Simultaneous spectrophotometric determination of Zinc(II) and Nickel(II) with 1-(2-pyridylazo)-2-naphthol

A new procedure for the simultaneous spectrophotometric determination of Zn(II) and Ni(II) with 1-(2-pyridylazo)-2-naphthol as chromogenic reagent has been developed. It is based on resolution of the mixed spectrum over the wavelength range 530–590 nm by applying a least-squares fitting program to standard spectra from each component. The spectra are recorded at an apparent pH of 5.0, provided by an acetate buffer in a mixed 6040 v/v 2-ethoxyethanol/water medium. The relative standard deviations for determination of 13.7 g of Ni and 31.0 g of Zn were 1.9 and 1.0%, respectively (8 replications). The method has been applied to the analysis of iron surfaces coated with a Zn-Ni alloy. The results are compared with those obtained by atomic-absorption spectrophotometry.     

Gas phase intramolecular proton transfer in cationized glycine and chlorine substituted derivatives (M-Gly, M = Na+, Mg2+, Cu+, Ni+, and Cu2+): existence of Zwitterionic structures?

The intramolecular proton transfer in cationized glycine and chlorine substituted derivatives with M = Na+, Mg2+, Ni+, Cu+, and Cu2+ has been studied with the three parameter B3LYP density functional method. The coordination of metal cations to the oxygens of the carboxylic group of glycine stabilizes the zwitterionic structure. For all monocations the intramolecular proton transfer occurs readily with small energy barriers (1-2 kcalmol(-1)). For the dication Mg2+ and Cu2+ systems, the zwitterionic structure becomes very stable. However, whereas for Mg2+, the proton transfer process takes place spontaneously, for Cu2+ the reaction occurs with an important energy barrier. The substitution of the hydrogens of the amino group by chlorine atoms decreases the basicity of nitrogen, which destabilizes the zwitterionic structure. For monosubstituted glycine complexed with Na+, the zwitterionic structure still exists as a minimum, but for disubstituted glycine no minimum appears for this structure. In contrast, for Mg2+ complexed to mono- and disubstituted glycine, the zwitterionic structure remains the only minimum, since the enhanced electrostatic interaction with the dication overcomes the destabilizing effect of the chlorine atoms.     

Hydrophilic–oleophobic coatings on cellulosic materials by plasma assisted polymerization in liquid phase and fluorosurfactant complexation

Materials with hydrophilic–oleophobic properties are of relevance due to their application to different fields such as self-cleaning coatings, liquid–liquid separation membranes and functional textiles for different technical applications. In this work, hydrophilic–oleophobic coatings have been deposited on cellulosic materials (filter paper and bleached cotton) by means of plasma assisted polymerization of acrylic acid solutions in water followed by cationic fluorosurfactant complexation. Chemical composition of the coatings on cellulosic materials was characterized by means of FTIR–ATR and XPS whereas their morphology was studied by SEM. Hydrophilic–oleophobic behavior was characterized by means of contact angle and wetting time. Additionally wetting properties of cationic, anionic and non-ionic surfactant solutions on the hydrophilic–oleophobic coatings were used to characterize the polyelectrolyte electrostatic forces upon the functionalized layer.     

Catalytic Effect of Electric Fields on the Kemp Elimination Reactions with Neutral Bases

The effect of solvent reaction fields and oriented electric fields on the Kemp elimination reaction between methylamine or imidazole and 5-nitrobenzisoxazole has been theoretically studied. The Kemp reaction is the most widely used for the design of new enzymes. Our results, using the SMD continuous model for solvents, are in quite good agreement with the experimental fact that the rate of the analogous reaction with butylamine is one order of magnitude smaller in water than in acetonitrile. In the case of external electric fields, our results show that they can increase or decrease the energy barrier depending on the magnitude and orientation of the field. A duly oriented electric field may have a notable catalytic effect on the reaction. So, external electric fields and reaction fields due to the medium can contribute to the design of new enzymes. Several factors that must be taken into account to increase the catalytic effect are discussed.     

Dissolving Hydroxyolite: A DNA Molecule into Its Hydroxyapatite Mold

In spite of the clinical importance of hydroxyapatite (HAp), the mechanism that controls its dissolution in acidic environments remains unclear. Knowledge of such a process is highly desirable to provide better understanding of different pathologies, as for example osteoporosis, and of the HAp potential as vehicle for gene delivery to replace damaged DNA. In this work, the mechanism of dissolution in acid conditions of HAp nanoparticles encapsulating double‐stranded DNA has been investigated at the atomistic level using computer simulations. For this purpose, four consecutive (multi‐step) molecular dynamics simulations, involving different temperatures and proton transfer processes, have been carried out. Results are consistent with a polynuclear decalcification mechanism in which proton transfer processes, from the surface to the internal regions of the particle, play a crucial role. In addition, the DNA remains protected by the mineral mold and transferred proton from both temperature and chemicals. These results, which indicate that biomineralization imparts very effective protection to DNA, also have important implications in other biomedical fields, as for example in the design of artificial bones or in the fight against osteoporosis by promoting the fixation of Ca²⁺ ions.     

Interaction of fullerenes with the concave surfaces of perchloroazatriquinacene

[reaction: see text] Crystal structures of the one-to-one co-crystals of C(60).perchloroazatriquinacene and C(70).perchloroazatriquinacene show that the rigid, chalice-like azatriquinacene packs between completely ordered fullerene molecules with multiple, close Cl...fullerene contacts.     

Sol-Gel Synthesis of Transparent Alumina Gel and Pure Gamma Alumina by Urea Hydrolysis of Aluminum Nitrate

-Alumina was synthesized by a sol-gel method with the aluminum ion hydrolysis control performed by urea. The initial saturated Al³⁺/urea solution presented urea coordinated with the aluminum ion, as shown in the ¹³C NMR and ²⁷Al NMR spectra and longitudinal relaxation times, T ₁, from the latter. The substitution of water molecules in the Al³⁺ coordination shell by urea controlled the hydrolysis process and provided an extensive nucleation during the initial steps of the aluminum hydroxide formation due to urea thermolysis at 90°C. The resulting sol, composed of Al(OH)₃ nanoparticles, coalesced and became a transparent gel permeated by a solution of urea and the polycation ion [Al₁₃O₄(OH)₂₄(H₂O)₁₂]⁷⁺. The freshly prepared gel was transformed, under heating at 300°C, directly to -alumina, characterized by FTIR, ²⁷Al-MAS-NMR and S_BET techniques, without - or -phases, as a consequence of the high degree of homogeneity of the -alumina precursor.     

Asymptotic Behaviour of the Number of Labelled Essential Acyclic Digraphs and Labelled Chain Graphs

We provide an asymptotic formula for the number of labelled essential DAGs a_n and show that lim_na_n/a_n=c, where a_n is the number of labelled DAGs and c13.65, which is interesting in the field of Bayesian networks. Furthermore, we present an asymptotic formula for the number of labelled chain graphs.Acknowledgment. I would like to thank Prof. Peter Grabner for his support and very helpful discussions, which where constitutive for this article. I am also thankful to the referees for their comments.This Research was supported by the Austrian Science Fund (FWF), START-Project Y96-MATFinal version received: January 28, 2004