Path to achieving molecular dispersion in a dense reactive mixture

A uniform dispersion of reactants is necessary to achieve a complete reaction involving multicomponents. In this study, we have examined the role of plasticizer in the reaction of two seemingly unlikely reactants: a highly crystalline hexamethylenetetramine (HMTA) and a strongly hydrogen bonded phenol formaldehyde resin. By combining information from NMR, infrared spectroscopy and differential scanning calorimetry, we were able to determine the role of specific intermolecular interactions necessary for the plasticizer to dissolve the highly crystalline HMTA and to plasticize the phenol formaldehyde resin in this crosslinking reaction. The presence of the plasticizer increased the segmental mobility, disrupted the hydrogen bonded matrix, and freed the hydroxyl units, which further increased the solubility of the HMTA. Both the endothermic and exothermic transitions are accounted for in the calorimetric data obtained. For the first time, it is possible to obtain the effective molar ratio of each component needed to complete the crosslinking reaction efficiently. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2015 , 53, 1519–1526     

Syntheses and properties of related polyoxadiazoles and polytriazoles

New aromatic poly-1,2,4-triazoles and poly-1,3,4-oxadiazoles are studied as thermally stable membrane materials. Various groups were introduced onto the pendant phenyl groups of poly-1,2,4-triazoles. Glass transition temperature, degradation temperature, and cold crystallization behavior were studied as a function of these groups. Cold crystallization appeared to be highly sensitive to macromolecular regularity. The solubility of poly-1,3,4-oxadiazoles was highly improved upon incorporation of 5-t-butylisophthalic, 1,1,3-trimethyl-3-phenylindane, 4,4′-(2,2′-diphenyl) hexafluoro propane, and diphenyl ether groups into the polymeric main chain, whereas the high glass transition temperatures and degradation temperatures typical for aromatic poly-1,3,4-oxadiazoles were maintained. © 1994 John Wiley & Sons, Inc.     

The polymerization of methyl methacrylate by ion pairs

The reactions of the polymethylmethacrylate anion have been investigated at 200 K and 250 K in both THF and 9/1 toluene/THF. Sodium-α methyl styrene tetramer and fluorenyl sodium were used as initiators. Only ion pair reactions were investigated. The rate constant of monomer addition to the ion pair at 200 K was determined to be 80 ± 6 M^?1 sec^?1. At 250 K in the presence of excess monomer, the poly MMA anion reacts with the monomer vinyl function and the monomer ester function at comparable rates. Once fully reacted, the poly MMA anion terminates very slowly in THF at 250 K by an intermolecular mechanism. This rate of termination is enhanced in the toluene/THF system. No evidence was found for different reaction mechanisms for the two initiators.     

Bombardment of alkali halide crystals with medium-energy atoms

The sputtering characteristics of KCl and NaCl alkali halide single crystals by bombardment with argon and mercury atoms are investigated. The sputtering coefficients are measured in the energy range 0.5–3 keV. Anisotropy is found in sputtering at various incident angles of the beam. The yield of charged particles during bombardment of thin specimens (of the order of 8–20 m) of KCl single crystals is investigated.Translated from Izvestiya Vysshikh Uchebnykh Zavedenii, Fizika, No. 7, pp. 55–59, July, 1984.     

Thermal denaturation of bovine serum albumin and its oligomers and derivativespH dependence

In a previous paper, we report a preliminary DSC study on bovine (BSA) and human (HSA) serum albumins. However, at accurate HPLC analysis the commercial proteins show three peaks: Fraction V-I, probably globulins (as declared by the producers), Fraction V-II (about 15–18% of the product) and Fraction V-III that represents pure BSA or HSA. A hypothesis is that the Fraction II is a covalent dimer, or trimer or a mixture of both, generated during the scalf-life of the commercial product. Denaturation enthalpies of the purified Fraction V-III and Fraction V-II of BSA, have been determined calorimetrically, at changing thepH, and the results of both compared with those obtained on the untreated protein. Few calorimetric experiments have been also carried on a BSA monomer derivative with sulphidril group protected. Computer program have been developed for the deconvolution of exo- and endothermic effects and for the analysis of thermal denaturation profiles.     

Determination of lead in seawater by inductively coupled plasma optical emission spectrometry after separation and pre-concentration with cocrystallized naphthalene alizarin

An analytical method for separation and pre-concentration of lead in seawater for determination by inductively coupled plasma optical emission spectrometry has been investigated. Lead was retained in the solid phase (0.5 g) composed of co-precipitated naphthalene and alizarin red. The solid phase quantitatively sorbs Pb(II) at pH 8–9, and the metal was eluted using 5.0 ml of 2 mol l⁻¹ nitric acid. The effect of NaCl, KCl, BaCl₂, CaCl₂, Na₂SO₄, MgCl₂ and Na₃PO₄ on the sorption of Pb(II) in the solid phase was studied. A set of solutions containing varying amounts of electrolytes (0.5; 1.0; 3.0 and 5.0% m/v) with Pb (50 μg) was prepared and the recommended procedure applied. The Na₃PO₄ was found to interfere; the other electrolytes did not interfere up to 5% m/v. A pre-concentration factor of 40 was obtained in this analytical procedure. The limit of detection and limit of quantification for Pb(II) were 53 and 176 μg l⁻¹, respectively. Lead was determined in seawater samples collected in Salvador city, Bahia, Brazil. The precision, expressed as R.S.D., was 1.8–4.6%, and the recovery of lead added to seawater samples was 95–97%.     

