Significance of the Geminal Dimethyl Group in the Odor Principle of Ambrox®

The diastereoisomeric 18-nor- and 19-norambrox ((6α)- and (6β)-dodecahydro-3a,6,9a-trimethylnaphtho[2,1-b]furans resp.) as well as the corresponding 18,19-dinor-derivatives (dodecahydro-3a,9a-dimethylnaphtho[2,1-b]furans) have been synthesized and subjected to sensory evaluation. Threshold data and odor determination give an enlarged insight into the structure-activity relationship (SAR) in ambrox-type ambergris fragrances. As a general conclusion, the accumulation of axial CH₃ groups in the tricyclic ethers 1 – 12 leads to the strongest receptor affinity.     

Special representations forn-bridge links

We describe a simple algorithm to obtain a catalogue of 3-bridge links by computer, depending upon 6-tuples of positive integers. This permits us to represent the genus two 3-manifolds by standardly constructed graphs with colored edges. Finally, we prove some results about the topological structure of these manifolds and extend the combinatorial representation ton-bridge links This work was performed under the auspices of the GNSAGA of the CNR (National Research Council) of Italy and financially supported by the Ministero della Universitá e della Ricerca Scientifica e Tecnologica of Italy within the project “Geometria Reale e Complessa”.     

Chromatic uniqueness of the generalized θ-graph

A generalized θ-graph in a connected graph with 3 paths between a pair of vertices of degree 3. It is shown that any graph having the same chromatic polynomial as a generalized θ-graph, must be isomorphic to the generalized θ-graph.     

Structure and bonding of the vanadium(III) hexa-aqua cation. 1. Experimental characterization and ligand-field analysis

Spectroscopic and crystallographic data are presented for salts containing the [V(OH(2))(6)](3+) cation, providing a rigorous test of the ability of the angular overlap model (AOM) to inter-relate the electronic and molecular structure of integer-spin complexes. High-field multifrequency EPR provides a very precise definition of the ground-state spin-Hamiltonian parameters, while single-crystal absorption measurements enable the energies of excited ligand-field states to be identified. The EPR study of vanadium(III) as an impurity in guanidinium gallium sulfate is particularly instructive, with fine-structure observed attributable to crystallographically distinct [V(OH(2))(6)](3+) cations, hyperfine coupling, and ferroelectric domains. The electronic structure of the complex depends strongly on the mode of coordination of the water molecules to the vanadium(III) cation, as revealed by single-crystal neutron and X-ray diffraction measurements, and is also sensitive to the isotopic abundance. It is shown that the AOM gives a very good account of the change in the electronic structure, as a function of geometric coordinates of the [V(OH(2))(6)](3+) cation. However, the ligand-field analysis is inconsistent with the profiles of electronic transitions between ligand-field terms.     

Synthesis and endosomolytic properties of poly(amidoamine) block copolymers

The poly(amidoamine)s (PAAs) ISA 1 and ISA 23 display pH-dependent conformational change and pH-dependent membrane perturbation. These properties confer potential for use as endosomolytic polymers for intracytoplasmic delivery of toxins and genes. Both polymers are relatively non-toxic, and moreover ISA 23 has the beneficial property in vivo, of being non hepatotropic when administered intravenously. Although ISA 23 and ISA 1 demonstrate ability to transfect cells, ISA 1 is also able to promote intracellular delivery of non-permeant toxins. The aim of this study was to synthesise random and block copolymers of ISA 1 and ISA 23 and investigate whether these second generation hybrids would allow optimisation of PAA biological characteristics. Random and block copolymers of ISA 1 and ISA 23 were synthesised by hydrogen transfer polyaddition to generate a library of PAAs with an ISA 23:ISA 1 molar ratios of 2:1 to 4:1. The resultant polymers have a pI slightly below 7.4 and a M(w) of 19,900-49,000 g/mol and a M(n) of 13,100-24,100 g/mol. Whereas none of the random or block copolymers were haemolytic at pH 7.4 all demonstrated pH-dependent membrane activity. At pH 5.5 they caused 50-60% haemoglobin (Hb) release over 1 h. This was slightly less than that seen for ISA 23 (80% Hb release). None of the copolymers were cytotoxic against B16F10 cells during a 72 h incubation (IC(50) > 2 mg/ml; MTT assay). The ability of the random and block copolymer PAAs to deliver the toxin gelonin was also examined, but only ISA 1 and the block copolymer B2 (ISA 23:ISA 1 at a 2:1 molar ratio) were able to promote intracellular delivery, as measured by cytotoxic activity. It would be interesting to study the body distribution of B2 and determine whether this toxin-delivering PAA is able to escape liver capture.     

