Yttrium(III) bonding to organic ligands: A comparison with the lanthanoid(III) cations

Summary The yttrium(III) bonding to organic substrates (oximes, -diketonates and (poly)amino-(poly)carboxylates) has been compared with that of the lanthanoid(III) cations. The complexation constants of Y³⁺ with the examined organic ligands are similar to those of some cations of the first half of the lanthanoid series, in contrast with the fact that the Y³⁺ ionic dimensions are similar to those of Ho³⁺. This has been explained by correlating the formation constants of the Y³⁺ and the lanthanoids(III) complexes by the equation logK ₁=C _AC_B+E _AE_B, where the parametersC andE indicate the tendency of each Lewis acidA and Lewis baseB to undergo covalent or ionic bonding, and where the ratioH=E/C indicates the charge control on the bond formation tendency of each speciesA orB. The results are commented in terms of the utility of Y³⁺ in assisting organic reactions.

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Bindung von Yttrium(III) an organische Liganden: Vergleich mit Lanthanoid(III)-Kationen

Zusammenfassung Es wurde die Bindung von Yttrium(III) an organische Substanzen [Oxime, -Diketonate und (Poly)Amino(poly)carboxylate] im Vergleich mit Lanthanoid(III)-Kationen behandelt. Die Komplexierungskonstanten von Y³⁺ sind ähnlich denen einiger Kationen der ersten Hälfte der Lanthanoidenserie; dies steht im Gegensatz zur Tatsache, daß die Dimensionen des Y³⁺-Ions denen des Ho³⁺ entsprechen. Die Erklärung wurde mittels der für die Bildungskonstanten der Y³⁺- und Lanthanoid(III)-Komplexe gültigen Gleichung logK ₁=C _AC_B+E _AE_B gefunden, wobeiC undE Parameter sind, die die Tendenz der Lewis-SäurenA und der Lewis-BasenB zum Eingehen von kovalenten oder ionischen Bindungen charakterisieren und wo das VerhältnisH=E/C den Steuerungseffekt der Ladung auf die Bindungstendenz der SpeziesA oderB beschreibt. Die Ergebnisse werden im Hinblick auf den Nutzen von Y³⁺ zur Unterstützung organischer Reaktionen diskutiert.

     

v-Triazolines. part XXI. Spiro[bicyclo[2.2.1]hept-2-ene[54']1',2'.s'-triazole]derivatives from cyclopentadiene and 5-amino-4-methylene-v-triazolines

1R^*, 4R^*, 5S^*, 5'S^*-5'-Amino-1'-(4-nitrophenyl)-4',5'-dihydrospiro[bicyclo [2.2. 1]hept-2-ene[5.4]-1',2',3'-triazoles]$\text{2}$ have been obtained both by ?4 +2]-cycloaddition of cyclopentadiene to amino-methylene-1-(4-nitrophenyl)-4,5-dihydro-v-triazoles $\text{1}$ and by [3+2]-cycloaddition of 4-nitrophenylazide to 5-aminomethylene-2-norborenes $\text{4}$. The configuration has been fully established by X-ray crystallographic analysis. The course of the cycloaddition and the thermal behaviour of $\text{2}$ are discussed.     

Determination of Bitterness of Extra Virgin Olive Oils by Amperometric Detection

A flow injection system with amperometric detection at potentials poised at +0.4 and +0.9 V was used to evaluate intensity of the bitter taste in monovarietal Extra Virgin Olive Oils (EVOO). Results from the proposed method were based on the extraction of the bitter constituents of the virgin olive oil samples in methanol‐water, followed by the direct amperometric measurement. These potentials were selected according to the hydrodynamic voltammogram of oleuropein, one of the most prominent and bitter phenolic compound found in EVOO. The amperometric detection was applied on 32 monovariatal EVOO samples. Results were correlated with the phenolic profile measured by high performance liquid chromatography (HPLC). The amperometric signal at +0.9 V mainly correlated with the total phenols of the samples (R²=0.81), whereas the signal at +0.4 V mainly correlated with oleuropein aglycone (3,4 DHPEA‐EDA, R²=0.79). Bitterness intensity of the samples was evaluated by a trained sensory panel of experts and the results compared to those obtained by the amperometric flow system. The best correlation with the bitter taste was achieved by the sensor at +0.4 V (R²=0.72). A calibration model based on partial least squares was built with three variables, namely the sensors set at +0.4 and +0.9 V and the total phenol content of the EVOO extracts. The model showed a moderate capacity to predict the bitterness of the EVOO samples using leave one out method, (R²=0.75) and in prediction of a test set of samples (R²=0.7). Such approach is very promising for future studies.     

On commuting polynomial automorphisms of {\mathbb{C}}^{k} , k ≥ 3

We characterize the polynomial automorphisms of ${\mathbb{C}}^3We characterize the polynomial automorphisms of , which commute with a regular automorphism. We use their meromorphic extension to and consider their dynamics on the hyperplane at infinity. We conjecture the additional hypothesis under which the same characterization is true in all dimensions. We give a partial answer to a question of S. Smale that in our context can be formulated as follows: can any polynomial automorphism of be the uniform limit on compact sets of polynomial automorphisms with trivial centralizer (i.e. )? Partially supported by Progetto MURST di Rilevante Interesse Nazionale Proprietà geometriche delle varietà reali e complesse. Supported by Istituto Nazionale Alta Matematica, “F. Severi”, Roma and G.N.S.A.G.A., Roma.     