Photophysical characterization of mixed micelles of n-butanol/SDS and n-hexanol/SDS. A study at low alcohol concentrations

 The effect of the addition of n-butanol (BuOH) and n-hexanol (HexOH) on the micellization of sodium dodecylsulfate (SDS) has been investigated using fluorescence quenching methods. The binding constants were calculated using an expression which relates the total concentration of alcohols and the micelle concentration. The values of K were 4.67 and 17.6 M^-1 for BuOH/SDS and HexOH/SDS, similar to values obtained by other methods. The cmc of SDS decreases on addition of alcohols and goes through a minimum for the BuOH/SDS system. Micellar aggregation numbers (N) were determined from linear plots of Ln (I ⁰/I) against [Quencher] at low alcohol concentrations. For 15 mM SDS, in the presence of BuOH the N values decrease on addition of alcohol up to 0.2 M. For HexOH, N can be assumed to be constant up to 4.8 mM, after which N decreases. The polarity of the micellar core containing alcohol was evaluated from the I ₁/I ₃ ratio of monomeric pyrene. The effect of addition of the alcohol causes a decrease in the I ₁/I ₃, which corresponds to a decrease in the polarity of the pyrene solubilization site. Received: 28 October 1996 Accepted: 10 January 1997     

Nanocomposite structures of polypyrrole derivatives and poly (acrylonitrile‐co‐itaconic acid) produced by in situ polymerization as carbon nanofiber precursor

This study aimed to produce nanoparticles of poly (acrylonitrile‐co‐itaconic acid) (P (AN‐co‐IA)) containing conjugated polymers of pyrrole, N‐Methylpyrrole, 2,5‐dimethylpyrrole, and 1‐(Triisopropylsilyl)pyrrole which were synthesized by emulsion polymerization. Nanocomposite structures of P (AN‐co‐IA)/polypyrrole and polymer of pyrrole derivatives were produced via in situ polymerization, and the nanoparticle formation were followed by morphologic and ultraviolet‐visible (UV‐Vis) spectroscopic methods. Characterizations were made by Fourier transform infrared‐attenuated total reflectance (FTIR‐ATR) and Raman spectroscopy. Atomic force microscopy (AFM) was used for investigating the surface characteristics of the nanoparticles. Characterization results revealed that nanoparticles containing conjugated polymers had rougher surface than P (AN‐co‐IA) nanoparticles. It was also observed that the nanoparticles were well‐distributed although having some agglomerates. Moreover, depending on the type of monomer of conjugated polymer, the shape and size of the produced nanoparticles differed by conjunction with their polymerization rate. These findings can be used as a startup information for production of carbon nanofibers (CNFs) with desired properties after oxidation and carbonization, and as a high‐performance and cost‐effective flame and heat‐resistant material (oxidized copolymers of polyacrylonitrile nanofiber).     

Bifunctional polytetrahydrofuran initiator for sequential photochemical and thermal initiation

The polymerization of tetrahydrofuran was initiated with 4,4′-azobis(4-cyanovaleryl chloride) in conjunction with silver hexafluoroantimonate and the living polytetrahydrofuran (PTHF) was terminated with pyridinium N-oxide derivatives. The resulting PTHF-macroinitiator possesses both a thermally and photochemically labile group.     

Electrospray ionization mass spectrometry and partial least squares discriminant analysis applied to the quality control of olive oil

Direct infusion electrospray ionization mass spectrometry in the positive ion mode [ESI(+)‐MS] is used to obtain fingerprints of aqueous–methanolic extracts of two types of olive oils, extra virgin (EV) and ordinary (OR), as well as of samples of EV olive oil adulterated by the addition of OR olive oil and other edible oils: corn (CO), sunflower (SF), soybean (SO) and canola (CA). The MS data is treated by the partial least squares discriminant analysis (PLS‐DA) protocol aiming at discriminating the above‐mentioned classes formed by the genuine olive oils, EV (1) and OR (2), as well as the EV adulterated samples, i.e. EV/SO (3), EV/CO (4), EV/SF (5), EV/CA (6) and EV/OR (7). The PLS‐DA model employed is built with 190 and 70 samples for the training and test sets, respectively. For all classes (1–7), EV and OR olive oils as well as the adulterated samples (in a proportion varying from 0.5 to 20.0% w/w) are properly classified. The developed methodology required no ions identification and demonstrated to be fast, as each measurement lasted about 3 min including the extraction step and MS analysis, and reliable, because high sensitivities (rate of true positives) and specificities (rate of true negatives) were achieved. Finally, it can be envisaged that this approach has potential to be applied in quality control of EV olive oils. Copyright © 2013 John Wiley & Sons, Ltd.