Intercalation of iron(III) hexacyano complex in a Ni,Al hydrotalcite-like compound

The product obtained by the intercalation of hexacyanoferrate(III) inside a Ni, Al hydrotalcite-like compound (Htlc) has been characterized using XRD, FT-IR, Raman, and XAS spectroscopy. The intercalation was carried out by anionic exchange of the originally existing chloride ions. The combined use of those techniques gave more insight on the insertion chemistry of Htlcs. Extended X-ray absorption fine structure spectra of the intercalated Htlc demonstrated that the native structure was stable during the iron complex insertion, whereas the exchange process occurred with a partial reduction of hexacyanoferrate(III). Both Raman and FT-IR spectroscopy pointed out the concomitant formation of K(2)NiFe(II)(CN)(6) and KNiFe(III)(CN)(6). The effect of aging on the intercalated product is also addressed.     

Investigation of extraction procedures and HPLC-DAD/MS for the determination of the brominated flame retardant tetrabromobisphenol A bis(2,3-dibromopropylether) in environmental samples

A method for the determination of the novel brominated flame retardant tetrabromobisphenol A bis(2,3-dibromopropylether), 1,1′-(isopropylidene)bis[3,5-dibromo-4-(2,3-dibromo-propoxy)-benzene] (TBBPA-dbpe), was developed. Technical TBBPA-dbpe was purified and the results of a thorough physical characterisation are reported. The application of APCI-MS is discussed and the fragmentation patterns are described. Quantification of TBBPA-dbpe was done by HPLC-DAD using external calibration. The validation of the method was accomplished using sediment and sewage sludge samples spiked with defined amounts of authentic TBBPA-dbpe. The average recovery rates of TBBPA-dbpe from spiked samples ranged from 35 to 91% (sediment) and from 57 to 98% (sewage sludge) depending on the respective extraction method. Pressurised fluid extraction (PFE) and fluidised bed extraction were superior to classical Soxhlet and sonication procedures and yielded recovery rates between 90 and 98% with relative standard deviations of 2%. The limits of detection (DTC), identification (ID) and determination (DTM) using HPLC-DAD were 10, 21 and 30 ng g⁻¹ in sediment and 22, 44 and 72 ng g⁻¹ in sewage sludge, respectively.     

Crystal structure, spectroscopy and thermodynamic properties of MVWO6(M – Li, Na)

In the present work lithium (sodium) vanadium tungsten oxides with brannerite structure is refined by the Rietveld method (space group C2/m, Z=2). IR and Raman spectroscopy was used to assign vibrational bands and determine structural particularities. The diffuse reflectance spectra allow to calculate bandgap for M^IVWO₆(M^I – Li, Na). The temperature dependences of heat capacity have been measured first in the range from 7 to 350 K for these compounds and then between 330 and 640 K, respectively, by precision adiabatic vacuum and dynamic calorimetry. The experimental data were used to calculate standard thermodynamic functions, namely the heat capacity C_p^o(T), enthalpy H^o(T)−H^o(0), entropy S^o(T)−S^o(0) and Gibbs function G^o(T)−H^o(0), for the range from T→0 to 640 K. The differential scanning calorimetry was applied to measure decomposition temperature of compounds under study.     

Antigenicity of heat-treated and trypsin-digested milk samples studied by an optical immunochip biosensor

Abstract  Individuals with known hypersensitivity or food allergy need to avoid ingestion of provoking food. Correct labelling of allergenic content in manufactured food products and the reliable determination of its residual immunoreactivity after several processing steps are therefore a major concern for the food industry. We evaluated the applicability of a new immunochip biosensor system to reveal the allergenic profile of the whey protein β-lactoglobulin (β-LG) in its natural biological cow’s milk matrix upon processing by tryptic digestion and extensive heat treatment. Colorimetric immunochemical signals generated by gold nanoparticles (Au NPs), in particular their functional optical property based on resonance-enhanced absorption of mirror-reflected light, were directly visible to the ‘naked’ eye of the analyst without the need of any instrumentation or enzyme-substrate for read-out. By using affinity-purified polyclonal rabbit IgG against the native protein, no antigenicity was detected for tryptic fragments. Both heat-denatured whey proteins and cow’s whole milk, however, did not lose their antibody-binding capacity even after a processing time of 20 min at 95°C for the whey proteins, and 60 min at 90°C for the milk, though the immunochemical response was considerably low compared to the unprocessed β-LG. Additionally, cross-reactivity and the false positive as well as false negative predictive value of the chip system were highlighted critically. Graphical abstract        

Structures and thermodynamics of biphenyl dihydrodiol stereoisomers and their metabolites in the enzymatic degradation of arene xenobiotics

