Synthesis and comparative solution properties of single‐, twin‐, and triple‐tailed associating ionic polymers based on diallylammonium salts

The cycloterpolymerizations of single‐, twin‐, and triple‐tailed hydrophobes with hydrophilic monomer N,N‐diallyl‐N‐carboethoxymethylammonium chloride and sulfur dioxide afforded a series of cationic polyelectrolytes (CPEs) in excellent yields. These CPEs, upon the acidic hydrolysis of the pendent ester groups, gave the corresponding pH‐responsive cationic acid salts, which, upon a treatment with sodium hydroxide, were converted to polybetaines (PBs), anionic polyelectrolytes (APEs), and PB/APE polymers containing various proportions of zwitterionic (PB) and anionic fractions (APE) in the polymer chain. At a shear rate of 0.36 s⁻¹ at 30 °C, salt‐free water solutions of the CPEs (2 g/dL) containing 8, 4, and 2.67 mol % of the single‐, twin‐, and triple‐tailed hydrophobes (all having 8 mol % octyloxy tails) had apparent viscosity values of 70, 2800, and 396,000 cps, respectively. The PB/APE polymer with a ratio of 33:67 for the zwitterionic and anionic fractions in the polymer chain gave the highest viscosity value. The superior viscosity behavior of the polymers containing the triple‐tailed hydrophobe was attributed to the blocky nature of the comonomer. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 5480–5494, 2006     

Flow injection-spectrophotometric determination of cresol compounds in water by reaction withp-aminophenol

A spectrophotometric method has been developed for the simultaneous determination ofo-cresol andm-cresol in water by reaction withp-aminophenol (PAP). Three different methodologies have been assayed; (i) batch analysis, after reaction in an alkaline medium in the presence of dissolved molecular oxygen as oxidizing agent, (ii) a stopped-flow procedure, carried out in the presence of KIO₄ and (iii) a flow injection method based on the same approach. The batch procedure requires 22 min for the full development of colour witho-cresol and 12 min form-cresol. In the stopped-flow mode, using KIO₄ and a reaction time of 12 min, better sensitivity can be obtained for both compounds and limits of detection of 10 g 1^–1 foro-cresol and 30 g 1^–1 form-cresol were found. The flow injection method has a lower sensitivity but permits more than 80 injections per hour. Based on the different maximum absorbance wavelengths obtained for the reaction products of PAP witho-cresol (614 nm) andm-cresol (632 nm), both compounds can be simultaneously determined in water samples and recoveries of 90 to 115% were found in spiked water samples of different types.     

Physico-chemical properties of iron-tin mixed oxide catalysts in cyclohexane oxidation

The state of mixed iron-tin oxide catalysts with a variable ratio of their metallic components has been studied by Mössbauer and ESCA spectroscopy. The results are compared with the activity of these catalysts in cyclohexane oxidation.

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Lower bounds for boundary roughness for droplets in Bernoulli percolation

We consider boundary roughness for the ``droplet' created when supercritical two-dimensional Bernoulli percolation is conditioned to have an open dual circuit surrounding the origin and enclosing an area at least l², for large l. The maximum local roughness is the maximum inward deviation of the droplet boundary from the boundary of its own convex hull; we show that for large l this maximum is at least of order l^1/3(logl)^–2/3. This complements the upper bound of order l^1/3(logl)^–2/3 proved in [Al3] for the average local roughness. The exponent 1/3 on l here is in keeping with predictions from the physics literature for interfaces in two dimensions. The research of the first author was supported by NSF grant DMS-9802368. The research of the second author was supported by NSF grants DMS-9802368 and DMS-0103790.Mathematics Subject Classification (2000): Primary 60K35; Secondary 82B20, 82B43     

Oblique interaction of electrostatic nonlinear structures in relativistically degenerate dense magnetoplasmas

We have investigated the interaction of obliquely propagating ion acoustic solitary waves in a magnetoplasma with relativistically degenerate electrons. Using the quantum hydrodynamics model and by employing the extended Poincaré–Lighthill–Kuo technique, we have derived a set of Korteweg de Vries equations for two solitons. We have observed that the system under consideration allows the formation of only compressive solitons and their velocities remain in the sub-acoustic limit. Furthermore, phase shifts of solitons as a result of their interaction have been calculated. The phase shifts have been observed to be dependent on the obliqueness and the physical parameters of plasma. It has also been noticed that phase shifts remain negative for the whole range of parameters generally found in white dwarf stars. We have observed that the phase shifts enhance with the enhancement in number density, however, the converse happens when the magnetic field is enhanced. It has also been observed that the phase shift is slightly greater for the solitons that are less oblique as compared to their more oblique counterparts. Furthermore, we have estimated the spatial scales of interaction of solitons using the parameters found in white dwarf stars.     

