Fluorescent behavior of B-phycoerythrin in microemulsions of aerosol OT/water/isooctane

Taking advantage of its unusual fluorescent properties, the incorporation of B-phycoerythrin (B-PE) in aerosol OT (AOT, sodium bis-(2-ethylhexyl) sulphosuccinate)/water/isooctane microemulsions was investigated by following their steady-state and time-resolved fluorescence as a function of the water-to-surfactant molar ratio, w(0). The fluorescent intensity at 575 nm increased continuously with increasing water content, saturating at a w(0) around 35 and staying practically constant at w(0)> or =40. The steady-state anisotropy showed an initial increase with increasing water content until w(0)=23 and then decreased strongly, staying practically constant when w(0)> or =40. The values of the fluorescent parameters, anisotropy and fluorescent intensity, were unchanged when the water content of the system increased in the range between w(0)=40 to 50. This implies the effective incorporation of B-PE in the microemulsion droplets with w(0)> or =40, as well as the equilibrium of the dispersion at these water/surfactant ratios, since higher water content does not affect the main surrounding microenvironment of the protein. The overall incorporation in the microemulsion droplets caused minor spectroscopic changes with respect to biliprotein in aqueous solution of 20 mM sodium phosphate buffer, pH 7.0, such as a blue absorption shift of 3 nm and an emission shift of 1.5 nm, as well as a slight increase in excitation anisotropy spectrum mainly caused by a decrease in protein mobility. Therefore, there are no important interactions between the chromophores and the AOT sulfonate head groups. Emission intensity decays followed complex kinetics in both aqueous and dispersion media. The stability with time and temperature of the biliprotein in the microemulsion was higher than in the aqueous solution. All the results can be explained in terms of B-PE inclusion in the water droplets of AOT microemulsions where the protein has similar configuration and conformation to that in aqueous solution but with the chromophores more protected.     

Sample preparation improvement in polycyclic aromatic hydrocarbons determination in olive oils by gel permeation chromatography and liquid chromatography with fluorescence detection

The determination of 15 polycyclic aromatic hydrocarbons (PAHs) in olive oil samples has been improved in order to obtain a fast methodology with a low limit of detection through the combination of liquid-liquid extraction with acetonitrile and preparative gel permeation chromatography (GPC) prior to the injection of purified extracts into a C18 column. Acetonitrile-water was used as the mobile phase with a gradient from 50 to 95%, w/w, acetonitrile in 30 min. The oven temperature was maintained at 15 degrees C, and fluorometric detection was made at a fixed excitation wavelength of 264 nm and variable, optimal emission wavelength for each analyte ranging from 352 nm for 11-H-benzo(b)fluorene to 500 nm for indeno(1,2,3-cd)pyrene. Recovery for all the compounds studied varied from 75 to 111%, and limit of detection values from 0.05 ng/g for benzo(k)fluoranthene to 0.48 ng/g for indeno(1,2,3-cd)pyrene, corresponding to 0.09 ng/g benzo(a)pyrene. Results were compared with those obtained by liquid-liquid extraction followed by a cleanup on silica and a direct GPC treatment of oil samples diluted in dichloromethane, 2 other methodologies that are appropriate for quantifying PAHs in olive oils. However, the proposed method improves the determination limits, reduces the time of analysis, and provides a highly stable baseline for sample chromatograms.     

UV index experimental values during the years 2000 and 2001 from the Spanish broadband UV-B radiometric network

An analysis is made of experimental ultraviolet erythemal solar radiation data measured during the years 2000 and 2001 by the Spanish UV-B radiation evaluation and prediction network. This network consists of 16 Robertson-Berger type pyranometers for evaluating solar erythemal radiation and five Brewer spectroradiometers for evaluating the stratospheric ozone. On the basis of these data the Ultraviolet Index (UVI) was evaluated for the measuring stations that are located either in coastal regions or in the more densely populated regions inland on the Iberian Peninsula. It has been checked that in most cases the maximum irradiance values corresponded to solar noon, although there were exceptions that could be explained by cloudiness. The maximum experimental values of the UVI were around 9 during the summer, though frequently passing this value at the inland measurement stations. The annual accumulated dose of irradiation on a horizontal plane has also been studied, as well as the evolution through the year in units of energy, standard erythemal doses and minimum erythemal doses, according to different phototypes.     

