Automated glycan assembly of a S. pneumoniae serotype 3 CPS antigen

Vaccines against S. pneumoniae, one of the most prevalent bacterial infections causing severe disease, rely on isolated capsular polysaccharide (CPS) that are conjugated to proteins. Such isolates contain a heterogeneous oligosaccharide mixture of different chain lengths and frame shifts. Access to defined synthetic S. pneumoniae CPS structures is desirable. Known syntheses of S. pneumoniae serotype 3 CPS rely on a time-consuming and low-yielding late-stage oxidation step, or use disaccharide building blocks which limits variability. Herein, we report the first iterative automated glycan assembly (AGA) of a conjugation-ready S. pneumoniae serotype 3 CPS trisaccharide. This oligosaccharide was assembled using a novel glucuronic acid building block to circumvent the need for a late-stage oxidation. The introduction of a washing step with the activator prior to each glycosylation cycle greatly increased the yields by neutralizing any residual base from deprotection steps in the synthetic cycle. This process improvement is applicable to AGA of many other oligosaccharides

Laser-fabricated porous alumina membranes (LF-PAM) for the preparation of metal nanodot arrays

We report on an efficient photonic-based method to prepare nanodot array of functional materials, independently of the nature of the substrate.Comment: Small (2008) Accepte

Sedimentation-consolidation of a double porosity material

This paper studies the sedimentation-consolidation of a double porosity material, such as lumpy clay. Large displacements and finite strains are accounted for in a multidimensional setting. Fundamental equations are derived using a phenomenological approach and non-equilibrium thermodynamics, as set out by Coussy [Coussy, Poromechanics, Wiley, Chichester, 2004]. These equations particularise to three non-linear partial differential equations in one dimensional context. Numerical implementation in a finite element code is currently being undertaken

Continuous variable quantum cryptography using coherent states

We propose several methods for quantum key distribution (QKD) based upon the generation and transmission of random distributions of coherent or squeezed states, and we show that they are are secure against individual eavesdropping attacks. These protocols require that the transmission of the optical line between Alice and Bob is larger than 50 %, but they do not rely on "non-classical" features such as squeezing. Their security is a direct consequence of the no-cloning theorem, that limits the signal to noise ratio of possible quantum measurements on the transmission line. Our approach can also be used for evaluating various QKD protocols using light with gaussian statistics.Comment: 5 pages, 1 figure. In v2 minor rewriting for clarity, references adde

Dynamics and hysteresis in square lattice artificial spin-ice

Dynamical effects under geometrical frustration are considered in a model for artificial spin ice on a square lattice in two dimensions. Each island of the spin ice has a three-component Heisenberg-like dipole moment subject to shape anisotropies that influence its direction. The model has real dynamics, including rotation of the magnetic degrees of freedom, going beyond the Ising-type models of spin ice. The dynamics is studied using a Langevin equation solved via a second order Heun algorithm. Thermodynamic properties such as the specific heat are presented for different couplings. A peak in specific heat is related to a type of melting-like phase transition present in the model. Hysteresis in an applied magnetic field is calculated for model parameters where the system is able to reach thermodynamic equilibrium.Comment: Revised versio

Consistently Solving the Simplicity Constraints for Spinfoam Quantum Gravity

We give an independent derivation of the Engle-Pereira-Rovelli spinfoam model for quantum gravity which recently appeared in [arXiv:0705.2388]. Using the coherent state techniques introduced earlier in [arXiv:0705.0674], we show that the EPR model realizes a consistent imposition of the simplicity constraints implementing general relativity from a topological BF theory.Comment: 6 pages, 2 figures, v2: typos correcte

A Search for Variations of Fundamental Constants using Atomic Fountain Clocks

Over five years we have compared the hyperfine frequencies of 133Cs and 87Rb atoms in their electronic ground state using several laser cooled 133Cs and 87Rb atomic fountains with an accuracy of ~10^{-15}. These measurements set a stringent upper bound to a possible fractional time variation of the ratio between the two frequencies : (d/dt)ln(nu_Rb/nu_Cs)=(0.2 +/- 7.0)*10^{-16} yr^{-1} (1 sigma uncertainty). The same limit applies to a possible variation of the quantity (mu_Rb/mu_Cs)*alpha^{-0.44}, which involves the ratio of nuclear magnetic moments and the fine structure constant.Comment: 4 pages, 3 figures, 1 table submitted to Phys. Rev. Let

Energy at Origins: Favorable Thermodynamics of Biosynthetic Reactions in the Last Universal Common Ancestor (LUCA)

Though all theories for the origin of life require a source of energy to promote primordial chemical reactions, the nature of energy that drove the emergence of metabolism at origins is still debated. We reasoned that evidence for the nature of energy at origins should be preserved in the biochemical reactions of life itself, whereby changes in free energy, ΔG, which determine whether a reaction can go forward or not, should help specify the source. By calculating values of ΔG across the conserved and universal core of 402 individual reactions that synthesize amino acids, nucleotides and cofactors from H2, CO2, NH3, H2S and phosphate in modern cells, we find that 95-97% of these reactions are exergonic (ΔG ≤ 0 kJ⋅mol-1) at pH 7-10 and 80-100°C under nonequilibrium conditions with H2 replacing biochemical reductants. While 23% of the core's reactions involve ATP hydrolysis, 77% are ATP-independent, thermodynamically driven by ΔG of reactions involving carbon bonds. We identified 174 reactions that are exergonic by -20 to -300 kJ⋅mol-1 at pH 9 and 80°C and that fall into ten reaction types: six pterin dependent alkyl or acyl transfers, ten S-adenosylmethionine dependent alkyl transfers, four acyl phosphate hydrolyses, 14 thioester hydrolyses, 30 decarboxylations, 35 ring closure reactions, 31 aromatic ring formations, and 44 carbon reductions by reduced nicotinamide, flavins, ferredoxin, or formate. The 402 reactions of the biosynthetic core trace to the last universal common ancestor (LUCA), and reveal that synthesis of LUCA's chemical constituents required no external energy inputs such as electric discharge, UV-light or phosphide minerals. The biosynthetic reactions of LUCA uncover a natural thermodynamic tendency of metabolism to unfold from energy released by reactions of H2, CO2, NH3, H2S, and phosphate