Organophosphorus reagents as extractants-part 3. Synergic effect of triphenyl phosphine oxide and bis(diphenyl phosphinyl) alkanes on extraction of iron(III) from thiocyanate medium with 2,4-pentdione

The extraction of iron(III) from thiocyanate medium was carried out with a synergic combination of 2,4-pentdione (Hacac) and either triphenyl phosphine oxide (Ph(3) PO) or bis (diphenylphosphinyl) alkanes, Ph(2)P(O)(CH(2))(n).P(O)PH(2) [ligand abbreviation, n: dpeO(2), 2; dpbO(2), 4]. Iron(III) was quantitatively separated from its binary mixture with chromium(III), manganese(III), cobalt(II), nickel(II), zinc(II), cadmium(II), mercury(II), lead(II), magnesium(II) and from steel samples. Copper(II) and silver(I) however, interfered. The percentage extraction was 99.0%. The respective extraction constants, K(HA), K(L) or K(syn), for the extracted species, [Fe(NCS)(acac)(2)(H(2)O)] (HA Hacac), Fe(NCS)(3)L(2) [L b Ph(3)PO, dpeO(2) or dpbO(2)], or Fe(NCS)(acac)(2)L were found to be: K(HA), 1.48 x 10(3), K(L), 1.80 x 10(2) (L Ph(3)PO), 2.02 x 10(2) (L dpeO(2) or dpbO(2)) and K(syn), 1.87 x 10(6) (L Ph(3)PO), 2.56 x 10(6) [L dpeO(2) or dpbO(2)].     

Efficient transesterification/acylation reactions mediated by N-heterocyclic carbene catalysts

Imidazol-2-ylidenes, a family of N-heterocyclic carbenes (NHC), are efficient catalysts in the transesterification involving numerous esters and alcohols. Low catalyst loadings of aryl- or alkyl-substituted NHC catalysts mediate the acylation of alcohols with enol acetates in short reaction times at room temperature. Commercially available and more difficult to cleave methyl esters react with primary alcohols in the presence of alkyl-substituted NHC to efficiently form the corresponding esters. While primary alcohols are selectively acylated over secondary alcohols with use of enol esters as acylating agents, methyl and ethyl esters can be employed as protective agents for secondary alcohols in the presence of the more active alkyl-substituted NHC catalysts. The NHC-catalyzed transesterification protocol was simplified by generating the imidazol-2-ylidene catalysts in situ.     

Tractable molecular theory of transport of Lennard-Jones fluids in nanopores

We present here a tractable theory of transport of simple fluids in cylindrical nanopores, which is applicable over a wide range of densities and pore sizes. In the Henry law low-density region the theory considers the trajectories of molecules oscillating between diffuse wall collisions, while at higher densities beyond this region the contribution from viscous flow becomes significant and is included through our recent approach utilizing a local average density model. The model is validated by means of equilibrium as well nonequilibrium molecular dynamics simulations of supercritical methane transport in cylindrical silica pores over a wide range of temperature, density, and pore size. The model for the Henry law region is exact and found to yield an excellent match with simulations at all conditions, including the single-file region of very small pore size where it is shown to provide the density-independent collective transport coefficient. It is also shown that in the absence of dispersive interactions the model reduces to the classical Knudsen result, but in the presence of such interactions the latter model drastically overpredicts the transport coefficient. For larger micropores beyond the single-file region the transport coefficient is reduced at high density because of intermolecular interactions and hindrance to particle crossings leading to a large decrease in surface slip that is not well represented by the model. However, for mesopores the transport coefficient increases monotonically with density, over the range studied, and is very well predicted by the theory, though at very high density the contribution from surface slip is slightly overpredicted. It is also seen that the concept of activated diffusion, commonly associated with diffusion in small pores, is fundamentally invalid for smooth pores, and the apparent activation energy is not simply related to the minimum pore potential or the adsorption energy as generally assumed.     

On-chip electrochromatography using sol-gel immobilized stationary phase with UV absorbance detection

A chromatography column on a chip was fabricated by immobilizing reversed-phase stationary phase particles (5 microm, C4) using sol-gel technology. Channels were fabricated in quartz using photolithography and wet etching. Localization of the stationary phase was achieved by immobilizing the stationary phase at the desired location in the separation channel prior to bonding of the cover plate. Cross channel design was employed for gated injection. An optical fiber setup was developed for carrying out on-chip UV absorbance detection. The effective optical path length was theoretically determined for the trapezoidal shaped channel and the result was shown to match closely with the experimentally determined value. The effect of applied voltage on velocity was evaluated using thiourea as an unretained marker. Separation performance of the stationary phase was demonstrated by separation of three peptides (Trp-Ala, Leu-Trp and Trp-Trp) under isocratic chromatographic conditions.     