A key step in the metabolic degradation of biphenyl xenobiotics is catechol formation upon dehydrogenation of cis‐ and trans‐dihydrodiols in prokaryotic and eukaryotic pathways, respectively. Structure and thermodynamics of stereoisomers of cis‐, trans‐2,3‐biphenyl‐dihydrodiols ( I ) and their dehydrogenation products (hydroxyketones, II ), as well as final catechol (2,3‐biphenyldiol, III ) are studied by means of ab initio MP2/6‐311++G(2df,2p)//MP2/6‐311G(d,p) calculations. Formation of stereoisomers I and II is exothermic and endergonic, whereas III is enthalpically and entropically driven. Dehydrogenations are endothermic (ΔH ～ 1.5–4 kcal mol^?1) and exergonic (ΔG ～ ?5 to ?7.5 kcal mol^?1) without noticeable differences between cis and trans pathways, although the same keto stereoisomer II ‐(2S) is found to be the more favored product from both cis‐ and trans‐ I . The final II → III tautomerization is thermodynamically enhanced (ΔH ～ ?27, ΔG ～ ?28 kcal mol^?1) but the process is shown to have a large activation energy if it had to occur via unimolecular path. Although this tautomerization is generally assumed to be a nonenzymatic process as it involves rearomatization of an oxygenated ring, proton transfer with an anionic intermediate might be a more probable process. © 2009 Wiley Periodicals, Inc. J Comput Chem, 2009     

Slice monogenic functions

In this paper we offer a new definition of monogenicity for functions defined on ℝ ⁿ⁺¹ with values in the Clifford algebra ℝ _n following an idea inspired by the recent papers [6], [7]. This new class of monogenic functions contains the polynomials (and, more in general, power series) with coefficients in the Clifford algebra ℝ _n . We will prove a Cauchy integral formula as well as some of its consequences. Finally, we deal with the zeroes of some polynomials and power series.     

Quantitative Determination of Isostearic Acid Isomers in Skin Creams by GC-MS-SIM

“Isostearic acid” is frequently listed as an ingredient of skin creams and other cosmetics. In the four skin creams analyzed, “isostearic acid” was esterified with isopropanol, as well as sorbitan or polyglycerols. “Isopropyl isostearate” was isolated by HCl treatment and saponification whereas emulsifiers (sorbitan or polyglycerol isostearates) were enriched by means of a C₁₈-cartridge. Fatty acids in the resulting lipid fraction were transferred into methyl esters. 25:0 and 19:0 methyl esters were used as internal standards. GC-EI-MS was used to determine that “isostearic acid” was a mixture of many methyl-branched isomers of stearic acid (18:0) in all four skin creams. Thus, it may be better termed “isostearic acids”. The branched-chain nature of isostearates was verified by formation and analysis of picolinyl esters of skin cream fatty acids by GC-EI-MS. Twenty-five 18:0 isomers were detected and the main products had one methyl branch on carbons C₁₀–C₁₄. Two late eluting isostearic acid isomers were identified as 16-methyl heptadecanoic acid (i18:0) and 15-methyl heptadecanoic acid (a18:0). GC-EI-MS in the selected ion monitoring (SIM) mode with m/z 87 as quantification ion was used for the determination of i18:0 methyl ester. The quantities of i18:0 in the samples amounted to 10–20 mg g^?1 skin cream. The contribution of i18:0 to the sum of all 18:0 isomers in the four skin cream samples was 8.5 ± 1.1%. Instead of determining all individual isostearates in a product, we suggest the quantitative determination of i18:0 followed by multiplication with factor 11.75 (~reciprocal value of 8.5%, see above) as a simple method for the quantification of isostearates in cosmetics.     

Occupational and consumer risk estimates for nanoparticles emitted by laser printers

Several studies have reported laser printers as significant sources of nanosized particles (<0.1 μm). Laser printers are used occupationally in office environments and by consumers in their homes. The current work combines existing epidemiological and toxicological evidence on particle-related health effects, measuring doses as mass, particle number and surface area, to estimate and compare the potential risks in occupational and consumer exposure scenarios related to the use of laser printers. The daily uptake of laser printer particles was estimated based on measured particle size distributions and lung deposition modelling. The obtained daily uptakes (particle mass 0.15–0.44 μg d⁻¹; particle number 1.1–3.1 × 10⁹ d⁻¹) were estimated to correspond to 4–13 (mass) or 12–34 (number) deaths per million persons exposed on the basis of epidemiological risk estimates for ambient particles. These risks are higher than the generally used definition of acceptable risk of 1 × 10⁻⁶, but substantially lower than the estimated risks due to ambient particles. Toxicological studies on ambient particles revealed consistent values for lowest observed effect levels (LOELs) which were converted into equivalent daily uptakes using allometric scaling. These LOEL uptakes were by a factor of about 330–1,000 (mass) and 1,000–2,500 (particle surface area) higher than estimated uptakes from printers. This toxicological assessment would indicate no significant health risks due to printer particles. Finally, our study suggests that particle number (not mass) and mass (not surface area) are the most conservative risk metrics for the epidemiological and toxicological risks presented here, respectively.     

Electromagnetic enhancement in lossy optical transition metamaterials

We investigate the effect of anomalous field enhancement in metamaterials (MMs) where the effective refractive index gradually changes from positive to negative values, i.e., transition MMs. We demonstrate that considerable field enhancement can be achieved in lossy optical transition MMs that have electromagnetic material properties obtained from experimental data. The field enhancement factor is found to be polarization dependent and largely determined by the material parameters and the width of the transition layer.