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.     

Bonding Properties of a Novel Inorganometallic Complex, Ru(SnPh(3))(2)(CO)(2)(iPr-DAB) (iPr-DAB = N,N'-Diisopropyl-1,4-diaza-1,3-butadiene), and its Stable Radical-Anion, Studied by UV-Vis, IR, and EPR Spectroscopy, (Spectro-) Electrochemistry, and Density Functional Calculations

Ru(SnPh(3))(2)(CO)(2)(iPr-DAB) was synthesized and characterized by UV-vis, IR, (1)H NMR, (13)C NMR, (119)Sn NMR, and mass (FAB(+)) spectroscopies and by single-crystal X-ray diffraction, which proved the presence of a nearly linear Sn-Ru-Sn unit. Crystals of Ru(SnPh(3))(2)(CO)(2)(iPr-DAB).3.5C(6)H(6) form in the triclinic space group P&onemacr; in a unit cell of dimensions a = 11.662(6) ?, b = 13.902(3) ?, c = 19.643(2) ?, alpha = 71.24(2) degrees, beta = 86.91(4) degrees, gamma = 77.89(3) degrees, and V = 2946(3) ?(3). One-electron reduction of Ru(SnPh(3))(2)(CO)(2)(iPr-DAB) produces the stable radical-anion [Ru(SnPh(3))(2)(CO)(2)(iPr-DAB)](*-) that was characterized by IR, and UV-vis spectroelectrochemistry. Its EPR spectrum shows a signal at g = 1.9960 with well resolved Sn, Ru, and iPr-DAB (H, N) hyperfine couplings. DFT-MO calculations on the model compound Ru(SnH(3))(2)(CO)(2)(H-DAB) reveal that the HOMO is mainly of sigma(Sn-Ru-Sn) character mixed strongly with the lowest pi orbital of the H-DAB ligand. The LUMO (SOMO in the reduced complex) should be viewed as predominantly pi(H-DAB) with an admixture of the sigma(Sn-Ru-Sn) orbital. Accordingly, the lowest-energy absorption band of the neutral species will mainly belong to the sigma(Sn-Ru-Sn)-->pi(iPr-DAB) charge transfer transition. The intrinsic strength of the Ru-Sn bond and the delocalized character of the three-center four-electron Sn-Ru-Sn sigma-bond account for the inherent stability of the radical anion.     

Necessity of aromatic carboxylate anions to be planar to induce growth of cationic micelles

It is well-known that some aromatic anions have the ability to induce viscoelastic transformation in aqueous solutions of cationic surfactants even at added salt concentrations as low as 10-20 mM. This behavior is associated with the formation of an entangled network of elongated micelles. However, the effect of aromatic ring substituents on the anion's ability to promote rapid micelle growth is not well-understood. We have performed ab initio calculations of the carbonyl group rotation barriers in a series of substituted benzoate and naphthoate anions at the MP2/STO-3G level of theory. It was found that aromatic carboxylates, known to be particularly effective in causing sphere-rod transition in cationic micelles, preferably adopt conformations with the COO(-) group in the same plane as the ring(s). This structural preference can be attributed to either intramolecular hydrogen bonding (o-hydroxyl derivatives) or pi-conjugation effects (m- and p-halogenated derivatives). In the former case the barrier to rotation is 40-50 kcal/mol, whereas in the latter case the threshold value is around 3.0 kcal/mol. Propensity for the planar conformation correlates with a greater depth of counterion penetration into the micelle surface, as inferred from NMR experiments, compared to the anions with less hindered carbonyl rotation. This points to favorable hydrophobic interactions between the surfactant methylene groups and the aromatic ring(s) of the anion as a possible explanation for the rapid growth of cationic micelles observed upon addition of certain aromatic carboxylates.     

Ab initio studies on polymers. VI. Torsional potential in regular polyethylene chains

Ab initio crystal orbital calculations have been performed on regular polyethylene chains applying basis sets of minimal and double-zeta quality. Relative stabilities of periodic all-trans, all-gauche, and alternating trans–gauche conformers have been evaluated, including extensive geometry optimization. Potential curves for a simultaneous rotation around C? C single bonds from the all-trans to the all-gauche conformation have been computed applying the rigid-rotor approximation, the flexible-rotor approximation, and an additional reoptimization of C? C distances. A rigid-rotor potential curve from the all-trans to the alternating trans-gauche conformation has been computed as well. Results obtained are compared with ab initio calculations on butane and pentane and with semiempirical and empirical force-field studies on polyethylene.     

