Electrokinetic molecular separation in nanoscale fluidic channels

This report presents a study of electrokinetic transport in a series of integrated macro- to nano-fluidic chips that allow for controlled injection of molecular mixtures into high-density arrays of nanochannels. The high-aspect-ratio nanochannels were fabricated on a Si wafer using interferometric lithography and standard semiconductor industry processes, and are capped with a transparent Pyrex cover slip to allow for experimental observations. Confocal laser scanning microscopy was used to examine the electrokinetic transport of a negatively charged dye (Alexa 488) and a neutral dye (rhodamine B) within nanochannels that varied in width from 35 to 200 nm with electric field strengths equal to or below 2000 V m-1. In the negatively charged channels, nanoconfinement and interactions between the respective solutes and channel walls give rise to higher electroosmotic velocities for the negatively charged dye than for the neutral dye, towards the negative electrode, resulting in an anomalous separation that occurs over a relatively short distance (<1 mm). Increasing the channel widths leads to a switch in the electroosmotic transport behavior observed in microscale channels, where neutral molecules move faster because the negatively charged molecules are slowed by the electrophoretic drag. Thus a clear distinction between "nano-" and "microfluidic" regimes is established. We present an analytical model that accounts for the electrokinetic transport and adsorption (of the neutral dye) at the channel walls, and is in good agreement with the experimental data. The observed effects have potential for use in new nano-separation technologies.     

Determination of coumarins by voltammetric techniques in micellar and emulsified media

An electroanalytical study of the oxidation processes of umbelliferone and hymecromone at a glassy carbon electrode in micellar solution and emulsified medium by different voltammetric techniques is described. The non-ionic surfactant Triton X-405 in acetate-buffered medium at pH 4.8 was found to be the most suitable. Different ranges of linearity were obtained in the micellar solutions, depending on the technique used; the limits of determination for differential pulse voltammetry (DPV) at a stationary electrode were 2.9×10^?6 mol l^?1 and 3.3×10^?6 mol l^?1 for umbelliferone and hymecromone, respectively. In the emulsified medium formed with a mixture of toluene and ethyl acetate (3:2), the oxidation processes yielded similar results. With DPV, linear calibration plots were obtained in the ranges 1.0×10^?5–9.0×10^?7 mol l^?1 umbelliferone and 1.0×10^?5–2.0×10^?6 mol l^?1 hymecromone. The media used are predominantly aqueous so that special reference electrodes and solvent purification are not needed.     

Dehydration and crystallization process in sol-gel zirconia

Sol-gel zirconia was characterized using high-resolution thermogravimetry (Hi-Res TG) and differential scanning calorimetry (DSC) and compared with X-ray diffraction, Raman scattering, and UV-Vis spectroscopy. ZrO_2-x(OH)_2x·yH₂O annealed below 400°C show typical behavior of amorphous material. As the annealing temperature is increased, the tetragonal and monoclinic phases crystallize. Typical Hi-Res TG curve shows that the samples are continuously dehydrated in a long temperature range, between room temperature and 600°C. The total mass loss relative to the initial mass is of about 29%. The DSC analysis coupled with TG and structural information, indicate that the exothermic processes about 355 and 447°C can be related to the nucleation process of the formation of tetragonal zirconia, with bulk crystallization at 447°C. This revised version was published online in July 2006 with corrections to the Cover Date.     

A novel synthesis of 3-cyanoindoles and a new route to indole-3-carboxylic acid derivatives

2-Alkyl-3-cyanoindoles are obtained when 1-alkylmethyl-2-chloro-(or 2-phenylsulfonyl)-3-phenylsulfonylindoles are reacted with excess azide ion (90°/DMF). The reaction is considered to occur by a fragmentation recombination process in which the Schiff's base $\text{12}$ is of central importance. This proposal is supported by the formation of 2-substituted indole-3-carboxylates $\text{17}$ from aldehydes and the α-phenylsulfonyl-$\text{o}$-aminophenylacetic acid ester derivative $\text{16}$.     

Phenol methylation over CrPO4 and CrPO4?AlPO4 catalysts

The vapor-phase catalytic alkylation of phenol with methanol and dimethyl carbonate on a series of differently prepared CrPO₄ (Cr/P=1) and CrPO₄-AlPO₄ (CrAIP) catalysts, has been studied at different temperatures (473–673 K). The reaction is first order in phenol, giving a mixture of O- and C-alkylated products (C-alkylation taking place preferentially at theortho-position). Moreover, dimethyl carbonate is a better methylating agent than methanol.     

