A linear semi-infinite programming strategy for constructing optimal wavelet transforms in multivariate calibration problems

A novel strategy for the optimization of wavelet transforms with respect to the statistics of the data set in multivariate calibration problems is proposed. The optimization follows a linear semi-infinite programming formulation, which does not display local maxima problems and can be reproducibly solved with modest computational effort. After the optimization, a variable selection algorithm is employed to choose a subset of wavelet coefficients with minimal collinearity. The selection allows the building of a calibration model by direct multiple linear regression on the wavelet coefficients. In an illustrative application involving the simultaneous determination of Mn, Mo, Cr, Ni, and Fe in steel samples by ICP-AES, the proposed strategy yielded more accurate predictions than PCR, PLS, and nonoptimized wavelet regression.     

Preparative mass‐spectrometry profiling of minor concentrated metabolites in Salicornia gaudichaudiana Moq by high‐speed countercurrent chromatography and off‐line electrospray mass‐spectrometry injection

Salicornia species have just been introduced to the European market as a vegetable named ‘samphire’, ‘green asparagus’, or ‘sea asparagus’. Due to its increasing attention, and associated value, minor compounds of Salicornia gaudichaudiana Moq were investigated. The use of countercurrent chromatography and mass spectrometry enabled the search for known, as well as potentially novel natural products. Their identification was achieved based on molecular weights and mass‐spectrometric fragmentation data. Low detection limits enabled the visualization of all compounds with their identification in almost real time close to the preparative countercurrent chromatography experiment. A list of known natural products from Salicornia genus guided the identification process of compounds occurring in Salicornia gaudichaudiana Moq by tandem mass spectrometry fragment comparison. The natural product classes were divided into four groups: chlorogenic acid derivatives; flavonoid derivatives; pentacyclic triterpenoid saponins; and other compounds.     

Development and validation of a glass-silicon microdroplet-based system to measure sulfite concentrations in beverages

Sulfite is often added to beverages as an antioxidant and antimicrobial agent. In fermented beverages, sulfite is also naturally produced by yeast cells. However, sulfite causes adverse health effects in asthmatic patients and accurate measurement of the sulfite concentration is therefore very important. Current sulfite analysis methods are time- and reagent-consuming and often require costly equipment. Here, we present a system allowing sensitive, ultralow-volume sulfite measurements based on a reusable glass-silicon microdroplet platform on which microdroplet generation, addition of enzymes through chemical-induced emulsion destabilization and pillar-induced droplet merging, emulsion restabilization, droplet incubation, and fluorescence measurements are integrated. In a first step, we developed and verified a fluorescence-based enzymatic assay for sulfite by measuring its analytical performance (LOD, LOQ, the dynamic working range, and the influence of salts, colorant, and sugars) and comparing fluorescent microplate readouts of fermentation samples with standard colorimetric measurements using the 5,5′-dithiobis-(2-nitrobenzoic acid) assay of the standard Gallery Plus Beermaster analysis platform. Next, samples were analyzed on the microdroplet platform, which also showed good correlation with the standard colorimetric analysis. Although the presented platform does not allow stable reinjection of droplets due to the presence of a tight array of micropillars at the fluidics entrances to prevent channel clogging by dust, removing the pillars, and integrating miniaturized pumps and optics in a future design would allow to use this platform for high-throughput, automated, and portable screening of microbes, plant, or mammalian cells.

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Characterization of the Zwitterionic Intermediate in 1,1‐Carboboration of Alkynes

The reaction of a Lewis acidic borane with an alkyne is a key step in a diverse range of main group transformations. Alkyne 1,1‐carboboration, the Wrackmeyer reaction, is an archetypal transformation of this kind. 1,1‐Carboboration has been proposed to proceed through a zwitterionic intermediate. We report the isolation and spectroscopic, structural and computational characterization of the zwitterionic intermediates generated by reaction of B(C₆F₅)₃ with alkynes. The stepwise reactivity of the zwitterion provides new mechanistic insight for 1,1‐carboboration and wider B(C₆F₅)₃ catalysis. Making use of intramolecular stabilization by a ferrocene substituent, we have characterized the zwitterionic intermediate in the solid state and diverted reactivity towards alkyne cyclotrimerization.     

Synthesis and characterization of new porphyrin/4-quinolone conjugates

New porphyrin/4-quinolone conjugates were synthesized from the Suzuki-Miyaura coupling reaction of a β-borylated porphyrin with bromo-4-quinolones containing N-ethyl and N-d-ribofuranosyl substituents. The use of electrospray ionization tandem mass spectrometry showed important information about the fragmentation pathways of the new compounds. It was possible to distinguish between those compounds with the porphyrin moiety linked at the 6-position of the quinolone unit from their 7-substituted isomers. The new compounds showed to be good singlet oxygen generators.     

