The Stille reaction in the synthesis of carotenoid butenolides: synthesis of 6'-epi-peridinin

A new strategy for carotenoid butenolides has been developed that is based in part in halogen-selective Stille cross-coupling of dihalogenated ylidenebutenolide segment 2 and highly functionalized alkenylstannanes. [reaction: see text]     

The isobutylene-isobutane alkylation process in liquid HF revisited

Details on the mechanism of HF catalyzed isobutylene-isobutane alkylation were investigated. On the basis of available experimental data and high-level quantum chemical calculations, a detailed reaction mechanism is proposed taking into account solvation effects of the medium. On the basis of our computational results, we explain why the density of the liquid media and stirring rates are the most important parameters to achieve maximum yield of alkylate, in agreement with experimental findings. The ab initio Car-Parrinello molecular dynamics calculations show that isobutylene is irreversibly protonated in the liquid HF medium at higher densities, leading to the ion pair formation, which is shown to be a minimum on the potential energy surface after optimization using periodic boundary conditions. The HF medium solvates preferentially the fluoride anion, which is found as solvated [FHF](-) or solvated F(-.)(HF)(3). On the other hand, the tert-butyl cation is weakly solvated, where the closest HF molecules appear at a distance of about 2.9 Angstrom with the fluorine termination of an HF chain.     

"Safe" Coulomb excitation of 30Mg

We report on the first radioactive beam experiment performed at the recently commissioned REX-ISOLDE facility at CERN in conjunction with the highly efficient gamma spectrometer MINIBALL. Using 30Mg ions accelerated to an energy of 2.25 MeV/u together with a thin (nat)Ni target, Coulomb excitation of the first excited 2+ states of the projectile and target nuclei well below the Coulomb barrier was observed. From the measured relative deexcitation gamma-ray yields the B(E2;0(+)gs-->2(+)1) value of 30Mg was determined to be 241(31)e2 fm4. Our result is lower than values obtained at projectile fragmentation facilities using the intermediate-energy Coulomb excitation method, and confirms the theoretical conjecture that the neutron-rich magnesium isotope 30Mg resides outside the "island of inversion."     

Mixing of non-Newtonian fluids in steadily forced systems

We investigate mixing in a viscoelastic and shear-thinning fluid-a very common combination in polymers and suspensions. We find that competition between elastic and viscous forces generates self-similar mixing, lobe transport, and other characteristics of chaos. The mechanism by which chaos is produced is evaluated both in experiments and in a simple model. We find that chaotic flow is generated by spontaneous oscillations, the magnitude and frequency of which govern the extent of chaos and mixing.     

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.