13C-NMR relaxation studies of alkali metal cryptate complexes

The ¹³C spin-lattice relaxation times (T₁'s) of cryptands [2.1.1], [2.2.1] and [2.2.2] as well as those of the corresponding cryptate complexes with Li⁺, Na⁺, and K⁺ in CDCl₃ and CH₃OH:D₂O (90:10) were measured and the results are interpreted in terms of molecular compression and desolvation effects.     

Nutritional parameters of commercially available milk samples by FTIR and chemometric techniques

A chemometric study on the prediction of the main nutritional aspects of milk has been carried out by using fourier transform infrared spectroscopy (FTIR) attenuated total reflectance (ATR) measurements of commercially available milk samples of different types. Whole, semi and skimmed milks, enriched or not with calcium, vitamins or modified by alteration of lipid or sugar composition were considered. After evaluating different strategies for data acquisition and ATR cleaning between samples, hierarchical cluster analysis (HCA) was carried out for classification of samples in order to choose the calibration set. The prediction capabilities of partial least squares (PLS) data treatment were evaluated in order to obtain information about total fat, total protein, total carbohydrates (CH), calories and calcium. On using the mean square error of cross-validation and prediction as control variables, a critical evaluation were made about the calibration set to be used, the spectral range to be considered and the data treatment (PLS-1 or PLS-2) to be performed. By selecting a calibration set of 33 samples the properties of 48 samples were predicted with relative precision of triplicates of 0.062, 0.040 and 0.039% w/v for total fat, protein and carbohydrates, and 0.66 kcal/100 ml for calories, and 2.1 mg of Ca/100 ml. The mean difference (d_x−y) between predicted and actual values and standard deviation of mean differences (s_x−y), were of 0.06 (0.38), 0.03 (0.18) and −0.15 (0.41), being s_x−y values between brackets, for total fat, proteins and carbohydrates, 0.06 (3.8) kcal/100 ml for calories and −4.5 (9) mg/100 ml for calcium.The sensitivity and selectivity of the methodology developed were evaluated on terms of the net analyte signal. Selectivity factors ranging from 2 to 7.6% have been calculated for the five parameters considered.     

Microwaves in organic synthesis. Thermal and non-thermal microwave effects

Microwave irradiation has been successfully applied in organic chemistry. Spectacular accelerations, higher yields under milder reaction conditions and higher product purities have all been reported. Indeed, a number of authors have described success in reactions that do not occur by conventional heating and even modifications of selectivity (chemo-, regio- and stereoselectivity). The effect of microwave irradiation in organic synthesis is a combination of thermal effects, arising from the heating rate, superheating or "hot spots" and the selective absorption of radiation by polar substances. Such phenomena are not usually accessible by classical heating and the existence of non-thermal effects of highly polarizing radiation--the "specific microwave effect"--is still a controversial topic. An overview of the thermal effects and the current state of non-thermal microwave effects is presented in this critical review along with a view on how these phenomena can be effectively used in organic synthesis.     

The consecutive [2+2] cycloaddition-ring expansion route to diastereomeric 1,4-diazepin-5-ones from imino-ketenimines. Alternative intramolecular transamidation of β-lactams

Azeto[1,2-a]imidazoles are prepared by a formal intramolecular [2+2] cycloaddition of imino-ketenimines in which an ethylene chain is linking the nitrogen atoms of both functionalities, bearing a methyl and a phenyl group on the terminal carbon atom of the heterocumulene. By acid-catalyzed hydrolysis these azeto[1,2-a]imidazoles are converted into 6,6,7-trisubstituted hexahydro-1,4-diazepin-5-ones, which have been alternatively prepared via intramolecular transamidation of N-(2-aminoethyl)-β-lactams.     

