State-specific reactions and autoionization dynamics of Ar produced by synchrotron radiation

The long-lived excited states of doubly charged rare gases can markedly affect their reactivity. In this paper we demonstrate the presence of strong state-specific effects in the charge exchange of Ar²⁺ (³P, ¹D and ¹S) with several neutral targets (He, Ne, Kr, Xe, D₂, and CH₄). State sensitive measurements have been performed by producing the different Ar²⁺ electronic states via tunable synchrotron radiation (Elettra-Trieste, Italy and SuperACO-Orsay, France). From the product ion yield data of charge transfer, state-selected total cross-sections have been deduced. Using the state-specific reactivity of Ar²⁺ towards different neutral targets, it has been possible to extract the photon-energy-dependent production branching of the three doubly charged states and to investigate the autoionization dynamics of neutral or singly charged Ar in the vicinity of the double ionization threshold.     

catena-Poly­[[di­aqua(1,10-phen­anthroline-N,N′)­manganese(II)]-μ-(thiosulfato-O:S)] and bis(2,2′-bipyridyl-N,N′)(tetra­thionato-O,O′)manganese(II)

The structures of [Mn(S₂O₃)₂(C₁₂H₈N₂)(H₂O)₂] and [Mn(S₄O₆)(C₁₀H₈N₂)₂] are presented. The former consists of pairs of polymeric chains formed by manganese polyhedra bridged by bidentate thio­sulfate anions, which are in turn related to each other by a pseudo-twofold screw axis. The latter has crystallographic twofold symmetry and consists of monomers in which manganese displays its typical octahedral coordination provided by the bidentate bites of two bi­pyridine bases and a tetra­thionate anion, which is, to our knowledge, the first chelating tetra­thionate to be reported in the literature.     

Density functional theory for a model of nonuniform liquid metal in partially ionized states

Summary The problem of the electronic, ionic and atomic density profiles in a nonuniform liquid metal which can locally exist in partially ionized states is examined using the density functional formalism. Ions and electrons are allowed to bind into atoms through a ?reaction? governed by the mass action law. Formally exact equations for the density profiles are given in terms of the inverse response matrix of the nonuniform system, which consists of two terms: the first corresponding to to a mixture of ions, electrons and structureless atoms and the other to the atomic internal degrees of freedom. Approximate schemes are proposed for both contributions, stressing, in partieular, i) how ionization of the atoms arises with increasing density and the relation with Mott’s criterion for the metal-insulator transition, and ii) the usefulness of a weak-coupling assumption for interspecies correlations. This formalism used together with properly parametrized trial functions for the density profiles should be particularly useful for studying the liquid-vapour interface of alkali metals.

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Riassunto Il lavoro usa il formalismo del funzionale di densità per discutere la determinazione dei profili di densità in un fluido non omogeneo che può trovarsi localmente in stati di ionizzazione parziale. Con riferimento specifico ai metalli alcalini, la formazione di atomi per legame di ioni ed electtroni è descritta come una ?reazione? governata dalla legge di azione di massa. Le condizioni di equilibrio microscopico del fluido sono espresse tramite una matrice di risposta in cui appaiono due contributi, associati rispettivamente ai gradi di libertà interni degli atomi e ad una miscela di tre specie di particelle senza struttura interna. Si propongono quindi schemi approssimati per il calcolo di questi due contributi, con attenzione particolare all’uso di teorie perturbative e alla relazione tra grado di ionizzazione locale e densità localle, in connessione col criterio di Mott per la transizione isolante-metallo. Il formalismo proposto è in particolare appropriato per lo studio dell’interfaccia liquido-vapore in metalli alcalini.

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Резюме Используя функционала плотности, исследуется проблема профилей электронной, ионной и атомой ллотностей В неоднодном зидком металле, которий мозет локалщно существоватщ в частично иониэированных состояних. Ионы и электроны могут şвяэыватщся в атомщ череэ ?реакцию, определяемую эаконом дейşтвуюших масс. Приводятся формалщно точные уравнения для профнлеи плотности в термина⇆ обратной матрици отклика для неоднородной системы, которая состоит иэ двух чуленов: первий соответствует ссмеси ионов, электронов и бесстрктурных атмов и второй член соответствует атомным внутренним степеням свобды. Предлагаются приближенные схемы для обоых вкладов, обрашая особое бнмание, в частности, 1) как иониэация атомов воэликает бри увеличени влотности, на свяэы с критерием Мота для берехода ?металл-иеолятор?, и 2) на полеэносты предположения слабой свяэи для межвидовых кореляций. Предложенный Формалиэм, исполыеовалный вместе с параметриэованными пробными функциями для профилей плотнорти, окаэываетця оробенне полеэным для исследования грраницы ?жидкостъ-пар? в шелочлых металлах.

     

N-propargylic beta-enaminones: common intermediates for the synthesis of polysubstituted pyrroles and pyridines.

N-Propargylic beta-enaminones have been used as common intermediates for the synthesis of polysubstituted pyrroles and pyridines. Best results have been obtained using DMSO as solvent. In the presence of Cs(2)CO(3) N-propargylic beta-enaminones are cyclized to pyrroles in good to high yields, whereas omitting bases and using CuBr leads to the selective formation of pyridines.     

