Conformations and base-catalyzed equilibrations of N-nitroso-decahydroquinolines and N-nitroso-2-methyldecahydroquinolines

Conformations of six title compounds were determined by¹³C-NMR spectroscopy. Equilibration of the 2-methyl-compounds gives as main products the derivatives of the amines least abundant in the product mixture of the catalytic hydrogenation.

---

Konformation und Base-katalysierte Äquilibrierungen von N-Nitroso-decahydrochinolinen und N-Nitroso-2-methyl-decakydrochinolinen (Kurze Mitt.)

Zusammenfassung Die Konformationen der sechs Titelverbindungen wurden mittels¹³C-NMR Spektroskopie bestimmt. Äquilibrierung der 2-Methyl-verbindungen ergab als Hauptprodukte die Derivate der bei katalytischer Hydrierung in geringster Menge entstandenen Amine.

     

Formation and Crystal Structure of Stable Five‐coordinate Diorgano Cobalt(III) Complexes

The mer‐octahedral complexes(2‐carbonyl)(4‐Me)(6‐tBu)phenolato[C,O]hydridotris(trimethylphosphine)cobalt(III) ( 1 ) or ‐(1‐carbonyl)(2‐oxo)(1,2‐diphenylethene)[C,O]hydridotris(trimethylphosphine)cobalt(III) ( 2 ) via formal insertion of propynoic acid ethyl ester into Co‐H functions afford pentacoordinate vinylcobalt(III) 3 and 4 , respectively, that are diamagnetic and attain a square pyramidal structure as exemplified by an X‐ray diffraction analysis of 3 .     

X-ray magnetic circular dichroism of Pseudomonas aeruginosa nickel(II) azurin

We show that X-ray magnetic circular dichroism (XMCD) can be employed to probe the oxidation states and other electronic structural features of nickel active sites in proteins. As a calibration standard, we have measured XMCD and X-ray absorption (XAS) spectra for the nickel(II) derivative of Pseudomonas aeruginosa azurin (NiAz). Our analysis of these spectra confirms that the electronic ground state of NiAz is high-spin (S = 1); we also find that the L(3)-centroid energy is 853.1(1) eV, the branching ratio is 0.722(4), and the magnetic moment is 1.9(4) mu(B). Density functional theory (DFT) calculations on model NiAz structures establish that orbitals 3d(x2-y2) and 3d(z2) are the two valence holes in the high-spin Ni(II) ground state, and in accord with the experimentally determined orbital magnetic moment, the DFT results also demonstrate that both holes are highly delocalized, with 3d(x2-y2) having much greater ligand character.     

Kalorimetrische Messungen an Mischungen von Nichtelektrolyten, 1. Mitt.: Molwärme des Systems 1,2-Dibromäthan-Benzol

Zusammenfassung Es wird der Aufbau eines Kalorimeters zur Bestimmung der spezif. Wärme von Flüssigkeiten beschrieben. Die Messungen werden nach einem kontinuierlichen adiabatischen Aufheizverfahren durchgeführt. Der Fehler in der Molwärme beträgt ca. ±0,4%. Die Methode erlaubt auch innerhalb relativ kleiner Temperaturbereiche eine Aussage über die Temperaturabhängigkeit der Wärmekapazität.Die Molwärme des Systems 1,2-Dibromäthan-Benzol wird zwischen 24 und 29°C über den ganzen Konzentrationsbereich vermessen. Die Mischungen zeigen negative C _p-Werte mit unsymmetrischem Konzentrationsverlauf. Für höhere Temperaturen ist eine Zunahme der Symmetrie zu erwarten.

---

A calorimeter has been described which serves to determine the heat capacities of liquids. In the measurements the calorimeter and the surroundings are heated continuously, so that adiabatic conditions prevail. The experimental error in the molar heat capacities is ca. ±0,4%. The method also permits the estimation of the temperature dependence of the heat capacities, even within relatively small temperature intervals.The molar heat capacity of the system 1,2-dibromoethane-benzene has been measured between 24° and 29°C for all concentrations. The C _p-values of the mixtures are negative and show an asymmetrical dependence on the concentration. For higher temperatures it is expected that the concentration dependence will become more nearly symmetrical.

