)-ethylidene-α-$\text{D}$-glucopyranose ($\text{5}$ and $\text{7}$), 3,4,6-tri-O-acetyl--1,2-O-(S)- and ($\text{R}$)-ethylidene-α-$\text{D}$-galactopyranose ($\text{6}$ and $\text{8}$), and 3,4,6-tri-$\text{O}$-acetyl-1,2-$\text{O}$-($\text{S}$)-and ($\text{R}$)-benzylidene-α-$\text{D}$-glucopyranose ($\text{9}$ and $\text{10}$) have been analyzed by using iterative computer methods and N.O.E. measurements. The results indicate that the major solution conformation of the pyranoid ring of the derivatives in the $\text{D}$-gluco series $\text{1}$, $\text{5}$ and $\text{9}$ may be described as flattened ⁴C₁ and that of $\text{7}$ and $\text{10}$ as ²$\text{S}$₅. The major solution conformation of the pyranoid ring in all compounds in the $\text{D}$-galacto series ($\text{2}$,$\text{4}$,$\text{6}$,$\text{8}$) may be described as flattened ⁴$\text{C}$₁.     

Synthesis,Structure and Reactivity of [1, 2‐Bis(diphenylphosphinite)ethane]bromotricarbonylmanganese(I) with Reactions of Phosphites,Phosphonites. and Phosphinites

The manganese carbonyl complex [MnBr(CO)₃ L ] ( 1 ), where L = Ph₂POCH₂CH₂OPPh₂, was prepared by reacting [MnBr(CO)₅] with the bidentate ligand 1, 2‐Bis(diphenylphosphinite)ethane. From this compound and the appropriate phosphite, phosphinite or phosphonite ligands were synthesized the complexes [MnBr(CO)₂ LL ′], where L ′ = P(OMe)₃ ( 2 ) or P(OEt)₃ ( 3 ) and [MnBr(CO)₃ L ′₂], where L ′ =PPh(OEt)₂ ( 4 ) or PPh₂(OEt) ( 5 ). The obtained compounds have been characterized by elemental analysis, mass spectrometry, IR and NMR (¹H, ¹³C and ³¹P) spectroscopies and X‐ray diffractometry for the complexes 1 , 4 and 5 .     

Voltammetric behavior of zaleplon and its differential pulse polarographic determination in capsules

In this work both the electrochemical behavior and the analysis of the hypnotic pyrazolopyrimidine derivative zaleplon were studied. Zaleplon in ethanol-0.1M Britton Robinson buffer solution (30-70) showed 2 irreversible, well-defined cathodic responses in the pH range of 2-12 using differential pulse polarography (DPP), tast polarography, and cyclic voltammetry. From chronocoulometric studies, it was possible to conclude that one electron was transferred in each reduction peak or wave. For analytical purposes, the DPP technique working at pH 4.5 for peak I was selected, which exhibited adequate repeatability, reproducibility, and selectivity. The recovery was 99.97 +/- 1.52%, and the detection and quantitation limits were 5.13 x 10(-7)M and 1.11 x 10(-6)M, respectively. The DPP method was applied successfully to the individual assay of capsules in order to verify the content uniformity of zaleplon. Treatment of the sample is not required because the excipients do not interfere, the method is not time consuming, and it is less expensive than column liquid chromatography.     

As, Bi, Sb and Sn determination in atmospheric particulate matter by direct solid sampling-hydride generation-electrothermal atomic absorption spectrometry

A novel, rapid and simple method by hydride generation-electrothermal atomic absorption spectrometry (HG-ETAAS) after direct As, Bi, Sb and Sn hydrides generation from untreated filters of atmospheric particulate matter (PM₁₀ and PM_2.5) was optimised. PM₁₀ and PM_2.5 were not subjected to any pre-treatment: circular portions between 0.28 and 6.28 cm² were directly placed into the reaction vessel of a batch mode generation system. A 2⁸ × 3/64 Plackett–Burman design was used as a multivariate strategy for the evaluation of the effects of several variables affecting the hydride generation, trapping and atomisation efficiencies. Trapping temperature was the most statistically significant variable for As, Bi and Sn. Atomisation temperature was also statistically significant for Sb determination. Optimum values of significant variables were selected by using univariate optimisation approaches. An aqueous calibration method was used throughout. The developed method has been found to be precise with relative standard deviations of 6.2, 5.3, 9.1 and 7.5% for 11 determinations in a filter sample containing 0.7, 1.0, 1.4 and 1.7 μg l⁻¹ for As, Bi, Sb and Sn, respectively. Results obtained by direct solid sampling-HG-ETAAS have been found statistically comparable with those obtained after conventional method based on an acid digestion followed to ICP-MS. Absolute detection limits were 37, 15, 30, and 41 ng l⁻¹ for As, Bi, Sb and Sn, respectively. Detection limits referred to the air volume sampled (in the range of 0.020–0.050 ng m⁻³) were low enough for the determination of several hydride-forming elements from PM₁₀ and PM_2.5 samples collected in a non-polluted suburban area of A Coruña (NW Spain).     

