Organic industrial products

AbstractsParticular products and fields of application

Organic industrial products     

A Landau theory of the Peierls-BCS transition

We introduce a Landau type theory of the Peierls instability-superconductor transition involving two complex order parameters. Under a particular inequality condition among expansion parameters, the theory predicts that the superfluid conductivity should vary as $\text{(T?T}{}_{\mathrm{<mtext>c</mtext>}}\text{)}{}^{\mathrm{<mtext>?3</mtext><mtext>2</mtext>}}$ above the critical region and as $\text{(T}{}^1{}_{\mathrm{<mtext>c</mtext>}}\text{?T)}{}^{\mathrm{<mtext>?3</mtext><mtext>2</mtext>}}$ below the critical region.     

Octopolar chromophores based on donor- and acceptor-substituted 1,3,5-tris(phenylethynyl)benzenes: impact of meta-conjugation on the molecular and electronic structure by means of spectroscopy and theory

The molecular and electronic structures of a series of all-meta-substituted phenylacetylene mesitylenes peripherally substituted with donor or acceptor (D-A) groups are studied. The impact of meta- and para-substitution patterns is also analyzed by employing Raman and optical spectroscopies in conjunction with theoretical calculations. Outer phenyl rings display a partial quinoid character induced by two different motifs: (i) outer phenyls --> triple bond charge transfer for the cases where these phenyls are substituted with electron-donors; (ii) double electron withdrawing effect in the molecules with the peripheral phenyls substituted with electron acceptors. A moderate tuning of the optical gap is observed in agreement with the partial blockade of pi-electron conjugation exerted by the meta disposition. The orbital structure of the compounds partially preserves that of the mesitylene group showing extra-conjugation due to the addition of the arms, so that conjugation is not entirely obstructed but partially impeded in the ground electronic state (i.e., electron occupied orbitals). As for the excited states, the low-lying energy empty orbitals offer better conditions for full conjugation over the whole molecular scaffold. Interesting optical properties such as overlapping centers along the lowest energy optical excitations and enhanced optical transparency with importance for the application of these materials in optoelectronics have been justified on the basis of the electronic structure. A greater degree of quinoidization, and more allowed pi-electron delocalization, over the entire molecule is recognized in the case of linear phenylacetylenes substituting in para positions the central core.     

Secoisolariciresinol dehydrogenase: mode of catalysis and stereospecificity of hydride transfer in Podophyllum peltatum

Secoisolariciresinol dehydrogenase (SDH) catalyzes the NAD+ dependent enantiospecific conversion of secoisolariciresinol into matairesinol. In Podophyllum species, (-)-matairesinol is metabolized into the antiviral compound, podophyllotoxin, which can be semi-synthetically converted into the anticancer agents, etoposide, teniposide and Etopophos. Matairesinol is also a precursor of the cancer-preventative "mammalian" lignan, enterolactone, formed in the gut following ingestion of, for example, various high fiber dietary foods, as well as being an intermediate to numerous defense compounds in vascular plants. This study investigated the mode of enantiospecific Podophyllum SDH catalysis, the order of binding, and the stereospecificity of hydride abstraction/transfer from secoisolariciresinol to NAD+. SDH contains a highly conserved catalytic triad (Ser153, Tyr167 and Lys171), whose activity was abolished with site-directed mutagenesis of Tyr167Ala and Lys171Ala, whereas mutagenesis of Ser153Ala only resulted in a much reduced catalytic activity. Isothermal titration calorimetry measurements indicated that NAD+ binds first followed by the substrate, (-)-secoisolariciresinol. Additionally, for hydride transfer, the incoming hydride abstracted from the substrate takes up the pro-S position in the NADH formed. Taken together, a catalytic mechanism for the overall enantiospecific conversion of (-)-secoisolariciresinol into (-)-matairesinol is proposed.     

Localized electropolymerization on oxidized boron-doped diamond electrodes modified with pyrrolyl units

This paper describes the functionalization of oxidized boron-doped diamond (BDD) electrodes with N-(3-trimethoxysilylpropyl)pyrrole (TMPP) and the influence of this layer on the electrochemical transfer kinetics as well as on the possibility of forming strongly adhesive polypyrrole films on the BDD interface through electropolymerization. Furthermore, localized polymer formation was achieved on the TMPP-modified BDD interface using the direct mode of a scanning electrochemical microscope (SECM) as well as an electrochemical scanning near-field optical microscope (E-SNOM). Depending on the method used polypyrrole dots with diameters in the range of 1-250 microm are electrogenerated.     

Proton-triggered octopolar NLO chromophores

C(3)-symmetric, octopolar 1,3,5-alkynylbenzenes with terminal pyridyl substituents are presented which show an increase up to 17-fold in the second-order NLO activity upon protonation while maintaining their octopolar character, as confirmed by the depolarization ratios measured.     

Inverting the local geodesic X-ray transform on tensors

We prove the local invertibility, up to potential fields, and stability of the geodesic X-ray transform on tensor fields of order 1 and 2 near a strictly convex boundary point, on manifolds with boundary of dimension n ≥ 3. We also present an inversion formula. Under the condition that the manifold can be foliated with a continuous family of strictly convex surfaces, we prove a global result which also implies a lens rigidity result near such a metric. The class of manifolds satisfying the foliation condition includes manifolds with no focal points, and does not exclude existence of conjugate points.     

Conical diffraction by multilayer gratings: a recursive integral equation approach

The paper is devoted to an integral equation algorithm for studying the scattering of plane waves by multilayer diffraction gratings under oblique incidence. The scattering problem is described by a system of Helmholtz equations with piecewise constant coefficients in ?² coupled by special transmission conditions at the interfaces between different layers. Boundary integral methods lead to a system of singular integral equations, containing at least two equations for each interface. To deal with an arbitrary number of material layers we present the extension of a recursive procedure developed by Maystre for normal incidence, which transforms the problem to a sequence of equations with 2×2 operator matrices on each interface. Necessary and sufficient conditions for the applicability of the algorithm are derived.     

Mechanical properties of silk: interplay of deformation on macroscopic and molecular length scales

Using an in situ combination of tensile tests and x-ray diffraction, we have determined the mechanical properties of both the crystalline and the disordered phase of the biological nanocomposite silk by adapting a model from linear viscoelastic theory to the semicrystalline morphology of silk. We observe a strong interplay between morphology and mechanical properties. Silk's high extensibility results principally from the disordered phase; however, the crystals are also elastically deformed.