Survival probability in one dimension for theA+B→B reaction with hard-core repulsion

We study the effect of hard-core repulsion (known as the bus effect) betweenB particles on the reaction-diffusion systemA+BB in the continuous-time random walk model in one dimension with theA particles stationary. We show rigorously that the survival probability of theA particles is asymptotically bounded asC ₁lim _t{[–logS(t)]/t ^0.5}C ₂, whereC ₁ andC ₂ are constants. We also do simulations to confirm our results.     

Spectrophotometric determination of ruthenium(III) using diphenylcarbazone

Summary The purple violet ruthenium(III)-diphenylcarbazone complex which is formed at p _h 5–7, and has an absorption maximum at 530 nm with molar absorption coefficient 16.2·10⁴l.cm^–1.mole^–1 is suggested for the estimation of 20–125g ruthenium(III) spectrophotometrically in 30–60% ethanol. The complex is stable over p _h range 3.2–8.4. The limits of interference due to foreign ions have been studied.

---

Zusammenfassung Der bei p _h 5 bis7 entstehende Ruthenium(III)-Diphenylcarbazon-Komplex hat ein Absorptionsmaximum bei 530 nm und einen Absorptionskoeffizienten von 16,2·10⁴ l.cm^–1.Mol^–1. Die spektrophotometrische Bestimmung von 20 bis 125g Ruthenium(III) in 30 bis 60%igem Äthanol mit Hilfe dieses zwischen p _h 3,2 und 8,4 beständigen Komplexes wurde vorgeschlagen. Die Störung durch Fremdionen wurde geprüft.

     

Use of zirconium(IV) and antimony(III) for structural investigation of flavonoids

Summary The absorption spectra (in the visible and ultraviolet) of the complexes formed in absolute methanol between Zr⁴⁺, V⁴⁺, Y³⁺ and Sb³⁺ with 3-hydroxyflavone, apigenin, hesperidin, naringenin, morin, kaempferol, quercetin, rutin and myricetin have been studied. Zr⁴⁺ and Sb³⁺ form complexes that are stable in acid medium. The stoichiometry of the vairous Zr⁴⁺-flavonoid complexes formed in methanol and methanol/HClO₄ media has been determined by the molar ratio method. The preferred sites for complex formation of flavonoids with Zr⁴⁺ are postulated. Zr⁴⁺ forms chelates with the 3-hydroxy-4-keto and 5-hydroxy-4-keto systems simultaneously. Sb³⁺ forms complexes only with the 3,5-dihydroxy system in flavonoids. The results permit estimation of the relative order of chelating power of each type of binding site and are useful in elucidation of the structure of the flavonoids.

---

Verwendung von Zirkonium(III) und Antimon(III) für die Erforschung der Flavonoide

Zusammenfassung Die Absorptions-Spektren (im sichtbaren und UV-Bereich) der in absolutem Methanol hergestellten Komplexe von Zr⁴⁺, V⁴⁺, Y³⁺ und Sb³⁺ mit 3-Hydroxyflavon, Apigenin, Hesperidin, Naringenin, Morin, Kaempferol, Quercetin, Rutin und Myricetin wurden untersucht. Zr⁴⁺ und Sb³⁺ bilden in saurem Milieu beständige Komplexe. Die Stöchiometrie der verschiedenen Zr⁴⁺-Flavonoid-Komplexe, die in Methanol bzw. Methanol/ HClO₄ hergestellt wurden, wurde durch Bestimmung der Molarverhältnisse ermittelt. Die für die Komplexbildung bevorzugten Stellen (im Molekül) wurden angegeben. Zr⁴⁺ bildet Chelate mit der 3-Hydroxy-4-keto- und mit der 5-Hydroxy~4-ketogruppe. Sb³⁺ bildet solche Komplexe nur mit der 3,5-Dihydroxy-4-keto-Gruppe in Flavonoiden. Die Untersuchungsergebnisse ermöglichen die Abschätzung der Komplexbildungsfähigkeit der verschiedenen Gruppierungen und sind für die Strukturaufklärung von Nutzen.

     

High-pressure adsorption capacity and structure of CO2 in carbon slit pores: theory and simulation

We present new simulation results for the packing of single-center and three-center models of carbon dioxide at high pressure in carbon slit pores. The former shows a series of packing transitions that are well described by our density functional theory model developed earlier. In contrast, these transitions are absent for the three-center model. Analysis of the simulation results shows that alternations of flat-lying molecules and rotated molecules can occur as the pore width is increased. The presence or absence of quadrupoles has negligible effect on these high-density structures.