On the output function in a Ginsburg’s machine

We give the form of the output function in Ginsburg’s machine in which the input and output dictionaries are abelian groups and the transition function is of a special form.     

Conductance of tetraalkylammonium salts in propylene carbonate at 25°C

Conductance measurements of 12 quaternary ammonium salts in propylene carbonate (PC) have been made at 25°C. The cations were either tetramethylammonium, tetraethylammonium, or tetra-n-butylammonium, and the concentrations of salt varied from about 2×10^–4 to 5×10^–3 M. The data were analyzed by the equation of Pitts. The results showed that the benzoate, nitrobenzoate, and pentachlorophenolate salts are completely dissociated. The nitrophenolate, chlorophenolate, methylsulfonate, and nitrate salts are only slightly associated (K _A from 2.5 to 6.5), while the acetate, phenylacetate, and nitrophenolate salts display somewhat more extensive association, with ionpair association constants from 17 to 45. Limiting molar conductances for the anions were derived. The factors affecting ionic mobilities in this dipolar aprotic solvent are discussed.On leave 1973–1975 from the University of Gdask, Poland.     

Indirect carbon–carbon spin–spin couplings across one,two and three bonds in pyridine and diazine systems: experiment and theory

An excellent linear correlation is found between a large body of experimental spin–spin carbon–carbon couplings, J(CC), across one, two and three bonds in pyridine and diazine ring systems and the corresponding B3PW91/6‐311++G(d,p)//B3PW91/6‐311++G(d,p) computations. The correlation does not differ significantly from the simplest relationship possible, J(CC)_exp. = J(CC)_calcd., within a small and random spread of about 1 Hz. There are 276 experimental values considered, and 124 out of these are new and come from the present work. The aromatic carbon–carbon couplings vary from ?7.6 through +78.5 Hz. It is shown that the correlation provides a reliable tool for predictions of the signs of aromatic J(CC)'s even if the magnitudes of the latter are of the order of 1 Hz. It is demonstrated, for the first time, that the relatively weak ² J(CC) couplings, in the heteroaromatic systems studied, can bear either sign and span a considerable range of about 11 Hz. The character of the correlation indicates that rovibronic effects on aromatic J(CC)'s and those of nuclear motions on aromatic J(CC)'s are practically negligible. All of this is in a perfect agreement with our recent extensive studies on aromatic J(CC)'s in analogous benzene ring system. Substituent effects on the aromatic J(CC)'s turn out to be significant not only for ¹J(CC)'s but also for most of ³J(CC)'s and ² J(CC)'s, and the computation neatly reciprocates these trends. Copyright © 2008 John Wiley & Sons, Ltd.     

Structure de l'automate plein,réduit et inversible

Sans résumé     

Molecular parameters describing intermolecular interactions in the electrooptical Kerr effect

Electrooptical Kerr effect has been studied in binary solutions of a dipolar liquid (-picoline, β-picoline) in a non-dipolar solvent (benzene, p-xylene) and 1,4-dioxane in the full range of concentrations of the dipolar component (0 ≤ f₂ ≤ 1). The experimental Kerr constant K_s of the solutions, refraction index n_s, density ρ_s and the dielectric constant ε_s have been measured and used for the calculation of the molar Kerr constants K_S^M within the Onsager local field model. Analysis of changes in the molar Kerr constants as a function of the solute concentration by fits of theoretical functions to the experimental ones has permitted a determination of the parameters characterizing intermolecular interactions in binary solutions.     

An adaptive critic neural network for motion control of a wheeled mobile robot

In this paper, we propose a new application of the adaptive critic methodology for the feedback control of wheeled mobile robots, based on a critic signal provided by a neural network (NN). The adaptive critic architecture uses a high-level supervisory NN adaptive critic element (ACE), to generate the reinforcement signal to optimise the associative search element (ASE), which is applied to approximate the non-linear functions of the mobile robot. The proposed tracking controller is derived from Lyapunov stability theory and can guarantee tracking performance and stability. A series of computer simulations have been used to emulate the performance of the proposed solution for a wheeled mobile robot.     