---

---

Mit 3 Abbildungen     

Synthesis of branched oxime-linked peptide mimetics of the MUC1 containing a universal T-helper epitope

Our goal was to develop mimics of MUC1, highly immunogenic to induce an efficient immune response against the tumor-associated form of MUC1, and sufficiently different from the natural antigen to bypass the tolerance barrier in humans. With the aim of obtaining a well-defined peptide construct as a means of evoking the precise immune responses required in immunotherapy, we synthesized artificial mimics of the MUC1 protein composed of two MUC1 repeat units of inverse orientation and a universal T-helper epitope. To synthesize these heteromeric peptide constructs, we followed a convergent approach using chemoselective ligation based on oxime chemistry. A stem peptide was first synthesized bearing two orthogonally masked aldehydes. After successive deprotection, two oxime bonds can be specifically generated. The proposed strategy proved to be concise and robust, and allowed the synthesis of the tri-branched protein in a very satisfactory yield. The different constructs were tested for their ability to generate antibodies able to recognize the MUC1 protein.     

New minimal geodesics in the group of symplectic diffeomorphisms

We compute the Hofer distance for a certain class of compactly supported symplectic diffeomorphisms of ²ⁿ. They are mainly characterized by the condition that they can be generated by a Hamiltonian flow _H ^t which possesses only constantT-periodic solutions for 0 <T 1. In addition, we show that on this class Hofer's and Viterbo's distances coincide.     

Surgery on 3-manifolds with \mathbb{S} 1-actions

We study the topological structure of all 3-manifolds obtained by surgery along principal fibers of a closed orientable -manifold. As a consequence, we give alternative proofs of some classical results due to W. Heil and L. Moser. Moreover, we completely specify the Seifert invariants for the considered manifolds. Finally we classify the manifolds obtained by surgery along certain Seifert links and determine geometric presentations of their fundamental groups.Work performed under the auspices of C.N.R. (National Research Council) of Italy and partially supported by Ministero della Ricerca Scientifica e Tecnologica within the projects Geometria Reale e Complessa and Topologia.     

High-temperature oxygen sensors for glass-forming melts

Electrochemical sensors are reported for the on-line measurement of oxygen partial pressures of oxidic glass-forming melts on a laboratory and technical scale. Based on the principle of solid electrolyte cells without transference, they are principally simple units. The extreme chemical and temperature conditions of their applications, however, demanded extensive fundamental investigations and resulted in specific forms of reference and measuring electrodes, a thermo-dynamic procedure of verifying the correct functioning of such cells, and a method of measuring thermoelectric voltages of non-isothermal glass melts.     

Asymptotic expansions in the integral and local limit theorems in banach spaces with applications to ω-statistics

LetB be a real separable Banach space and letX,X ₁,X ₂,...∈B denote a sequence of independent identically distributed random variables taking values inB. DenoteS _n =n ^?1/2(X ₁+...X _n ). Let π:B→R be a polynomial. We consider (truncated) Edgeworth expansions and other asymptotic expansions for the distribution function of the r.v. π(S _n ) with uniform and nonuniform bounds for the remainder terms. Expansions for the density of π(S _n ) and its higher order derivatives are derived as well. As an application of the general results we get expansions in the integral and local limit theorems for ω-statistics $$\omega _n^p (q)\mathop { = n^{{p \mathord{\left/ {\vphantom {p 2}} \right. \kern-\nulldelimiterspace} 2}} }\limits^\Delta \smallint _{(0,1)} \{ F_n (x) - x\} ^p q(x)dx$$ and investigate smoothness properties of their distribution functions. Herep≥2 is an even number,q: [0, 1]→[0, ∞] is a measurable weight function, andF _n denotes the empirical distribution function. Roughly speaking, we show that in order to get an asymptotic expansion with remainder termO(n ^?α), α<p/2, for the distribution function of the ω-statistic, it is sufficient thatq is nontrivial, i.e., mes{t∈(0, 1):q(t)≠0}>0. Expansions of arbitrary length are available provided the weight functionq is absolutely continuous and positive on an nonempty subinterval of (0, 1). Similar results hold for the density of the distribution function and its derivatives providedq satisfies certain very mild smoothness condition and is bounded away from zero. The last condition is essential since the distribution function of the ω-statistic has no density whenq is vanishing on an nonempty subinterval of (0, 1).