New [Mo(eta3-allyl)(CO)2L3]+ complexes with monodentate or tridentate nitrogen-donor ligands

Cationic complexes [Mo(eta(3)-allyl)(CO)2L3]+ (L3 = either nitrogen-donor tridentate ligand or three monodentate ligands) were prepared in high yield and under mild conditions using as precursors either the triflato complex [Mo(eta(3)-allyl)(OTf)(CO)2(NCMe)2] or the combination of the chloro complex [Mo(eta(3)-allyl)Cl(CO)2(NCMe)2] and the salt NaBAr'(4)(Ar'= 3,5-bis(trifluoromethyl)phenyl). The tridentate ligands employed were 2,2':6',2'-terpyridine (terpy) and cis,cis-1,3,5-cyclohexanetriamine (CHTA), whereas the monodentate ligands imidazole (im) and 3,5-dimethylpyrazole (dmpz) were chosen. In order to stabilize the labile intermediates, an excess of acetonitrile was used in most of the syntheses. However, the pyrazole complex was prepared through a nitrile-free route to avoid reactions at the coordinated nitrile. The solid state structures of [Mo(eta(3)-methallyl)(CO)2(terpy)]OTf (2), [Mo(eta(3)-methallyl)(CO)2(CHTA)]BAr'4 (3), [Mo(eta(3)-methallyl)(CO)2(NCMe)3]BAr'4 (4), [Mo(eta(3)-allyl)(CO)2(im)3]OTf (5) and [Mo(eta(3)-allyl)(CO)2(dmpz)3]BAr'4 (6) were determined by means of single-crystal X-ray diffraction.     

Identifying acetylated lignin units in non-wood fibers using pyrolysis-gas chromatography/mass spectrometry

A series of non-wood plant fibers, namely kenaf, jute, sisal and abaca, have been analyzed upon pyrolysis-gas chromatography/mass spectrometry (Py-GC/MS) of the whole material. The pyrolysis products mainly arise from the carbohydrate and lignin moieties of the fibers. The lignin-derived phenols belonged to the p-hydroxyphenylpropanoid (H), guaiacylpropanoid (G) and syringylpropanoid (S) structures, and showed a high S/G ratio of between 2.0 and 5.4, the highest corresponding to kenaf. Among the lignin-derived phenols released, small amounts of sinapyl and coniferyl acetates (in both cis- and trans-forms) were identified for the first time upon Py-GC/MS of lignocellulosic materials. Acetylation of the sinapyl and coniferyl alcohols was at the gamma-position of the side chain. The release of these alcohols derived from intact acetylated lignin units upon pyrolysis seems to indicate that the native lignin in the fibers selected for this study is at least partially acetylated. Sinapyl (and coniferyl) acetates have recently been suggested to be authentic lignin precursors involved in the polymerization of lignin along with the normal sinapyl and coniferyl alcohols. Py-GC/MS will offer a convenient and rapid tool for analyzing naturally acetylated lignins, as well as to screen plant materials for the presence of acetylated units in lignin.     

Rationally functionalized deltahedral zintl ions: synthesis and characterization of [Ge9-ER3]3-, [R3E-Ge9-ER3]2-, and [R3E-Ge9-Ge9-ER3]4- (E=Ge, Sn; R=Me, Ph)

Six new derivatized deltahedral Zintl ions have been synthesized by reactions between the known Zintl ions Ge(9) (n-) with the halides R(3)EX and/or the corresponding anions R(3)E(-) for E=Ge or Sn. This rational approach is based on our previous discovery that these derivatization reactions are based on nucleophilic addition to the clusters. All species were structurally characterized as their salts with potassium countercations sequestered in 2,2,2-crypt or [18]crown-6 ether. The tin-containing anions were characterized also in solutions by (119)Sn NMR spectroscopy. The reaction types for such substitutions and the structures of the new anions are discussed.