Mass spectrometric behaviour of carboxylated polyethylene glycols and carboxylated octylphenol ethoxylates

Mass spectrometric behaviour of mono- and di-carboxylated polyethylene glycols (PEGCs and CPEGCs) and carboxylated octylphenol ethoxylates (OPECs) are discussed. The tendency for ionisation (deprotonation, protonation and cationisation by alkali metal cations) of carboxylated PEGs was compared with that of non-carboxylated correspondents by using both secondary ion mass spectrometry (SIMS) and electrospray ionisation (ESI). The fragmentation of the PEGCs and CPEGCs is discussed and also compared with their neutral correspondents, PEGs. The B/E mass spectra were recorded, using secondary ion mass spectrometry as a method for generation, for deprotonated and protonated molecules and molecules cationised by alkali metal cations. The fragmentation behaviour of PEGs is found to be different from that of CPEGCs, The presence of carboxylic groups may be confirmed not only by the determination of molecular weights of the ethoxylates studied, but also on the basis of the fragment ions formed. The metastable decomposition of the [OPEC-H](-) ions proceed through the cleavage of the bond between the octylphenol moiety and the ethoxylene chain leading to the octylphenoxy anions. It permits determination of the mass of the hydrophobic moiety of the studied carboxylated alkylphenol ethoxylate. ESI mass spectra recorded in the negative ion mode were found to be more suitable for the determination of the average molecular weight of carboxylated ethoxylates than SI mass spectra.     

A Microfluidic Co-Flow Route for Human Serum Albumin-Drug–Nanoparticle Assembly

Nanoparticles are widely studied as carrier vehicles in biological systems because their size readily allows access through cellular membranes. Moreover, they have the potential to carry cargo molecules and as such, these factors make them especially attractive for intravenous drug delivery purposes. Interest in protein-based nanoparticles has recently gained attraction due to particle biocompatibility and lack of toxicity. However, the production of homogeneous protein nanoparticles with high encapsulation efficiencies, without the need for additional cross-linking or further engineering of the molecule, remains challenging. Herein, we present a microfluidic 3D co-flow device to generate human serum albumin/celastrol nanoparticles by co-flowing an aqueous protein solution with celastrol in ethanol. This microscale co-flow method resulted in the formation of nanoparticles with a homogeneous size distribution and an average size, which could be tuned from ≈100 nm to 1 μm by modulating the flow rates used. We show that the high stability of the particles stems from the covalent cross-linking of the naturally present cysteine residues within the particles formed during the assembly step. By choosing optimal flow rates during synthesis an encapsulation efficiency of 75±24 % was achieved. Finally, we show that this approach achieves significantly enhanced solubility of celastrol in the aqueous phase and, crucially, reduced cellular toxicity.     

Separation and determination of homogenous fatty alcohol ethoxylates by liquid chromatography with mulitstage mass spectrometry

Alcohol ethoxylates (AEs) are a significant component of a stream of surfactants directed to the aquatic environment. The aim of this work was the investigation of the dependence of the analytical signals of homogeneous AE homologues on liquid chromatography with tandem mass spectrometry conditions, as well as the separation of AEs from the water matrix and, on this basis, the development of an analytical procedure suitable for the determination of AEs in environmental samples. Homogeneous homologues containing dodecyl moiety and 2–9 oxyethylene subunits were investigated. The analytical signals of the investigated homologues were optimized in terms of concentration of ammonium acetate in the mobile phase (optimum 5 mM) and a column temperature (optimum 35°C) of the liquid chromatography with tandem mass spectrometry system. A separation of AEs from the water matrix by liquid–liquid extraction (ethyl acetate, chloroform) or solid‐phase extraction (C₁₈, styrene divinylbenzene, H‐RX) was investigated. In a model investigation, the best recoveries (>90%) were obtained with a styrene divinylbenzene cartridge eluted with a 1:1 mixture of chloroform and methanol. However, much worse recoveries were obtained from the river water sample. Better results were obtained for liquid–liquid extraction with ethyl acetate. Recoveries of 62–80% were obtained for homologues having 4–9 oxyethylene subunits, at the lowest spike.     

Simultaneous Determination of Major Constituents of Honeybee Venom by LC-DAD

The aim of the study was to develop an LC method for honeybee venom analysis, using cytochrome c as an internal standard. The SynChropack C8 6.5 μm, 4.6 × 100 mm column was applied. The bee venom was separated by linear gradient 5–80% B at 30 min (eluent A—0.1% TFA in water, eluent B—0.1% TFA in acetonitrile:water (80:20)). The flow rate of mobile phase was maintained at 1 mL min^?1, injection volume: 40 μL, separation temperature: 25 °C. The analysis was monitored at 220 nm. Several honeybee venom constituents were separated and the content of four of them (apamine, mast cell degranulating peptide, phospholipase A₂ and melittin) were determined. By applying this methodology differences in chemical composition of honeybee venom were evaluated. In order to confirm the data obtained, the following steps and parameters were taken into account for the validation of the method: selectivity, precision (injection repeatability, analysis repeatability), accuracy (recovery), linearity and operating range, limit of detection and limit of quantitation. All steps of validation proved that the developed analytical procedure was suitable for its intended purpose (standardization). Due to its simplicity, the developed method can be easily automated and incorporated into routine operations both in the bee venom identification, quality control and assay tests.