Synthesis of ring-oxidized retinoids as substrates of mouse class I alcohol dehydrogenase (ADH1)

Ring-oxidized retinoids have been synthesized stereoselectively using the Stille cross-coupling reaction. Kinetic constants of mouse class I alcohol dehydrogenase (ADH1) with these retinoids were determined.     

Ion soft-landing into liquids: Protein identification,separation, and purification with retention of biological activity

Protein ions, after mass spectrometric separation, can be soft-landed into liquid surfaces with preservation of their native structures. Retention of biological activity is strongly favored in glycerol-based surfaces but not in self-assembled monolayer solid surfaces. Soft-landing efficiency for multiply-charged hexokinase ions was found to be some four times higher for a glycerol/fructose liquid surface than for a fluorinated self-assembled monolayer surface. Soft-landing into liquid surfaces is also shown to allow (1) protein purification, (2) on-surface identification of the soft-landed material using MALDI, and (3) protein identification by in-surface tryptic digestion. Pure lysozyme was successfully isolated from different mixtures including an oxidized, partially decomposed batch of the protein and a partial tryptic digest. Liquid glycerol/carbohydrate mixtures could be used directly to record MALDI spectra on the soft-landed compounds provided they were fortified in advance with traditional MALDI matrices such as p-nitroaniline and alpha-cyano-4-hydroxycinnamic acid. Various proteins were soft-landed and detected on-target using these types of liquid surface. Soft-landing of multiply-charged lysozyme ions onto fluorinated self-assembled monolayer surfaces was found to occur with a limited amount of neutralization, and trapped multiply-charged ions could be desorbed from the surface by laser desorption. Initial data is shown for a new approach to protein identification that combines top-down and bottom-up approaches by utilizing protein ion soft-landing from a protein mixture, followed by tryptic digestion of the landed material and detection of characteristic tryptic fragments by MALDI.     

Breaking a secure communication scheme based on the phase synchronization of chaotic systems

A security analysis of a recently proposed secure communication scheme based on the phase synchronization of chaotic systems is presented. It is shown that the system parameters directly determine the cipher text waveform, hence it can be readily broken by system parameter estimation from the cipher text signal.     

Excited states in 163,164Ho populated through incomplete-fusion reactions

High-spin states in ^163,164Ho were investigated by means of in-beam -ray spectroscopy techniques using the multidetector array GASP. Excited states in ^163,164Ho were populated predominantly through the incomplete-fusion mechanism in the ¹⁶⁰Gd (¹¹B reaction at a beam energy of 61 MeV. Known rotational bands in ¹⁶³ Ho have been extended to higher spins and a three-quasiparticle band has been observed in this nucleus. Rotational bands have been identified in ¹⁶⁴Ho and their configurations have been discussed. Empirical Gallagher-Moszkowski (GM) splitting energies were extracted from the and GM doublets. Alignments, band crossing frequencies, and electromagnetic properties have been analyzed in the framework of the cranking model.Received: 13 February 2004, Revised: 18 March 2004, Published online: 14 September 2004PACS: 21.10.Re Collective levels - 21.60.Ev Collective models - 23.20.Lv transitions and level energies - 27.70. + q      

Molecular structure-dynamics relationships in glassy poly(isophthalamide)s as revealed by wide angle x-ray scattering, dielectric loss spectroscopy, and molecular modelling

The effect of molecular structure on the gamma relaxation dynamics has been studied in a set of aromatic poly(isophthalamide)s. This polymer family differ in the bridge group between phenylene rings [hexafluoroisopropylidene (C(CF(3))(2)) or ether] and also in the presence of t-butyl groups (C(CH(3))(3)) as pendant substituent on the five position of isophthalic ring. The results obtained from wide angle x-ray scattering in the glassy state indicated that both (C(CF(3))(2)) and (C(CH(3))(3)) groups favor the separation between chains, which is reflected on different interchain average distances. Dielectric experiments showed that both bulky groups favor the mobility in the glassy state. Molecular modelling methods were used to know the kind of molecular motions associated to the dielectric relaxation observed below the glass transition temperature.     

Insulating,superconducting, and large-compressibility phases in nanotube ropes

The superconducting properties of carbon nanotube ropes are studied using a new computational framework that incorporates the renormalization of intratube interactions and the effect of intertube Coulomb screening. This method allows one to study both the limits of thin and thick ropes ranging from purely one-dimensional physics to the setting of 3D Cooper-pair coherence, providing good estimates of the critical temperature as a function of the rope physical parameters. We discuss the connection of our results with recent experiments.     

Exchange coupling in carboxylato-bridged dinuclear copper(II) compounds: a density functional study

A computational study of the exchange coupling is presented for a selected sample of carboxylato-bridged dinuclear copper(II) compounds. Model calculations have been used to examine the influence of several factors on the coupling constants: a) the electron-withdrawing power of the bridging ligands; b) the nature of the axial ligands; c) the number of bridging carboxylato groups; d) some structural distortions frequently found in this family of compounds; and e) the coordination mode of the carboxylato bridge. Coupling constants calculated for some complete structures, as determined by X-ray diffraction, are in excellent agreement with experimental data, confirming the ability of the computational strategy used in this work to predict the coupling constant for compounds for which experimental data are not yet available.     

Allelopathic agents from Cyrtocymura cincta

The sesquiterpenoid fractions from the chloroform extracts of roots and aerial parts of the weed Cyrtocymura cincta (Griseb.) H. Robinson (Compositae) were tested to observe the effects on seed germination and growth of three dicot and four monocot species. Promotion and inhibition effects were observed according to the examined compound, specific seed or cultivar, and concentration.     

Delayed crossing in the \pi h_{9/2} 1/2-[541] band of 173 Lu

High-spin states in the odd-proton nucleus ¹⁷³Lu have been populated in a ¹⁷⁰Er(⁷Li,4n) reaction and the emitted -radiation was detected with the GASP array. The favoured and unfavoured sequences of the band have been considerably extended. The favoured sequence does not show any indication of a band crossing up to a rotational frequency of 0.45 MeV. This is the largest crossing frequency ever observed for 1/2^- [541] bands of odd-proton nuclei with and . Previous Cranked Shell Model (CSM) calculations underestimate the crossing frequency by 100 keV.Received: 19 May 2003, Published online: 11 November 2003PACS: 21.10.-k Properties of nuclei; nuclear energy levels - 21.10.Re Collective levels - 23.20.Lv transitions and level energies - 27.70. + q      

Persistence of well-defined collective excitations in a molten transition metal

Well-defined microscopic collective excitations are found in liquid Ni at 1763 K by means of inelastic neutron scattering. Such excitations are supported by the liquid despite an anharmonic character of its thermodynamic functions. Consideration of the detailed shape of the interionic pair potential provides a way to understand why atomic motions at microscopic scales behave in a way much closer to the alkali metals than to the liquefied rare gases.