New insight into solvent effects on the formal HOO. + HOO. reaction

The 2,2'-azobis(isobutyronitrile)(AIBN)-induced autoxidation of gamma-terpinene (TH) at 50 degrees C produces p-cymene and hydrogen peroxide in a radical-chain reaction having HOO* as one of the chain-carrying radicals. The kinetics of this reaction in cyclohexane and tert-butyl alcohol show that chain termination involves the formal HOO. + HOO. self-reaction over a wide range of gamma-terpinene, AIBN, and O2 concentrations. However, in acetonitrile this termination process is accompanied by termination via the cross-reaction of the terpinenyl radical, T., with the HOO. radical under conditions of relatively high [TH] (140-1000 mM) and low [O2] (2.0-5.5 mM). This is because the formal HOO. + HOO. reaction is comparatively slow in acetonitrile (2k approximately 8 x 10(7) M(-1) s(-1)), whereas, this reaction is almost diffusion-controlled in tert-butyl alcohol and cyclohexane, 2k approximately 6.5 x 10(8) and 1.3 x 10(9) M(-1) s(-1), respectively. Three mechanisms for the bimolecular self-reaction of HOO. radicals are considered: 1) a head-to-tail hydrogen-atom transfer from one radical to the other, 2) a head-to-head reaction to form an intermediate tetroxide, and 3) an electron-transfer between HOO. and its conjugate base, the superoxide radical anion, O2-.. The rate constant for reaction by mechanism (1) is shown to be dependent on the hydrogen bond (HB) accepting ability of the solvent; that by mechanism (2) is shown to be too slow for this process to be of any importance; and that by mechanism (3) is dependent on the pH of the solvent and its ability to support ionization. Mechanism (3) was found to be the main termination process in tert-butyl alcohol and acetonitrile. In the gas phase, the rate constant for the HOO. + HOO. reaction (mechanism (1)) is about 1.8 x 10(9) M(-1) s(-1) but in water at pH< or =2 where the ionization of HOO. is completely suppressed, this rate constant is only 8.6 x 10(5) M(-1) s(-1). The very large retarding effect of water on this reaction has not previously been explained. We find that it can be quantitatively accounted for by using Abraham's HB acceptor parameter, beta(2)(H), for water of 0.38 and an estimated HB donor parameter, alpha(2)(H), for HOO. of about 0.87. These Abraham parameters allow us to predict a rate constant for the HOO. + HOO. reaction in water at 25 degrees C of 1.2 x 10(6) M(-1) s(-1) in excellent agreement with experiment.     

Synthesis and characterization of oxygen and sulfur bridged aromatic macrocycles

The synthesis of nine 16–18–20–22 membered, oxygen and sulfur bridged aromatic macrocycles is reported, and reaction pathways to macrocycles formation are described. Molecular characterization of the nine compounds has been achieved by their mass spectra. Due to the cyclic nature of the compounds analyzed, the mass spectra are of particular interest. The 16–18-membered macrocycles, containing single oxygen and sulfur bridges, display very strong molecular ion intensities, while the 20–22-membered macrocycles, containing double bridges, show lower stability to electron-impact, and the molecular ion intensities are lower. Some of the salient features of the electron fragmentation processes are briefly discussed in the text.     

Mass spectrometry in the proteome analysis of mature cereal kernels

In the last decade, the improved performance and versatility of the mass spectrometers together with the increasing availability of gene and genomic sequence database, led the mass spectrometry to become an indispensable tool for either protein and proteome analyses in cereals. Mass spectrometric works on prolamins have rapidly evolved from the determination of the molecular masses of proteins to the proteomic approaches aimed to a large-scale protein identification and study of functional and regulatory aspects of proteins. Mass spectrometry coupled with electrophoresis, chromatographic methods, and bioinformatics tools is currently making significant contributions to a better knowledge of the composition and structure of the cereal proteins and their structure-function relationships. Results obtained using mass spectrometry, including characterization of prolamins, investigation of the gluten toxicity for coeliac patients, identification of proteins responsible of cereal allergies, determination of the protein pattern and its modification under environmental or stress effects, investigation of genetically modified varieties by proteomic approaches, are summarized here, to illustrate current trends, analytical troubles and challenges, and suggest possible future perspectives.     