The inclusion of succinylacetone as marker for tyrosinemia type I in expanded newborn screening programs

In expanded newborn screening programs by liquid chromatography/tandem mass spectrometry false negatives for tyrosinemia type I are a significant problem. We describe a method for inclusion of succinylacetone in order to avoid false negatives. We studied spots from 13,000 neonates born in Tuscany (January-May 2007) and ten spots from six patients with tyrosinemia type I. The traditional screening method was modified by adding dioxooctanoid acid (or 13C2-succinylacetone) as an internal standard to the methanolic solution of deuterated acylcarnitines and amino acids. A hydrazine solution was added to the mixture. The times of extraction, butylation and drying were only slightly prolonged. Specific multiple reaction monitoring for derivatized and labelled succinylacetone and dioxooctanoic acid was carried out. The assays were linear up to 100 micromol/L for succinylacetone. Intra- and inter-day imprecision data were in the range of 1.34% to 7.09% and 3.50% to 4.49%. Limits of detection and of quantification were 0.2 micromol/L and 0.4 micromol/L, respectively. Recovery ranged from 97.02% to 100.29%. Succinylacetone levels in samples from unaffected neonates were very close to the detection limit. Of the 46 recalls, eight (17.4%) were for abnormal tyrosine levels and all these cases had succinylacetone levels within the normal range (<2.4 micromol/L). In ten spots from six affected patients succinylacetone values ranged from 3.3 to 35.0 micromol/L. Including succinylacetone in newborn screening programs for amino acids and acylcarnitines avoids false-negative results for tyrosinemia type I. Newborn screening laboratories should consider implementing these modifications.     

Highly atom-economic one-pot formation of three different C-P bonds: general synthesis of acyclic tertiary phosphine sulfides

The reaction of benzothiadiphosphole 1 with an equimolar mixture of R1MgBr and R2MgBr gave intermediate A', which, after only 4-5 min, was treated with an equimolar amount of R3MgBr, giving the asymmetric phosphine PR1R2R3 in 45% overall yield (75-80% yield when R1 = R2 and 85-90% yield when R1 = R2 = R3) and the byproduct 6 in 90% yield. The treatment of 6 with PCl3 quantitatively regenerates the starting reagent 1. Treatment of the phosphines with elemental sulfur gave the corresponding sulfides.     

Contractive Metrics for a Boltzmann Equation for Granular Gases: Diffusive Equilibria

We quantify the long-time behavior of a system of (partially) inelastic particles in a stochastic thermostat by means of the contractivity of a suitable metric in the set of probability measures. Existence, uniqueness, boundedness of moments and regularity of a steady state are derived from this basic property. The solutions of the kinetic model are proved to converge exponentially as t to this diffusive equilibrium in this distance metrizing the weak convergence of measures. Then, we prove a uniform bound in time on Sobolev norms of the solution, provided the initial datum has a finite norm in the corresponding Sobolev space. These results are then combined, using interpolation inequalities, to obtain exponential convergence to the diffusive equilibrium in the strong L¹-norm, as well as various Sobolev norms.     

Positronium-oxygen interaction in hexane

Summary The role played by the O₂ molecule in the decay of Ps in air-saturated hexane was investigated by measurements of lifetime and by an experiment of magnetic quenching. The results indicate thata) O₂ reduces the overlap probability |φ(O)|² of the interacting positron-electron pair in Ps by a factor 1.6,b) Ps may react with the O₂ molecule forming a short-lived compound with a rate constantk _q=5.7·10⁻¹¹ cm³ s⁻¹ andc) it may undergo exchange collisions with unpaired electrons of the O₂ molecule with a rate constant γ_q=2.5 · 10^-11 cm³ s⁻¹.

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Riassunto L'interazione tra atomo di positronio e molecole di ossigeno, in esano saturo d'aria, è stata studiata mediante misure di vita media dell'ortopositronio e mediante un esperimento di spegnimento magnetico. I risultati indicano chea) l'ossigeno abbassa, di un fattore 1.6, la densità elettronica nell'origine del sistema legato elettrone-positone;b) il positonio si lega in un complesso a vita media molto corta con una costantek _q =5.7·10⁻¹¹ cm³ s⁻¹;c) le collisioni di scambio del positonio con gli elettroni dell' O₂ determinano transizioni orto-para caratterizzati da una costante γ_q=2.5 · 10^-11 cm³ s⁻¹.

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Реэюме Иэмерения времени жиэни и эксперимент по магнитной эакалке исполъ-зуются для исследования роли, которую играет молекула O₂ при распалде Ps в тексане. Полученные рэзулътаты показывают:a) O₂ уменъшает вероятностъ пе-рекрытия |φ(O)|² для взаимодействующей позитрон-электонной пары в Ps в 1.6 раза;b) Ps может реагироватъ с молекулой O₂, образуя короткоживыщее соединение с постояннойk _q=5.7·10⁻¹¹ см³ c⁻¹ иc) Ps может испытыватъ овменные соударения с не спаренныни электронами молекулы O₂ с постоянной γ_q=2.5 · 10^-11 см³ c⁻¹.

     

On the lifetime of charged charmed particles first direct observation of a charmed baryon decay

Two new examples of production by neutrinos and subsequent decay of charged charmed hadrons are reported. Together with two similar events reported previously they show that the lifetime of charged charmed particles is in the neighbourhood of 5 × 10^?13 s, as expected from current theoretical models. One of the new events is identified as a baryon λ_c⁺ of mass 2.295 ± 0.015 GeV/c² which undergoes the decay process λ_c⁺ → pπ⁺K^? with a proper decay time (7.3 ± 0.1) × 10^?13 s.