Single-crystal 2H NMR of deuterated 1,10-decanedicarboxylic acid included in hydrogenated urea channels

The intergrowth of 1,10-decanedicarboxylic acid and urea give infinite hydrogen-bonded chains of the guest included in the hexagonal urea host. A deuterium high-resolution solid-state NMR study of the selectively deuterated intergrowth compound 1,10-decanedicarboxylic acid/hydrogenated urea at variable temperature in the range 90 < or = T < or = 300 K was performed on a single crystal. The analysis of the second moment as a function of temperature is shown to be compatible with the known phase transition occurring near T(c) = 203 K. Moreover, the spectra indicate that the orientational disorder is strong, and is compared to an axial uniform disorder. For this purpose, the general equation for the second moment of a system with uniform two-dimensional axial orientational disorder is given, and a method to take into account the non-uniform excitation of the pulse sequence is proposed.     

Heterogeneous oxidation of pyrimidine and alkyl thioethers in ionic liquids over mesoporous Ti or Ti/Ge catalysts

Heterogeneous catalytic oxidation of a series of thioethers (2-thiomethylpyrimidine, 2-thiomethyl-4,6-dimethyl-pyrimidine, 2-thiobenzylpyrimidine, 2-thiobenzyl-4,6-dimethylpyrimidine, thioanisole, and n-heptyl methyl sulfide) was performed in ionic liquids by using MCM-41 and UVM-type mesoporous catalysts containing Ti, or Ti and Ge. A range of triflate, tetrafluoroborate, trifluoroacetate, lactate and bis(trifluoromethanesulfonyl)imide-based ionic liquids were used. The oxidations were carried out by using anhydrous hydrogen peroxide or the urea-hydrogen peroxide adduct and showed that ionic liquids are very effective solvents, achieving greater reactivity and selectivity than reactions performed in dioxane. The effects of halide and acid impurities on the reactions were also investigated. Recycling experiments on catalysts were carried out in order to evaluate Ti leaching and its effect on activity and selectivity.     

Calculation of the electronic properties of neutral and ionized divalent-metal clusters

The electronic properties of neutral and ionized divalent-metal clusters have been studied using a microscopic theory, which takes into account the interplay between van der Waals (vdW) and covalent bonding in the neutral clusters, and the competition between hole delocalization and polarization energy in the ionized clusters. By calculating the ground-state energies of neutral and ionized Hg _n clusters, we determine the size dependence of the bond character and the ionization potentialI _p (n). For neutral Hg _n clusters we obtain a transition from van der Waals to covalent behaviour at the critical sizen _c ～10–20 atoms. Results forI _p (Hg _n ) withn≤20 are in good agreement with experiments, and suggest that small Hg _n ⁺ clusters can be viewed as consisting of a positive trimer core Hg ₃ ⁺ surrounded byn?3 polarized neutral atoms.     

Nitrosation of peptide bonds. Cleavage of nitrosated peptides by pyrrolidine and α-amino esters

The reaction of several α-amino acids and peptides (containing Gly, L-Ala, L-Leu, L- or DL-Phe, and/or L- or D-Val) with air-diluted nitrogen oxides has been studied to roughly mimic the N-nitrosation of peptide bonds that the contaminated urban air might produce in pulmonary tissues. Most N-protected α-amino acids give practically quantitative yields of N-nitroso derivatives. N-Protected dipeptides afford either dinitrosated peptides, mixtures of di- and mononitrosated compounds, selectively mononitrosated products, or no reaction at all, depending mainly on steric effects. The same trends are observed for some higher peptides. The (po1y)nitrosated Peptides, which retain the chirality of the starting materials, have been characterized by ¹H and ¹³C NMR spectroscopy and are cleaved by pyrrolidine and amino esters under mild conditions to give (new) amides or peptides plus diazo derivatives.     

KMo5O13 and KNb1.76Sb3.24O13

The title compounds, potassium pentamolybdenum oxide, KMo₅O₁₃, and potassium niobate antimonate or potassium niobium antimony oxide (1/1.76/3.24), KNb_1.76Sb_3.24O₁₃, were synthesized by solid‐state reactions and are isomorphous in space group Cmcm. The structure of the Mo complex has three unique Mo atoms and consists of MoO₆ octahedra sharing edges to form Mo₂O₆ pairs and Mo₃O₉ triplets, which, in turn, form layers by sharing corners. These layers are linked together in the [100] direction, yielding a three‐dimensional network similar to that of KSb₅O₁₃. This framework delimits interconnected tunnels, running approximately along the [110] and [10] directions, in which K⁺ ions are located. In the isomorphous KNb_1.76Sb_3.24O₁₃ structure, one of the Mo sites in KMo₅O₁₃ is replaced by Sb and the other two Mo sites have been replaced by Nb/Sb.