Electrostatic charging of nonpolar colloids by reverse micelles

Colloids dispersed in a nonpolar solvent become charged when reverse micelles are added. We study the charge of individual sterically stabilized poly(methyl methacrylate) spheres dispersed in micellar solutions of the surfactants sodium bis(2-ethyl 1-hexyl) sulfosuccinate [AOT], zirconyl 2-ethyl hexanoate [Zr(Oct)2], and a copolymer of poly(12-hydroxystearic acid)-poly(methyl methacrylate) [PHSA-PMMA]. Although the sign of the particle charge is positive for Zr(Oct)2, negative for AOT, and essentially neutral for PHSA-PMMA, the different micellar systems display a number of common features. In particular, we demonstrate that over a wide range of concentrations the particle potential is a constant, independent of the number of micelles added and independent of the colloid size. A simple thermodynamic model, in which the particle charge is generated by the competitive adsorption of both positive and negative micelles, is in good agreement with the experimental data.     

Solution-, solid-phase, and fluorous synthesis of beta,beta-difluorinated cyclic quaternary alpha-amino acid derivatives: a comparative study

The diastereoselective synthesis of cyclic beta,beta-difluorinated alpha-amino acid derivatives bearing a quaternary stereocenter is described. The process relies on the chemo- and diastereoselective addition of allylic organometallic reagents to fluorinated alpha-imino esters and a subsequent ring-closing metathesis reaction (RCM). Complete selectivity in the nucleophilic addition was achieved with (R)-phenylglycinol methyl ether as a chiral auxiliary. The resulting amino acids were introduced into peptide chains, which could facilitate the preparation of potentially bioactive dipeptide derivatives. In addition, the solution synthesis of these cyclic fluorinated alpha-amino acids was successfully adapted to solid-phase and fluorous-phase techniques. The reaction times and final deprotection were clearly more favorable in the latter, in which a fluorous trimethylsilylethanol (TMSE) tag was used. The tag was then easily removed upon treatment with TBAF in a high-yield transesterification process.     

Regioselective formylation of pyrazolo[3,4-b]pyridine and pyrazolo[1,5-a]pyrimidine systems using Vilsmeier-Haack conditions

Regioselective formylation behavior has been found in the reaction of pyrazolo[3,4-b]pyridines and pyrazolo[1,5-a]pyrimidines via Vilsmeier-Haack conditions. While the 4,5- and 6,7-dihydro derivatives afforded pyrazolo[3,4-b]pyridine-5-carbaldehydes and 4,7-dihydropyrazolo[1,5-a]pyrimidine-3,6-dicarbaldehydes, respectively, the aromatic analogs rendered the pyrazolo[1,5-a]pyrimidine-3-carbaldehyde only, and no reaction took place at the pyrazolopyridine derivatives.     

Peptide fingerprinting of snake venoms by direct infusion nano-electrospray ionization mass spectrometry: potential use in venom identification and taxonomy

Fingerprinting by mass spectrometry has been increasingly used to study venom variations and for taxonomic analyses based on venom components. Most of these studies have concentrated on components heavier than 3 kDa, but Bothrops snake venoms contain many biologically active peptides, principally C-type natriuretic peptides and bradykinin-potentiating peptides (BPPs). In this work, we have examined the peptide profile of Bothrops venoms (B. alternatus, B. erythromelas, B. insularis, B. jararaca, B. jararacussu, B. leucurus and B. moojeni) using direct infusion nano-electrospray ionization mass spectrometry (nano-ESI-MS) subjecting the data further to principal components analysis (PCA) to assess whether the peptide distributions are reliable in distinguishing the venoms. ESI-MS of a low molar mass fraction obtained by ultrafiltration of each venom (5 kDa nominal cutoff filters) revealed that the venoms have a variety of peptides in common but that each venom also contains taxonomic marker peptides not shared with other venoms. One BPP peptide, QGGWPRPGPEIPP, was found to be common to the seven Bothrops species examined. This peptide may represent a specific marker for this genus since it was not found in the venom of the South American rattlesnake, Crotalus durissus terrificus. PCA on the ESI-MS data reveals a close relationship between B. jararaca, B. jararacussu and B. moojeni venoms, with B. leucurus and B. erythromelas being more distant from these three; B. alternatus and B. insularis were also located distant from these five species, as was C. d. terrificus. These results agree partially with established phylogenetic relationships among these species and suggest that ESI-MS peptide fingerprinting of snake venoms coupled with PCA is a useful tool for identifying venoms and for taxonomic analyses.     

-bounds for the Beurling-Ahlfors transform

Let denote the Beurling-Ahlfors transform defined on , . The celebrated conjecture of T. Iwaniec states that its norm where . In this paper the new upper estimate

is found.