Laser induced reorder in Pb implanted Ge

Ge samples implanted with 40 keV Pb at a fluence of 3×10¹⁵/cm² were irradiated with ruby laser single pulses of 15ns duration. Reordering of the damaged layer occurs for energy density irradiation above 0.6 J/cm². The Pb atoms redistribute with a large component at the sample surface which is easily etched off. The remaining part of Pb impurities is substitutionally located, and the concentration exceeds the solid solubility limit by three order of magnitude. The formation of the metastable solution is explained in terms of a transient liquid layer produced during laser irradiation.     

Hydrolysis of (CH3)3Sn+ in Various Salt Media

The hydrolysis of trimethyltin(IV) has been studied by potentiometry (H⁺ -glass electrode) and calorimetry in various salt media (NaNO₃, NaCl, KCl, Na₂SO₄, and NaNO₃—NaCl mixtures). The effect of ionic strength on the hydrolysis constants is accounted for by a simple Debye–Hückel type equation and by Pitzer equations. The results allow us to obtain H for hydrolysis and the temperature dependence of the Pitzer parameters. The resulting coefficients can be used to examine the speciation of (CH₃)₃Sn⁺ in multicomponent electrolyte solutions, such as natural waters, over a wide range of temperature and ionic strength.     

Acid–Base Properties, Solubility, Activity Coefficients and Na+ Ion Pair Formation of Complexons in NaCl(aq) at Different Ionic Strengths

The protonation constants and solubilities of three complexons [ethylenediamine-N,N′-disuccinic acid (EDDS), ethylene glycol bis(2-aminoethyl ether)-N,N,N′,N′-tetraacetic acid (EGTA) and 1,2-cyclohexanediamine-N,N,N′,N′-tetraacetic acid (CDTA)] are reported in aqueous solutions of NaCl with different ionic strength values (0 ≤ I ≤ 4.8 mol·L^?1) and, in the case of CDTA, in (CH₃)₄NCl (0.1 ≤ I ≤ 2.7 mol·L^?1). The dependence on ionic strength of the protonation constants of these three complexons and four other complexons that were previously reported (NTA, EDTA, DTPA and TTHA), is analyzed in NaCl solution; the ionic strength influences quite strongly the protonation constants (as an example for CDTA, log₁₀ K ₁ = 10.54 and 9.25 at I = 0.1 and 1 mol·L^?1, respectively), while the effect of (CH₃)₄NCl concentration is lower. Based on the total solubility S ^T and the protonation constant data at different salt concentrations, the solubility of the neutral species S ⁰ and the solubility products K _S0 are obtained. The Setschenow coefficients k _m and the solubility values S ₀ ⁰ in pure water are also reported (S ₀ ⁰  = 0.55, 0.21 and 0.75 mmol·kg^?1 for EDDS, EGTA and CDTA, respectively). The dependence of the protonation constants on ionic strength is also interpreted in terms of ion pair formation, and the formation constants of Na⁺ species are reported.     

Does a Reinforced Kinetic Macrocyclic Effect Exist? The Demetallation in Strong Acid of Copper(II) Complexes with Open and Cyclic Tetramines Containing a Piperazine Fragment

The demetallation in acidic solution of the Cu(II) complexes with open-chain and cyclic tetramines containing a piperazine unit (2 and 3) has been investigated in terms of its kinetic aspects and compared with the behaviour of unsubstituted counterparts (tetramines 1 and 4). The presence of the piperazine fragment slows demetallation of the open-chain-ligand complex owing to the activation barrier associated with the conformational change from boat-to-half-boat; however, it does not affect the demetallation of the macrocyclic complex, which involves the spontaneous boat-to-twist conformational change. Thus, lateral reinforcement of a cyclam-like ligand does not add any further contribution to the typical inertness in demetallation of macrocyclic complexes.