The use of emulsions for the determination of methylmercury and inorganic mercury in fish-eggs oil by cold vapor generation in a flow injection system with atomic absorption spectrometric detection

An on-line time based injection system used in conjunction with cold vapor generation atomic absorption spectrometry and microwave-aided oxidation with potassium persulfate has been developed for the determination of the different mercury species in fish-eggs oil samples. A three-phase surfactant-oil-water emulsion produced an advantageous flow when a peristaltic pump was used to introduce the highly viscous sample into the system. The optimum proportion of the oil-water mixture ratio was 2:3 v/v with a Tween 20 surfactant concentration in the emulsion of 0.008% v/v. Inorganic mercury was determined after reduction with sodium borohydride while total mercury was determined after an oxidation step with persulfate prior to the reduction step to elemental mercury with the same reducing agent. The difference between total and inorganic mercury determined the organomercury content in samples. A linear calibration graph was obtained in the range 0.1-20 micrograms l-1 of Hg2+ by injecting 0.7 ml of samples. The detection limits based on 3 sigma of the blank signals were 0.11 and 0.12 microgram l-1 for total and inorganic mercury, respectively. The relative standard deviation of ten independent measurements were 2.8 and 2.2% for 10 micrograms l-1 and 8.8 and 9.0% for 0.1 microgram l-1 amounts of total and inorganic mercury, respectively. The recoveries of 0.3, 0.6 and 8 micrograms l-1 of inorganic and organic mercury added to fish-eggs oil samples ranged from 93.0 to 94.8% and from 100 to 106%, respectively. Good agreement with those values obtained for total mercury content in real samples by electrothermal atomic absorption spectrometry was also obtained, differences between mean values were < 7%. With the proposed procedure, 22 proteropterous catfish-eggs oil samples from the northwestern coast of Venezuela were measured; while the organic mercury lay in the range 2.0 and 3.3 micrograms l-1, inorganic mercury was not detected.     

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.

     

Stereoselective synthesis of unnatural α-amino acid derivatives through photoredox catalysis

A protocol for stereoselective C-radical addition to a chiral glyoxylate-derived N-sulfinyl imine was developed through visible light-promoted photoredox catalysis, providing a convenient method for the synthesis of unnatural α-amino acids. The developed protocol allows the use of ubiquitous carboxylic acids as radical precursors without prior derivatization. The protocol utilizes near-stoichiometric amounts of the imine and the acid radical precursor in combination with a catalytic amount of an organic acridinium-based photocatalyst. Alternative mechanisms for the developed transformation are discussed and corroborated by experimental and computational studies.

A protocol for stereoselective C-radical addition to a chiral glyoxylate-derived N-sulfinyl imine was developed through visible light-promoted photoredox catalysis, providing a convenient method for the synthesis of unnatural α-amino acids.     

Modelling and mutation studies on the histamine H1-receptor agonist binding site reveal different binding modes for H1-agonists: Asp116 (TM3) has a constitutive role in receptor stimulation

Summary A modelling study has been carried out, investigating the binding of histamine (Hist), 2-methylhistamine (2-MeHist) and 2-phenylhistamine (2-PhHist) at two postulated agonistic binding sites on transmembrane domain 5 (TM5) of the histamine H₁-receptor. For this purpose a conformational analysis study was performed on three particular residues of TM5, i.e., Lys²⁰⁰, Thr²⁰³ and Asn²⁰⁷, for which a functional role in binding has been proposed. The most favourable results were obtained for the interaction between Hist and the Lys²⁰⁰/Asn²⁰⁷ pair. Therefore, Lys²⁰⁰ was subsequently mutated and converted to an alanine, resulting in a 50-fold decrease of H₁-receptor stimulation by histamine. Altogether, the data suggest that the Lys²⁰⁰/Asn²⁰⁷ pair is important for activation of the H₁-receptor by histamine. In contrast, analogues of 2-PhHist seem to belong to a distinct subclass of histamine agonists and an alternative mode of binding is proposed in which the 2-phenyl ring binds to the same receptor location as one of the aromatic rings of classical histamine H₁-antagonists. Subsequently, the binding modes of the agonists Hist, 2-MeHist and 2-PhHist and the H₁-antagonist cyproheptadine were evaluated in three different seven--helical models of the H₁-receptor built in homology with bacteriorhodopsin, but using three different alignments. Our findings suggest that the position of the carboxylate group of Asp¹¹⁶ (TM3) within the receptor pocket depends on whether an agonist or an antagonist binds to the protein; a conformational change of this aspartate residue upon agonist binding is expected to play an essential role in receptor stimulation.Abbreviations 2-MeHist 2-methylhistamine - 2-PEA 2-pyridyl-ethylamine - 2-PhHist 2-phenylhistamine - CHO Chinese hamster ovary - E_int interaction energy - E_str strain energy - GES global energy structure - gpH₁R guinea pig H₁-receptor - GPCR G-protein coupled receptor - Hist histamine - N proximal nitrogen - N tele nitrogen - TM transmembrane domain - WT wild type