AlPO4?ZrO2 catalysts, II. Synthesis, textural properties and crystal structure of systems obtained in ethylene oxide

The effects of surface dehydration on textural properties, crystallinity and the structure of AlPO₄–ZrO₂ (weight ratio AlPO₄/ZrO₂=3) systems precipitated with ethylene oxide have been studied by N₂ adsorption and XRD measurements. The increase in calcination temperature in the range 773–1273 K decreases the textural parameters as a consequence of AlPO₄ crystallization to the tridymite form.

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, AlPO₄–ZrO₂ ( AlPO₄/ZrO₂=3), , N₂ - . 773 1273 , AlPO₄ .

     

Use of dynamically coated capillaries with added cyclodextrins for the analysis of opium using capillary electrophoresis

A rapid, precise, accurate, and robust method using capillary electrophoresis (CE) with dynamically coated capillaries for the analysis of the major opium alkaloids in opium is presented. Dynamic coating of the capillary surface is accomplished using a commercially available reagent kit (polycation coating followed by polyanion coating). The addition of dual cyclodextrins (hydroxypropyl-beta-cyclodextrin and dimethyl-beta-cyclodextrin) to the run buffer imparts excellent selectivity for the opium alkaloids. For the determination of morphine, papaverine, codeine, noscapine and thebaine in opium gum and opium latex samples (using tetracaine as an internal standard) good agreement with values obtained by gradient high-performance liquid chromatography is obtained. Compared to the latter technique, CE affords better resolution with significantly faster analysis time (12 min versus 29 min). Dynamically coated capillaries, which give rise to a relatively high and robust electroosmotic flow (EOF) at the background electrolyte pH of 2.5, allow for rapid analysis and excellent migration time and peak area precision (RSDs < or = 0.12% and < or = 1.2%, respectively). Reproducible separations (relative migration times) for over 500 samples have been obtained on a single capillary. The nature of the injection solvent, the injection time and the contents of the waste vials have a profound effect on the pressure injection precision of the relatively hydrophobic solutes. The CE conditions reported in this study are also applicable to the analysis of lysergic acid diethylamide (LSD) exhibits.     

Simultaneous determination of iron, cobalt, nickel and copper by UV-visible spectrophotometry with multivariate calibration

A method for the simultaneous spectrophotometric determination of the divalent ions of iron, cobalt, nickel and copper based on the formation of their complexes with 1,5-bis(di-2-pyridylmethylene) thiocarbonohydrazide (DPTH) is proposed. The resolution of quaternary mixtures of these metallic ions was accomplished by several chemometric approaches. A comparative study of the results obtained for simultaneous determinations in mixture by using principal component regression (PCR) and partial least-squares regression (PLS-1 and PLS-2) for absorbance, first-derivative and second-derivative data is presented. In general, the best recovery values are obtained by the PLS-2 method for absorbance data. This procedure allows the simultaneous determination of the cited ions in alloys and biological materials Good reliability of the determination was proved.     

Selection of the cis and trans phosph(III)azane macrocycles [{P(mu-NtBu)}2(1-Y-2-NH-C6H4)]2(Y=O, S)

The 1 : 1 reactions of [ClP(mu-NtBu)]2 with the difunctional aromatic amines 1,2-1-YH-2-NH2-C6H4 in the presence of Et3N give the dimeric phosph(III)azane macrocycles [{P(mu-NtBu)2(1-Y-2-HN-C6H4)]2, predominantly as the cis isomer in the case of Y=O (1.cis) and as the trans isomer for Y=S (2.trans). Model M.O. calculations suggest that the selection of the cis and trans isomers is not thermodynamically controlled. The alternative isomers 1.trans and 2.cis are generated exclusively by the deprotonation of the model intermediates [(1-Y-2-NH2-C6H4)P(mu-NtBu)]2[Y=O (3), S (4)] with nBuLi followed by cyclisation with [ClP(mu-NtBu)]2. The solid-state structures of 1.cis/trans(50 : 50), 2.cis, 3 and 4 are reported.     