Carbon paste electrode modified with Fe<Subscript>3</Subscript>O<Subscript>4</Subscript> nanoparticles and BMI.PF<Subscript>6</Subscript> ionic liquid for determination of estrone by square-wave voltammetry

A carbon paste electrode (CPE) modified with Fe₃O₄ nanoparticles (Fe₃O₄ NP) and the ionic liquid 1-butyl-3-methylimidazolium hexafluorophosphate (IL BMI.PF₆) was employed for the electroanalytical determination of estrone (E1) by square-wave voltammetry (SWV). At the modified electrode, cyclic voltammograms of E1 in B–R buffer (pH 12.0) showed an adsorption-controlled irreversible oxidation peak at around +0.365 V. The anodic current increased by a factor of five times and the peak potential shifted 65 mV to less positive values compared with the unmodified CPE. Under optimized conditions, the calibration curve obtained showed two linear ranges: from 4.0 to 9.0 μmol L^?1 and from 9.0 to 100.0 μmol L^?1. The limits of detection (LOD) and quantification (LOQ) attained were 0.47 and 4.0 μmol L^?1, respectively. The proposed modified electrode was applied to the determination of E1 in pork meat samples. Data provided by the proposed modified electrode were compared with data obtained by UV–vis spectroscopy. The outstanding performance of the electrochemical device indicates that Fe₃O₄ NP and the IL BMI.PF₆ are promising materials for the preparation of chemically modified electrodes for the determination of E1.     

Intraspecific variation in the essential oils from Drimys brasiliensis leaves and stem barks

The essential oils from leaves and stem barks of Drimys brasiliensis Miers (Winteraceae), collected in July and December 2008, were analyzed by GC/FID and GC/MS. The stem bark oils were composed mainly of monoterpenes (July, 45 +/- 3%; December, 92 +/- 4%), while the oils from leaves showed the predominance of sesquiterpenes (July, 47 +/- 1%; December, 55 +/- 1%). The variation in the relative amount of constituents could be associated, at least in part, to several microclimatic parameters such as precipitation, temperature and/or phenological state, which were different for each collection of D. brasiliensis.     

Three-dimensional triazenido layers attained through classical and non-classical hydrogen interactions and its coordination to palladium under prolific occurrence of bifurcated hydrogen bonding

The new ligand 1,3-bis(3-methoxy-4-methylbenzoate) triazene (1, bmmbt), and the already known ligand 1,3-bis(4-acetylphenyl)triazene (bapht), yield the two new palladium(II) complexes [(bmmbt)Pd(PPh₃)₂Cl]·DMSO (2) and [(bapht)Pd(PPh₃)₂Cl] (3) (Ph = phenyl; DMSO = dimethylsulfoxide). Compound 1 shows the existence of more than one interaction promoting the coupling between the triazene chains. Other remarkable types of interactions in 1 are bifurcated hydrogen contacts and non-classical CH···π bonding. Complexes 2 and 3 present a planar geometry, supported also through bifurcated intramolecular Cl···H-C interactions, as well as the occurrence of trifurcated Cl···H-C intermolecular interactions.     

Structural characterization and dielectric properties of the solid solutions AgPb(Sb,Bi)S3

The new solid solutions AgPbSb_1 − x Bi _x S₃ were prepared by solid state reactions. The phases were characterized by powder X-ray diffractions (XRD), scanning electron microscopy, and thermal analysis. The XRD patterns of different members (x = 0.5, 0.7, 0.8, and 1.0) are consistent with pure phases crystallizing in the cubic PbS-type structure. The electrical characterization was carried out using ac impedance spectroscopy and dc methods. The temperature dependence of the dc conductivity shows typical semiconductor Arrhenius behavior. The impedance measurements were performed in the frequency range of 0.1 Hz to 10 MHz and at the temperature range of 15 °C to 350 °C. The ac conductivity conforms to Jonscher’s universal power law. The frequency dependence of the dielectric permittivity follows the normal dielectric material behavior, and the relaxation is thermally activated. The frequency and temperature dependences of the electrical data are found to follow Summerfield scaling formalism.     

Potentiometric studies on the complexation of copper(II) by phenolic acids as discrete ligand models of humic substances

Studies on the complexation of copper(II) by phenolic acids, as ligand models of humic substances were done by potentiometry. The acids under study were: 3,4-dihydroxyhydrocinnamic acid or hydrocaffeic acid (1), 3,4-dihydroxyphenylacetic acid (2) and 3,4-dihydroxybenzoic acid or protocatechuic acid (3). Acidity constants of the ligands and the formation constants of metal-ligand complexes were evaluated by computer programs. The carboxylic group of the phenolic acids has different pK_a1 values, being the dissociation constants intrinsically related with the distance between the function and the aromatic nucleus. The results obtained allow concluding that acidity constants of the catechol moiety of the compounds are similar with pK_a2 and pK_a3 values between 9.47-9.41 and 11.55-11.70. The complexation properties of the three ligands towards copper(II) ion are quite similar, being the species found not different either in nature or stability. Although the model ligands have some structural differences no significant differences were found in their complexation properties towards copper(II). So, it can be postulated that complexation process is intrinsically related with the presence of a catechol group.