Reactions of activated aryl sydnones with electrophiles

Electrophilic substitution on the aryl or sydnone ring of some ortho-substituted activated N-aryl-sydnones is reported.     

Sorption of dyes on cellulose II: effect of alkali treatment of fibre and dye structure

Cellulose is a linear 1,4-β-glucan polymer where the units are able to form highly ordered structures, as a result of extensive interaction through intra- and intermolecular hydrogen bonding of the three hydroxyl groups in each cellulose unit. Alkali has a substantial influence on morphological, molecular and supramolecular properties of cellulose II polymer fibres causing changes in crystallinity. Lyocell fibres pre-treated with 0.0, 2.0, and 4.0 mol dm⁻³ aqueous NaOH solution were dyed with hydrolyzed reactive dyes that had different molecular shapes and sizes. Overall exhaustion (q _e), value of K, and −ΔG increased for lyocell samples pre-treated with aqueous NaOH solution in the following order: 2.0 > 4.0 > 0.0 mol dm⁻³ NaOH. The same trends were observed for colour strength (K/S) values of the dyeings. Pre-treatment of lyocell with 2.0 mol dm⁻³ NaOH creates the substrate that achieves the most thermodynamically favourable system for sorption of hydrolyzed reactive dyes, as at this concentration crystallinity decreases (with respect to 0.0 mol dm⁻³ NaOH treated lyocell) to afford higher sorption; however, at higher alkali concentrations the macro-sorbent forms a compacted unit that limits diffusion within the sorbent interior. Molecular size of the sorbate dye has a significant effect on the sorption process: for the largest dye structure the sorption isotherm is most closely correlated to a Langmuir isotherm; as the size of the dye decreases correlation to a Langmuir isotherm is observed, but with good correlation to the Freundlich isotherm; as the size of the dye is decreased further sorption is more typical of a Freundlich isotherm.     

Determination of trace elements in Nigerian kola-nuts by instrumental neutron activation analysis

The trace elements content of Cola acuminata and three varieties of Cola nitida have been determined using neutron activation analysis. The samples have been irradiated at the Joint Universities Research Reactor, Risley, England for 7^1/2 hours in a neutron flux of 2.5·10¹² n·cm^–2s^–1 and analysed using high resolution lithium drifted germanium detector coupled to a Canberra 35 microprocessor as a 4096 channel gamma spectrometer. The elements: Na, K, Br, W, Fe, Cs, Co, Zn, and Sc were detected.     

Sorption of poly(hexamethylenebiguanide) on cellulose: mechanism of binding and molecular recognition

Antimicrobial agents such as poly(hexamethylene biguanide) (PHMB) find application in medical, apparel, and household textile sectors; although it is understood that certain concentrations need to be applied to achieve suitable performance, there has been very little work published concerning the interactions of the polymer and its adsorption mechanism on cellulose. In this paper, such physical chemistry parameters are examined and related to computational chemistry studies. Adsorption isotherms were constructed: at low concentrations, these were typical Langmuir isotherms; at higher concentrations, they were more indicative of Freundlich isotherms, attributed to a combination of electrostatic and hydrogen-bonding forces, which endorsed computational chemistry proposals. At lower concentrations, electrostatic interactions between PHMB and carboxylic acid groups in the cellulose dominate with a contribution to binding through hydrogen bonding; as the concentration of PHMB increases, hydrogen bonding with cellulose becomes increasingly dominant. At high PHMB concentrations, observations of increasing PHMB adsorption are attributed to monolayer aggregation and multilayer stacking of PHMB through electrostatic interactions with counterions and hydrogen bonding of biguanide groups.     

Fermi surface topology and the superconducting gap function in UPd2Al3: a neutron spin-echo study

We report on a single crystal neutron spin-echo investigation of the low-energy dynamic response in the heavy-fermion superconductor UPd2Al3 in the vicinity of the antiferromagnetic wave vector Q(0)=(0 0 0.5). Well inside the superconducting phase, antiferromagnetic quasielastic scattering, which is present in the normal state, is absent for relaxation times up to 10 ns, equivalent to an energy resolution of approximately 1 microeV. This places strong constraints on possible models for this magnetic superconductor.     

On the complexity of the herding attack and some related attacks on hash functions

In this article, we analyze the complexity of the construction of the 2 ^k -diamond structure proposed by Kelsey and Kohno (LNCS, Vol 4004, pp 183–200, 2006). We point out a flaw in their analysis and show that their construction may not produce the desired diamond structure. We then give a more rigorous and detailed complexity analysis of the construction of a diamond structure. For this, we appeal to random graph theory (in particular, to the theory of random intersection graphs), which allows us to determine sharp necessary and sufficient conditions for the message complexity (i.e., the number of hash computations required to build the required structure). We also analyze the computational complexity for constructing a diamond structure, which has not been previously studied in the literature. Finally, we study the impact of our analysis on herding and other attacks that use the diamond structure as a subroutine. Precisely, our results shows the following:

1. The message complexity for the construction of a diamond structure is ${\sqrt{k}}$ times more than the amount previously stated in literature.

1. The time complexity is n times the message complexity, where n is the size of hash value.

Due to the above two results, the herding attack (Kelsey and Kohno, LNCS, Vol 4004, pp 183–200, 2006) and the second preimage attack (Andreeva et?al., LNCS, Vol 4965, pp 270–288, 2008) on iterated hash functions have increased complexity. We also show that the message complexity of herding and second preimage attacks on “hash twice” is n times the complexity claimed by Andreeva et?al. (LNCS, Vol 5867, pp 393–414, 2009), by giving a more detailed analysis of the attack.     

A self-learning predictive model of articulator movements during speech production

A model is presented which predicts the movements of flesh points on the tongue, lips, and jaw during speech production, from time-aligned phonetic strings. Starting from a database of x-ray articulator trajectories, means and variances of articulator positions and curvatures at the midpoints of phonemes are extracted from the data set. During prediction, the amount of articulatory effort required in a particular phonetic context is estimated from the relative local curvature of the articulator trajectory concerned. Correlations between position and curvature are used to directly predict variations from mean articulator positions due to coarticulatory effects. Use of the explicit coarticulation model yields a significant increase in articulatory modeling accuracy with respect to x-ray traces, as compared with the use of mean articulator positions alone.     

Aqueous solutions containing amino acids and peptides. Part 22 - free energetic and enthalpic virial coefficients at 25°C for some interactions of isofunctional amides

The excess free energies of aqueous solutions containing N-acetyl-L-prolinamide, N-acetyl-N-methyl-L-alaninamide and binary mixtures of these have been determined at 25°C from isopiestic measurements. The corresponding excess enthalpies for the last two systems have been obtained from enthalpy of dilution measurements. The results derived have been considered using the Savage-Wood group additivity principle, and it is shown that this works remarkably well although deviations are observed which are probably significant.Presented at the sixth Italian meeting on Calorimetry and Thermal Analysis (AICAT) held in Naples, December 4–7, 1984.