Asymmetric Induction in the Synthesis of 3,4,5-Trisubstituted Ferrocenyl-4,5-dihydropyrazoles

The asymmetric induction in the synthesis of 3,4,5-trisubstituted 4,5-dihydropyrazoles with ferrocenyl substituents, starting from the E and Z isomers of ,-unsaturated ketones was studied. A high diastereoselectivity was revealed at the 1,2 chiral center chiral center induction, which is independent of the configuration of the starting chalcones.     

(Z)-3-p-tolylsulfinylacrylonitrile as a chiral dienophile: diels-alder reactions with furan and acyclic dienes

The behavior of (Z)-3-p-tolylsulfinylacrylonitrile (1) as a chiral dienophile has been evaluated from its reactions with furan and acyclic dienes. Electrostatic interactions of the cyano group with the sulfinyl one restrict the conformational mobility around the C-S bond, thus controlling the pi-facial selectivity, which is almost complete in all cases, the approach of the diene from the less-hindered face of the dienophile (that bearing the lone electron pair) in the predominant rotamer being the favored one. The regioselectivity is also completely controlled by the cyano group. Additionally, the reactivity of compound 1 as well as its endo-selectivity are both higher than those observed for the corresponding (Z)-3-sulfinylacrylates, thus proving the potential of sulfinylnitriles as chiral dienophiles.     

Separation of proteins with a molecular mass difference of 2 kDa utilizing preparative double-inverted gradient polyacrylamide gel electrophoresis under nonreducing conditions: application to the isolation of 24 kDa human growth hormone

A method for separating proteins with a molecular mass difference of 2 kDa using SDS-PAGE under nonreducing conditions is presented. A sample mixture containing several human growth hormone (hGH) isoforms was initially separated on a weak anion-exchange column. Fractions rich in 24 kDa hGH as determined by analytical SDS-PAGE were pooled and further separated by cation-exchange chromatography. The fractions pooled from the cation-exchange chromatography contained two hGH isoforms with a 2 kDa molecular mass difference according to SDS-PAGE analysis, 22 and 24 kDa hGH. The 22 and 24 kDa hGH were separated using continuous-elution preparative double-inverted gradient PAGE (PDG-PAGE) under nonreducing conditions. The preparative electrophoresis gel was composed of three stacked tubular polyacrylamide matrices, a 4% stacking gel, a 13-18% linear gradient gel, and a 15-10% linear inverted gradient gel. Fractions containing purified 24 kDa hGH were pooled and Western blot analysis displayed immunoreactivity to antihGH antibodies. PDG-PAGE provides researchers with an electrophoretic technique to preparatively purify proteins under nonreducing conditions with molecular mass differences of 2 kDa.     

The complexation of Cr(III) and Cr(VI) with flavones in micellar media and its use for the spectrophotometric determination of chromium

The complexation of chromium by different flavonoid dyes in micellar media has been studied, in particular the reaction between chromium and quercetin. Micellar effects, the reaction pathway proposed and the application of the method to the determination of Cr(VI) and Cr(VI) + Cr(III) mixtures are discussed.     

Evaluation of soybean seed protein extraction focusing on metalloprotein analysis

Two methods of protein extraction for soybean seeds were evaluated in terms of preservation of the metal ions bound to proteins after the extraction and separation procedures. The proteins were firstly separated according to their molar masses by polyacrylamide gel electrophoresis. Then, the protein bands were mapped by synchrotron radiation X-ray fluorescence in order to establish which metal ions were present in each one. Finally, some mapped protein bands were decomposed by microwave-assisted combustion and Ca, Cu, K, Mg, Mn, and Zn were quantified by inductively coupled plasma mass spectrometry or inductively coupled plasma optical emission spectrometry. The extraction methods studied were Method A (based on the treatment of ground soybean seeds with hexane and their extraction with Tris–HCl and β-mercaptoethanol) and Method B (based on the treatment of ground soybean seeds with petroleum ether and their extraction with Tris–HCl, dithiothreitol, phenylmethanesulfonyl fluoride, sodium dodecyl sulfate and potassium chloride). The best method was Method B, in which a 78% higher extraction efficiency was obtained when compared to Method A. Additionally, the metal-protein interactions were more appropriately preserved when Method B was applied, where the most affected ions were those that are bound weakly to proteins, such as Ca, K, and Mg.