Structural Elucidation of an Atropisomeric Entcassiflavan-(4β→8)-Epicatechin Isolated from Dalbergia monetaria L.f. Based on NMR and ECD Calculations in Comparison to Experimental Data

A rare dihydoxyflavan-epicatechin proanthocyanidin, entcassiflavan-(4β→8)-epicatechin, was isolated from Dalbergia monetaria, a plant widely used by traditional people from the Amazon to treat urinary tract infections. The constitution and relative configuration of the compound were elucidated by HR-MS and detailed 1D- and 2D-NMR measurements. By comparing the experimental electronic circular dichroism (ECD) spectrum with the calculated ECD spectra of all 16 possible isomers, the absolute configuration, the interflavan linkage, and the atropisomers could be determined.     

Disposable pipette tips extraction: Fundamentals,applications and state of the art

Disposable pipette tips extraction consists of a solid‐phase extraction in which the sorbent is poorly dispersed in a pipette tip, which allows a quick and dynamic contact between the aspirated analyte from the sample and the solid phase. It is a technique used particularly in food and forensic analysis, since it requires a small amount of sample and solvent. This article highlights the principles, advantages and disadvantages of the disposable pipette tips extraction method and reviews recent applications.     

Effects of alkyl chain lengths of gallates upon their distribution and reactivity towards diphenylpicryl hydracil radicals in Triton X‐100 micellar solutions

The reactivity of ethyl‐, propyl‐ and octylgallate towards diphenylpicryl hydracil radicals has been measured in homogeneous solution (ethanol) and in Triton X‐100 micellar solutions. Similar reactivities were measured in homogeneous solutions, indicating that the length of the alkyl chain does not influence the reactivity of the phenolic groups. On the other hand, different reactivities were measured in micellar solutions, particularly at low (5 mM) surfactant concentrations. Data obtained at different surfactant concentrations allow estimation of partitioning of the gallates and their intramicellar bimolecular rate constant. The values obtained indicate that all the observed differences in reactivity are attributable to differences in substrate partitioning between the micellar and aqueous pseudophases. In fact, similar values of the intramicellar rate constants were obtained, suggesting that the average location of the reactive groups inside the micelles is independent of the solute alkyl chain length. Copyright © 2009 John Wiley & Sons, Ltd.     

A novel cacalolide from Psacalium decompositum

A new cacalolide sesquiterpenoid, named as Romo-A, was isolated from the roots of Psacalium decompositum, Asteraceae, a Mexican medicinal shrub with antidiabetic properties. Its structure was elucidated by NMR, MS, IR, UV, and confirmed by X-ray diffraction studies.     

Transition probabilities of lines belonging to the 5p-nd (n = 4,5,6,7) transition arrays of Kr(I)

Relative transition probabilities for lines belonging to the 5p-nd (n = 4,5,6,7) transition arrays of neutral krypton have been determined by means of emission line-intensity measurements. The experimental values of the present work are compared with the experimental and theoretical data given by other authors. The relative transition probabilities for lines arising from some levels belonging to the 4p⁵nd (n = 6,7) configurations have been put on an absolute scale, taking into account experimental and theoretical data.     

Natural product based inhibitors of the thioredoxin-thioredoxin reductase system

Spiroketal naphthodecalins are readily assembled by Barton's base mediated Ullmann binaphthyl ether coupling, Dakin reactions and hypervalent iodine spirocyclization. The core structures can be further diversified by enone addition and Stille coupling reactions. Nanomolar inhibitors for the Trx/TrxR redox control system were prepared by this approach and compared to series of natural product isolates. Cytotoxicity in MCF-7 cell assays ranged from an IC50 of 1.6 to >100 microM.     

Fast and heteroclinic solutions for a second order ODE related to Fisher-Kolmogorov’s equation

We study the existence of fast and heteroclinic solutions of an ODE that arises in connection with travelling wave solutions of Fisher-Kolmogorovs equation. They are obtained by solving a minimum or constrained minimum problem. A variational characterization of the minimum speed for which heteroclinic solutions exist is obtained.Received: 14 November 2003, Accepted: 29 January 2004, Published online: 2 April 2004M. Arias: Supported by MCYT, Acción Integrada HP2000-0039, SpainJ. Campos: Supported by MCYT, BFM2002-01308 and Acción Integrada HP2000-0039, SpainA.M. Robles-Pérez: Supported by Acção Integrada E-15/01 and Fundaçâo para a Ciência e a Tecnologia, Portugal     

On the acoustic modes in a cylindrical duct with an arbitrary wall impedance distribution

The present paper considers the propagation of sound in a cylindrical duct, with a wall section of finite length covered by an acoustic liner whose impedance is an arbitrary function of position. The cases of (i) uniform wall impedance, and wall impedance varying along the (ii) circumference or (iii) axis of the duct, or (iv) both simultaneously, are explicitly considered. It is shown that a nonuniform wall impedance couples modes with distinct azimuthal l or axial m wave numbers, so that their radial wave numbers k can no longer be calculated separately for each pair (m,l). The radial wave numbers are the roots of an infinite determinant, in the case when the wall impedance varies either (i) circumferentially or (ii) radially. If the wall impedance varies (iv) both radially and circumferentially, then the radial wave numbers are the roots of a doubly infinite determinant, i.e., an infinite determinant in which each term is an infinite determinant. The infinite determinants specifying the radial wave numbers are written explicitly for sound in a cylindrical nozzle with a uniform axial flow, in which case the radial eigenfunctions are Bessel functions; the method of calculation of the radial wave numbers applies equally well to a cylindrical nozzle with shear flow and/or swirling flows, with the Bessel functions replaced by other eigenfunctions. The radial wave numbers are calculated by truncation of the infinite determinants, for several values of the aspect ratio, defined as the ratio of length to diameter. It is shown that a nonuniform wall impedance will give rise to additional modes compared with a uniform wall impedance. The radial wave numbers specify the eigenfrequencies for the acoustic modes in the duct; the imaginary parts of the eigenfrequencies specify the decay of the sound field with time, and thus the effectiveness of the acoustic liner.