Characteristics and safety of nano-sized cellulose fibrils

A finely ground fibrillated cellulose was fractionated into separate size fractions. The characteristics of the smallest size fractions were studied, and the toxicity to humans was tested as part of a safety assessment. Morphological studies performed with state-of-the-art methods, such as scanning electron microscopy and atomic force microscopy, showed that the fraction obtained consisted of long thin fibrils but also larger fibril agglomerates, and spherical particles were present. The finest fraction did not show any sub-lethal effects as assessed by RNA inhibition test in vitro, nor were there any indications of genotoxicity as tested by the Ames test in vitro. Systemic effects tested in vivo with the nematode were also absent. No cytotoxic effects were seen in the highest tolerated dose test in vitro, but some indication of cytotoxicity was observed in the total protein content test in vitro at the highest sample concentration. The significance of this toxicity test result should be addressed in relation to the other toxicity tests, in which no toxicity was observed, with special emphasis on the in vivo test. Given this, the overall toxicity analyses support the conclusion that nano-scale cellulose fibrils can be considered to be safe towards humans. However, the reason for the positive cytotoxicity test result and, in addition, the effect of the biocide used in sample preservation on the toxicity tests need to be clarified before generalizing these results and declaring nanocellulose to be unambiguously safe.     

Effervescence-assisted carbon nanotubes dispersion for the micro-solid-phase extraction of triazine herbicides from environmental waters

Extraction techniques are surface-dependent processes since their kinetic directly depends on the contact area between the sample and the extractant phase. The dispersion of the extractant (liquid or solid) increases this area improving the extraction efficiency. In this article, the dispersion of a nanostructured sorbent at the very low milligram level is achieved by effervescence thanks to the in situ generation of carbon dioxide. For this purpose, a special tablet containing the effervescence precursors (sodium carbonate as carbon dioxide source and sodium dihydrogen phosphate as proton donor) and the sorbent [multiwalled carbon nanotubes (MWCNTs)] is prepared. All the microextraction steps take place in a glass beaker containing 100 mL of the sample. After the extraction, the MWCNTs, enriched with the extracted analytes, are recovered by vacuum filtration. Methanol was selected to elute the retained analytes. The extraction mode is optimized and characterized using the determination of nine herbicides in water samples as model analytical problem. The absolute recoveries of the analytes were in the range 48–76 %, while relative recoveries were close to 100 % in all cases. These values permit the determination of these analytes at the low microgram per liter range with good precision (relative standard deviations lower than 9.3 %) using ultra performance liquid chromatography (UPLC) combined with ultraviolet detection (UV).     

Clean and reactive nanostructured cellulose surface

A simple, solvent-free and low cost method to activate the surface of nanofibrillated cellulose films for further functionalization is presented. The method is based on the oxidative properties of UV radiation and ozone, to effectively remove contaminants from nanocellulosic surface, which remains clean and reactive for at least a week. The efficiency of the method is demonstrated by X-ray photoelectron spectroscopy (XPS) and contact angle measurements. In clear contrast to previous results on nanoscaled cellulose the relative atomic concentration of non-cellulosic carbon atoms was only 4 %, and water completely wetted the surface within seconds. After activation, neither chemical degradation nor morphological changes on cellulose were observed. This surface activation is essential for further functionalization of the film in dry state or nonpolar media. The surface activation was confirmed by silylation and a four times higher degree of substitution was achieved on the activated sample compared to non-activated reference film, as monitored with XPS.     

Electrodes based on zeolites modified with cobalt and/or molybdenum for pesticide degradation: part II—2,4,6-trichlorophenol degradation

Journal of Solid State Electrochemistry - 2,4,6-trichlorophenol (TCP) is a persistent pollutant introduced in water by industrial processes and pesticides. We have studied the electrooxidation of...     

Evaluation of the Storage Conditions and Type of Cork Stopper on the Quality of Bottled White Wines

The effects of different storage conditions, light exposure, temperature and different commercially available cork stoppers on the phenolic, volatile and sensorial profile of Verdejo wines were studied. Two natural corks of different visual quality and a microgranulated cork stopper were investigated over one year at two different storage conditions. One simulating light exposure and temperature in retail outlets and the other simulating optimal cellar conditions (darkness and 12 °C). The wines stored under commercial conditions showed greater losses of total and free SO₂ and higher levels of brown-yellowish tones, related to the oxidation of flavan-3-ols. Although these wines underwent a decrease in the total content of stilbenes, a significant increase in trans-piceid was observed. In addition, these wines suffered important changes in their volatile and sensory profile. Volatile compounds with fruity and floral aromas decreased significantly, while volatile compounds related to aged-type characters, as linalool oxides, vitispirane, TDN or furan derivatives increased. Wines stored in darkness at 12 °C underwent minor changes and their sensory profiles were similar to wine before bottling. The high-quality natural corks and microgranulated corks better preserved the quality of the white wines from a sensory point of view. These results showed that temperature and light exposure conditions (diffuse white LEDs and 24 ± 2 °C) in retail outlets considerably decrease the quality of bottled white wines and, consequently, their shelf life, due to the premature development of aged-type characters.