Gene expression profiling using advanced mass spectrometric approaches

In the era of systems biology, computational and high-throughput experimental biological approaches are increasingly being combined to provide global snapshots of entire genomes and proteomes under tissue- and disease-specific conditions. The aim is to identify proteins changing in concentration and/or post-translational state and/or location, and develop a better molecular level understanding of the operation of biological systems. Here we describe an approach for comparative proteomics that builds upon the combination of high-performance nano-scale separations with the high-mass measurement accuracy, mass-resolving power and sensitivity of Fourier transform ion cyclotron resonance mass spectrometry to provide broad dynamic range, comprehensive and quantitative proteome measurements.     

Stereoselective one-pot preparation of 1,2,4,5-tetraalkylidene- and 1,4-dialkylidenecyclohexanes

1,2,4,5-Tetraalkylidene- and 1,4-dialkylidenecyclohexanes were prepared by the regio- and stereoselective homocoupling of skip-type diynes and enynes, and their Diels-Alder reaction to form a polycyclic compound was demonstrated.     

Investigating nonlinear dynamics from time series: The influence of symmetries and the choice of observables

When a dynamical system is investigated from a time series, one of the most challenging problems is to obtain a model that reproduces the underlying dynamics. Many papers have been devoted to this problem but very few have considered the influence of symmetries in the original system and the choice of the observable. Indeed, it is well known that there are usually some variables that provide a better representation of the underlying dynamics and, consequently, a global model can be obtained with less difficulties starting from such variables. This is connected to the problem of observing the dynamical system from a single time series. The roots of the nonequivalence between the dynamical variables will be investigated in a more systematic way using previously defined observability indices. It turns out that there are two important ingredients which are the complexity of the coupling between the dynamical variables and the symmetry properties of the original system. As will be mentioned, symmetries and the choice of observables also has important consequences in other problems such as synchronization of nonlinear oscillators. (c) 2002 American Institute of Physics.     

Thermodynamic study of alkali sulphates: Calculation of enthalpy,entropy and Gibbs free energy

Joined with measures of specific heat at low temperature , a calorimetric study of alkali sulphates from ordinary temperature to 1500 K has allowed the calculation of enthalpy, entropy and Gibbs free energy of these salts. The value of entropy at melting point is compared with the value assessed by an acoustical method.     

Robust discretizations versus increase of the time step for the Lorenz system

When continuous systems are discretized, their solutions depend on the time step chosen a priori. Such solutions are not necessarily spurious in the sense that they can still correspond to a solution of the differential equations but with a displacement in the parameter space. Consequently, it is of great interest to obtain discrete equations which are robust even when the discretization time step is large. In this paper, different discretizations of the Lorenz system are discussed versus the values of the discretization time step. It is shown that the sets of difference equations proposed are more robust versus increases of the time step than conventional discretizations built with standard schemes such as the forward Euler, backward Euler, or centered finite difference schemes. The nonstandard schemes used here are Mickens' scheme and Monaco and Normand-Cyrot's scheme.     

Bone matrix like assemblies of collagen: from liquid crystals to gels and biomimetic materials

Skeletal tissues associate in close interaction, a dense organic matrix and a mineral network. In bone, the major structural protein is type I collagen, associated with inorganic crystals of hydroxyapatite. The three-dimensional arrangement of collagen fibrils in compact bone forms regularly ordered networks and a parallel was evidenced between these structures and molecular assemblies described in liquid crystals. Similar structures are now obtained in vitro. Indeed, when purified type I collagen is highly concentrated in an acid soluble state, the protein spontaneously assembles into ordered liquid crystalline phases. After a sol/gel transition triggered by pH increase, biomimetic materials are formed which resemble the exact compact bone matrix architecture over distances reaching centimetres and more. The properties of these highly ordered materials will be reviewed recalling their supramolecular arrangement and the corresponding patterns when visualised in polarised light microscopy (birefringence) and transmission electron microscopy (TEM). The association of inorganic phases (amorphous silica) to form chiral hybrid materials will also be described so as the behaviour of cells (fibroblast adhesion and migration) when seeded on these dense biomimetic matrices.     

Studies on the titanium-catalyzed cyclopropanation of nitriles

The Ti-mediated reaction of Grignard reagents with nitriles was investigated with sub-stoichiometric amounts of titanium isopropoxide. Cyanoesters were converted to spirocyclopropanelactams in good yields using as low as 0.05 eq of Ti(O(i)Pr)4. Under similar conditions, cyanocarbonates led to spirocyclopropane oxazolidinones and/or aminocyclopropylcarbinols. A very short synthesis of the naturally occurring aminocyclopropanecarboxylic acid illustrates the usefulness of this methodology.     

Interferometric technique for measuring broadband ultrashort pulses at the sampling limit

We present a new technique for measuring ultrashort optical pulses by use of spectral phase interferometry for direct electric-field reconstruction that is suitable for large bandwidth pulses. The method does not require generation of a replica of the pulse to be measured and encodes the spectral phase information in a spatial interference pattern. A major advantage of this method is that the spectral sampling saturates the Whittaker-Shannon bound. Moreover, the technique allows for the characterization of some types of space-time coupling. An experimental demonstration of the technique is presented.     

Complete characterization of periodic optical sources by use of sampled test-plus-reference interferometry

An interferometric technique measuring the time-dependent electric field of a periodic optical source that uses samples of its interference with a reference source of short optical pulses is presented. Compared with other test-plus-reference techniques such as spectral interferometry and Fourier-transform spectroscopy, the technique is applicable when the signal under test and the reference signal do not originate from the same source. It is highly sensitive and allows the direct real-time characterization of optical sources and the extraction of a coherent periodic signal in an incoherent background.