Electrochemical Kinetic Characterization of Redox Mediated Glucose Oxidase Reactions: A Simplified Approach

One of the main drawbacks affecting first‐generation electrochemical biosensors in the analysis of real matrices is the interference of electroactive species present in the sample under investigation. Several approaches have been attempted to overcome this problem in the past ten years but the best results were achieved by using mediated based electrochemical biosensors. Despite this, the kinetic of the redox mediators‐enzymatic proteins interaction has not been studied deeply enough. In this work we have developed a theoretical‐methodological approach for the characterization of the kinetic of interaction between redox enzymes and substrates and/or redox mediators. Particularly, the interaction of glucose oxidase (GOx) with several commercially available redox mediators has been studied by means of amperometry and cyclic voltammetry. The main kinetic parameters for different mediators were exploited and discussed with the aim of finding the best mediator for a glucose biosensor to be used on real samples.     

Carbohydrate-Based Scaffolds for the Generation of Sortiments of Bioactive Compounds

Summary.  The polyfunctionality and conformational rigidity of carbohydrates make this class of compounds ideal scaffolds for the production of sortiments¹ of bioactive compounds. Examples of carbohydrate-derived peptidomimetics of biological interest, such as somatostatin agonists and integrin antagonists, are presented. In order to have access to solid phase supported sortiments of compounds, orthogonally protected or unprotected carbohydrates were linked to polymers and reacted in the solid phase employing different regioselective strategies. Original bicyclic and tricyclic glycidic scaffolds were easily obtained starting from natural sugars such as D-arabinose and D-fructose. Manipulation of these conformationally blocked compounds afforded different carbohydrate-based derivatives, among which azidoacids are useful precursors of β-turn peptidomimetics. Received September 10, 2001. Accepted November 2, 2001     

EEG Fractal Analysis Reflects Brain Impairment after Stroke

Stroke is the commonest cause of disability. Novel treatments require an improved understanding of the underlying mechanisms of recovery. Fractal approaches have demonstrated that a single metric can describe the complexity of seemingly random fluctuations of physiological signals. We hypothesize that fractal algorithms applied to electroencephalographic (EEG) signals may track brain impairment after stroke. Sixteen stroke survivors were studied in the hyperacute (<48 h) and in the acute phase (∼1 week after stroke), and 35 stroke survivors during the early subacute phase (from 8 days to 32 days and after ∼2 months after stroke): We compared resting-state EEG fractal changes using fractal measures (i.e., Higuchi Index, Tortuosity) with 11 healthy controls. Both Higuchi index and Tortuosity values were significantly lower after a stroke throughout the acute and early subacute stage compared to healthy subjects, reflecting a brain activity which is significantly less complex. These indices may be promising metrics to track behavioral changes in the very early stage after stroke. Our findings might contribute to the neurorehabilitation quest in identifying reliable biomarkers for a better tailoring of rehabilitation pathways.     

Effects of pH and Carbon Source on <Emphasis Type="Italic">Synechococcus</Emphasis> PCC 7002 Cultivation: Biomass and Carbohydrate Production with Different Strategies for pH Control

Synechococcus PCC 7002 is an interesting species in view of industrial production of carbohydrates. The cultivation performances of this species are strongly affected by the pH of the medium, which also influences the carbohydrate accumulation. In this work, different methods of pH control were analyzed, in order to obtain a higher production of both Synechococcus biomass and carbohydrates. To better understand the influence of pH on growth and carbohydrate productivity, manual and automatic pH regulation in CO₂ and bicarbonate system were applied. The pH value of 8.5 resulted the best to achieve both of these goals. From an industrial point of view, an alternative way to maintain the pH practically constant during the entire period of cultivation is the exploitation of the bicarbonate-CO₂ buffer system, with the double aim to maintain the pH in the viability range and also to provide the amount of carbon required by growth. In this condition, a high concentration of biomass (6 g L^?1) and carbohydrate content (around 60 %) were obtained, which are promising in view of a potential use for bioethanol production. The chemical equilibrium of C-N-P species was also evaluated by applying the ionic balance equations, and a relation between the sodium bicarbonate added in the medium and the equilibrium value of pH was discussed.     

Immobilization and Stabilization of Beta-Xylosidases from Penicillium janczewskii

β-Xylosidases are critical for complete degradation of xylan, the second main constituent of plant cell walls. A minor β-xylosidase (BXYL II) from Penicillium janczewskii was purified by ammonium sulfate precipitation (30% saturation) followed by DEAE-Sephadex chromatography in pH 6.5 and elution with KCl. The enzyme presented molecular weight (MW) of 301 kDa estimated by size exclusion chromatography. Optimal activity was observed in pH 3.0 and 70–75 °C, with higher stability in pH 3.0–4.5 and half-lives of 11, 5, and 2 min at 65, 70, and 75 °C, respectively. Inhibition was moderate with Pb⁺² and citrate and total with Cu⁺², Hg⁺², and Co⁺². Partially purified BXYL II and BXYL I (the main β-xylosidase from this fungus) were individually immobilized and stabilized in glyoxyl agarose gels. At 65 °C, immobilized BXYL I and BXYL II presented half-lives of 4.9 and 23.1 h, respectively, therefore being 12.3-fold and 33-fold more stable than their unipuntual CNBr derivatives (reference mimicking soluble enzyme behaviors). During long-term incubation in pH 5.0 at 50 °C, BXYL I and BXYL II glyoxyl derivatives preserved 85 and 35% activity after 25 and 7 days, respectively. Immobilized BXYL I retained 70% activity after 10 reuse cycles of p-nitrophenyl-β-D-xylopyranoside hydrolysis.