Excitons in carbon nanotubes: an ab initio symmetry-based approach

The optical absorption spectrum of the carbon (4,2) nanotube is computed using an ab initio many-body approach which takes into account excitonic effects. We develop a new method involving a local basis set which is symmetric with respect to the screw-symmetry of the tube. Such a method has the advantages of scaling faster than plane-wave methods and allowing for a precise determination of the symmetry character of the single-particle states, two-particle excitations, and selection rules. The binding energy of the lowest, optically active states is approximately 0.8 eV. The corresponding exciton wave functions are delocalized along the circumference of the tube and localized in the direction of the tube axis.     

Algorithms for the matrix <Emphasis Type="Italic">p</Emphasis>th root

New theoretical results are presented about the principal matrix pth root. In particular, we show that the pth root is related to the matrix sign function and to the Wiener–Hopf factorization, and that it can be expressed as an integral over the unit circle. These results are used in the design and analysis of several new algorithms for the numerical computation of the pth root. We also analyze the convergence and numerical stability properties of Newtons method for the inverse pth root. Preliminary computational experiments are presented to compare the methods. AMS subject classification 15A24, 65H10, 65F30Numerical Analysis Report 454, Manchester Centre for Computational Mathematics, July 2004.Dario A. Bini: This work was supported by MIUR, grant number 2002014121.Nicholas J. Higham: This work was supported by Engineering and Physical Sciences Research Council grant GR/R22612 and by a Royal Society – Wolfson Research Merit Award.     

Mass spectrometric synthesis. V. The gas-phase ion-molecule dimerization of some sulfur containing heterocycles

The gas-phase, ion-molecule reactions occurring in the ion source of a mass spectrometer between differently substituted thiazoles, employed as starting compounds for synthesis of polymers exhibiting semiconducting properties, have been studied in detail. The structural characterization of the dimeric moieties so obtained has been carried out by exact mass measurements, linked scans for metastable analysis and collisional spectroscopy.     

Simultaneous determination of Zilpaterol and other beta agonists in calf eye by gas chromatography/tandem mass spectrometry

Adrenergic drugs for growth promotion have been outlawed in European meat production; however, molecules such as Ractopamine and Zilpaterol are licensed for feeding swine and cattle in the United States, Mexico, and South Africa. Analysis of bovine retinal extracts has recently shown considerable extension in the detection period following withdrawal. Previous studies demonstrated that residual concentrations of Clenbuterol and related substances in retinal tissue were > 100 ng/g at day 50 of withdrawal. A method was developed to identify and simultaneously quantify Clenbuterol-like substances with anilinic moieties and drugs with phenolic and catecholic moieties, such as Ractopamine and Zilpaterol, in retinal tissue. The method was validated according to SANCO/1805/2000. After extraction in 0.1 N HCl, samples were cleaned up on C18 non-endcapped solid-phase extraction columns and analyzed as trimethylchlorosilane derivatives by gas chromatography/tandem mass spectrometry, electron impact mode. At concentrations of agonists between 62.5 and 250.0 ng/g in bovine retina, mean recoveries ranged from 85.3 to 94.8%, repeatability was < 9.6%, and within-laboratory reproducibility was < 10.5%. The decision limits (CCalpha) were within the range of 66.3-70.4 ng/g, and the detection capability (CCbeta) varied from 73.9 to 79.8 ng/g. Results are discussed in terms of a multiresidue approach to improve reliability of the monitoring strategy.