Role of the n+1 amino acid residue on the deamidation of asparagine in pentapeptides

Deamidation plays an important role in biochemical phenomena such as aging. The role of the n + 1 residue on the deamidation of asparagine (asparagine being the nth residue) in three pentapeptide chains (GGNGG, GGNMG and GGNIG) has been analysed with hybrid computational tools. Potentials of mean force at 300 K were calculated from the MD/replica exchange simulations using weighted histogram analysis (WHAM) in explicit water. The snapshots were clustered taking into account the requirements of the plausible deamidation mechanisms, as such the tautomerisation of the asparagine side chain as initial step has been confirmed, based on the proximity of water to the deamidation site. The ultimate goal being to gain an insight on the peptide backbone N-H acidity, quantum mechanical calculations have been carried out. For this purpose, the distribution of Φ/Ψ, Φ₂/Ψ and end-to-end distances deduced from the WHAM diagrams have been considered and a total of 110 structures have been sampled. These neutral pentapeptides as well as their corresponding anions have been optimised (B3LYP/6-31++G(d,p)) in implicit water in order to gain an insight on the peptide backbone N-H acidity. In this study, we have shown that the open conformations of the neutrals and the anions, which display a β sheet like structure are well populated and their pK_as rank in the same order as the deamidating half-lives, that is the peptides that deaminate fastest can more readily access conformations that are more acidic.     

The hall effect in some liquid alloys

The Hall coefficient has been measured for (a) liquid CuTe, AgTe and AuTe₂ and (b) liquid Cu-Sn alloy. The results are discussed in terms of the possible semiconducting nature of liquids comprising group (a) and in terms of bound state formation around the Sn atoms for those in group (b).     

Characteristics of high energy interactions II. Production spectra of Gamma-rays in graphite

Twenty high energy nuclear interactions produced in the graphite units of an emulsion chamber were recorded. The emulsion chamber was exposed to cosmic rays at an atmospheric depth of 10 g cm⁻² for about 7 hr over Hyderabad, India. Fourteen interactions which radiated energyΣ E _r⩾1000 GeV in the form ofγ-rays were analysed in detail. The median energy 〈Σ E _r〉 of the interactions was 1600 GeV. Results concerning the multiplicity, the transverse and longitudinal momentum distributions, and the fractional energy distribution ofγ-rays in these interactions are presented. The average transverse momentum ofπ ⁰—mesons <pt _π ⁰> is found to increase very slowly with the primary energyE ₀ and it can be approximated by the function <pt _π ⁰>=0·238E ₀ ^0.06 .     

Characteristics of high energy interactions I. High energy gamma-ray spectra near the top of the atmosphere

An emulsion chamber was used to study the characteristics of high energy nuclear interactions from the production spectra ofγ-rays. The emulsion chamber, which comprised of two parts, namely the detector and the graphite producer unit, was exposed to cosmic rays for about 7 hr at an atmospheric depth of 10 g cm⁻² at Hyderabad (geomagnetic latitude 7·6°N). 720 electromagnetic cascades due toγ-rays were recorded in the detector. These cascades were classified into three groups; (a)γ-rays from nuclear interactions in the detector (b)γ-rays from nuclear interactions in the producer unit and (c)γ-rays of atmospheric origin. The energies of the cascades were determined using photometric method. The spectra ofγ-rays from groups (a) and (c) were determined and compared with similar spectra obtained at greater atmospheric depths. The spectra were found to obey a power law. The spectrum ofγ-rays of atmospheric origin was found to steepen at high energies,E _r>2200 GeV.