A new polymorph of tetraphenyldiboroxane

A new polymorph of tetraphenyldiboroxane [or oxybis(diphenylborane)], C₂₄H₂₀B₂O, (Ia), has been found. It is monoclinic, like the already known form, (Ib), and can be refined in the same space group, namely P2₁/c, or in the equivalent setting P2₁/n. The molecular conformations of the two polymorphs differ in the rotations of two of the phenyl rings about the B—C bonds, leading to markedly different packing patterns and cell dimensions.     

Quasielastic nucleon and hyperon production by neutrinos and antineutrinos with energies below 30 GeV

The cross sections of neutrino and antineutrino quasielastic reactions \(vn \to \mu ^ - p,\bar vp \to \mu ^ + n,\bar vp \to \mu ^ + \Lambda\) were studied in the neutrino energy range between 3 and 30 GeV. In comparison withV-A theory axial mass parameters ofM _A =(1.06±0.05±0.14) GeV/c² from neutrino andM _A =(0.71±0.10±0.20) GeV/c² from antineutrino data were found. The total cross-section for the hyperon production process can be described byM _A =1.0 GeV/c².     

Final results on μe-pair production in neutrino interactions in the SKAT freon bubble chamber experiment

We present the final results from the search for μe pairs produced in neutrino interactions using the freon filled bubble chamber SKAT. The rate of μ^? e ⁺ pairs to charged current events above the charm threshold is \(R_{\mu ^ - e^ + } = (4.8 \pm 1.1)10^{ - 3} \) . Assuming charm particle production to be the origin of the positron we calculate \(R_{\Lambda _c^ + } = (6.2 \pm 3.1)10^{ - 2} \) andR _D =(2.8±0.9)10^?2. We observe no considerable μ^? e ^? pair production above the background. In the regionE _v >3 GeV,p _μ,e >1.0 GeV/c andp _μ>p _e we find with a 90% confidence level the limit \(R_{\mu ^ - e^ - }< 1.7 10^{ - 4} \) .     

Determination of 11 aminoglycosides in meat and liver by liquid chromatography with tandem mass spectrometry

A method using liquid chromatography with tandem mass spectrometry was developed for the determination of 11 commonly used aminoglycoside antibiotics in meat. The proposed method is sufficiently sensitive (detection limits of 15 to 40 ppb for the various antibiotics) and highly selective. It is suitable for the quantitation and confirmation of aminoglycosides in a variety of matrixes (pork muscle, fish, and veal liver). Any multiresidue method for aminoglycosides must take into account their high affinity toward sample proteins and the significantly different pK values of the various analytes. The developed method uses a low-pH extraction with trichloracetic acid to ensure complete extraction of the analytes from the matrix. An anion-exchange step is used to remove the acid from the centrifuged extract. Aminoglycosides in this solution of low ionic strength can be quantitatively retained and afterwards eluted from a weak cation-exchanger solid-phase extraction (SPE) cartridge. The highly selective SPE steps produce clean extracts, which minimize possible suppression of the mass spectrometer signal.     

An explicit formula for the discussion of stability in autonomous Hamiltonian systems

The well known theorem of Arnold and Moser gives (in most cases) an answer to the question of the stability of the equilibria of autonomous Hamiltonian systems which can be reduced to two degrees of freedom. To apply their theorem, the Hamiltonian has to be transformed into its Birkhoff normal form of order two. In this paper this transformation is reduced to the multiplication of polynomials, which can easily be performed algebraically on a computer. The conical precessions of a dynamically symmetric satellite in a circular orbit serve as an example.

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Zusammenfassung Der bekannte Satz von Arnold und Moser liefert (auer in wenigen Ausnahmefällen) eine Antwort auf die Frage nach der Stabilität von Gleichgewichtslagen autonomer Hamiltonscher Systeme, die sich auf zwei Freiheitsgrade reduzieren lassen. Damit dieser Satz angewendet werden kann, mu die Hamiltonfunktion auf ihre Birkhoff-Normalform der Ordnung zwei transformiert werden. Diese Transformation wird hier auf Multiplikationen von Polynomen reduziert, die einfach, in symbolischer Weise, auf dem Computer ausgeführt werden können. Als Beispiel dienen die konischen Präzessionen eines dynamisch symmetrischen Satelliten auf einer Kreisbahn.

     

A study of [Co2(alkyne)(binap)(CO)4] complexes (BINAP=(1,1'-binaphthalene)-2,2'-diylbis(diphenylphosphine))

Understanding the interaction of chiral ligands, alkynes, and alkenes with cobaltcarbonyl sources is critical to learning more about the mechanism of the catalytic, asymmetric Pauson-Khand reaction. We have successfully characterized complexes of the type [Co2(alkyne)(binap)(CO)4] (BINAP=(1,1'-binaphthalene)-2,2'-diylbis(diphenylphosphine)) and shown that diastereomer interconversion occurs under Pauson-Khand reaction conditions when alkyne=HC[triple bond]CCO2Me. Attempts to isolate [Co2(alkyne)(binap)(CO)x] complexes with coordinated alkenes led to the formation of cobaltacyclopentadiene species.     

Covalent chemistry and conformational dynamics of topologically chiral amide-based molecular knots

The readily available in gram quantities tris(allyloxy)knot of the amide-type 5 (knotane) can be completely and partially deprotected with nBu(3)SnH in the presence of a palladium catalyst resulting in hydroxyknotanes 7-9. These, in turn, react with diethylchlorophosphate giving rise to knotanes equipped with between one and three phosphoryl groups. Sulfonylation of bis(allyloxy)monohydroxyknotane 8 with p-toluenesulfonyl chloride and, following removal of one or two allyl groups from the intermediate monosulfonate 13, give rise to sulfonyloxy-allyloxy-hydroxy- and sulfonyloxy-dihydroxy-knotanes 15 and 14, respectively. This provides a convenient method for the preparation of knotanes with any substitution pattern. All new knotanes have been isolated in preparative amounts and as highly pure substances with an exception of allyloxy-dihydroxyknotane 9. This compound could only be obtained as a mixture with the corresponding monohydroxy-derivative 8. The structures of all synthesized compounds were established by means of FAB and MALDI TOF mass spectrometry, (1)H and (31)P NMR spectroscopy. The triphosphorylated knotane 10 exhibits high solubility in alcohols, allowing its complete enantiomeric resolution with a commercially available chiral HPLC column. (1)H,(1)H DQF-COSY correlation spectroscopy along with H/D exchange experiments and ab initio calculations provided the first detailed (1)H NMR signal assignments of knotanes in [D(6)]DMSO solution. The combination of variable temperature (1)H and (31)P NMR spectroscopy and molecular modeling has been applied to study the conformational behavior of the new knotanes in different solvents. It has been shown that in DMSO solution at room temperature knotanes exist in a relatively rigid nonsymmetrical conformation similar to that found in the solid state while faster conformational exchange leading to the average D(3) symmetrical structure was detected in a number of other solvents.     

Palladium-catalyzed, stereoselective rearrangement of a tetracyclic allyl cyclopropane under arylation

The first example of a pi,sigma domino-Heck reaction under concomitant rearrangement of the tetracyclic allylcyclopropane endo,exo-bishomobarrelene (5) is reported; the stereoselective reaction proceeds via an intramolecular insertion of a primarily-formed carbopalladation intermediate into a strained cyclopropane C-C sigma-bond, giving 9.