     

The Solute Polarization and Structural Effects on the Nonlinear Optical Response of Based Chromone Molecules

The solute polarization due to solvent is a an electrostatic quantum effect that impacts diverse molecular properties, including the nonlinear optical response of a material. An iterative procedure that allows updating the solute charge distribution in the presence of the solvent is combined with a sequential Monte Carlo/Quantum Mechanics methodology and Density Functional Theory methods to evaluate the nonlinear optical (NLO) response using the hyper Rayleigh scattering (HRS) of a series of chromones recently identified in Chamaecrista diphylla, an herbaceous plant abundant throughout the Americas and used in folk medicine. From this study, it is determined that from gas to solvent environment, the systems acquire low refractive index (n) and an improvement of the first hyperpolarizability (β_HRS), signaling potential NLO uses. It is shown that the octupolar contributions (β^J=3) superate the dipolar ones (β^J=1) and dominate the second-order optical response in both gas and liquid phases, which indicate nontrivial optical materials. Moreover, the solvent environment and structural changes in the periphery can tune significantly the dipolar/octupolar balance, showing a key to control the decoupling between these contributions.     

The electronic delocalization in para‐substituted β‐nitrostyrenes probed by resonance Raman spectroscopy and quantum‐chemical calculations

The electronic (UV‐vis) and resonance Raman (RR) spectra of a series of para‐substituted trans‐β‐nitrostyrenes were investigated to determine the influence of the electron donating properties of the substituent (X = H, NO₂, COOH, Cl, OCH₃, OH, N(CH₃)₂, and O⁻) on the extent of the charge transfer to the electron‐withdrawing NO₂ group directly linked to the ethylenic (C = C) unit. The Raman spectra and quantum chemical calculations show clearly the correlation of the electron donating power of the X group with the wavenumbers of the ν_s(NO₂) and ν (C = C)_sty normal modes. In conditions of resonance with the lowest excited electronic state, one observes for X = OH and N(CH₃)₂ that the symmetric stretching of the NO₂, ν_s(NO₂), is the most substantially enhanced mode, whereas for X = O⁻, the chromophore is extended over the whole molecule, with substantial enhancement of several carbon backbone modes. Copyright © 2008 John Wiley & Sons, Ltd.     

Disorder‐induced symmetry lowering in Ba(Y1/2Nb1/2)O3 ceramics probed by Raman spectroscopy

This work investigates the evolution of the crystal structure of microwave‐hydrothermal synthesized Ba(Y_1/2Nb_1/2)O₃ powders as a function of firing temperature by Raman spectroscopy. The samples were produced at 200 °C and fired at temperatures ranging from 600 to 1600 °C. Raman spectra were obtained at room temperature for all samples and the results showed that materials fired at 1600 °C exhibited tetragonal (I4/m or ) structure, whereas those fired at lower temperatures exhibited the triclinic (P1 or C_i¹) structure. The results were compared with those observed for ceramics obtained by conventional solid‐state methods. It is believed that the lowering of the symmetry verified in materials fired below 1600 °C is a consequence of the local disorder of Y⁺³ and Nb⁺⁵ ions in octahedral sites. Copyright © 2008 John Wiley & Sons, Ltd.     

Large Communities in a Scale-Free Network

We prove the existence of a large complete subgraph w.h.p. in a preferential attachment random graph process with an edge-step. That is, we consider a dynamic stochastic process for constructing a graph in which at each step we independently decide, with probability \(p\in (0,1)\), whether the graph receives a new vertex or a new edge between existing vertices. The connections are then made according to a preferential attachment rule. We prove that the random graph \(G_{t}\) produced by this so-called generalized linear preferential (GLP) model at time t contains a complete subgraph whose vertex set cardinality is given by \(t^\alpha \), where \(\alpha = (1-\varepsilon )\frac{1-p}{2-p}\), for any small \(\varepsilon >0\) asymptotically almost surely.     

Analysis of corrosion residues by WDXRF

In this article, a methodology for the wavelength dispersive X‐ray fluorescence analysis of corrosion residues is described. Corrosion residues are generally composed of elements that are, total or partially, in a reduced state. Therefore, to prepare fused beads to be measured by wavelength dispersive X‐ray fluorescence, it is necessary to oxidize species and to avoid any analyte loss, as sulfur, which is present in residues composition. The combination of an oxidizing agent (LiNO₃) and a flux (Li₂B₄O₇ + LiBO₂), at a mass ratio residue : oxidizing agent : flux of 1:5:12, is demonstrated to be suitable for the quantitative retention of sulfur in the sample preparation. The addition of silica to the mixture (residue : oxidizing agent : flux) for the formation of homogeneous fused beads is also studied. The optimal parameters for the sample preparation are as follows: A temperature of 600 °C for 15 min for the oxidation process and a fusion temperature of 950 °C for fused beads preparation. The quantitative retention of sulfur in the entire process was validated by an independent method, combustion and infrared detection, and analyzation reference materials. Moreover, minor and major elements (Al, Ca, Cr, Cu, Fe, K, Mg, Mn, Mo, Na, Ni, P, S, and Ti) present in corrosion residues were simultaneously measured with low uncertainty. Copyright © 2017 John Wiley & Sons, Ltd.