Folding and unfolding of an elastinlike oligopeptide: "inverse temperature transition," reentrance, and hydrogen-bond dynamics

The temperature-dependent behavior of a solvated oligopeptide, GVG(VPGVG), is investigated. Spectroscopic measurements, thermodynamic measurements, and molecular dynamics simulations find that this elastinlike octapeptide behaves as a two-state system that undergoes an "inverse temperature" folding transition and reentrant unfolding close to the boiling point of water. A molecular picture of these processes is presented, emphasizing changes in the dynamics of hydrogen bonding at the protein/water interface and peptide backbone librational entropy.     

Spectroscopy of 40Ca and negative-parity bands

We have studied the reactions as well as the binary channel , in order to search for deformed states, which form rotational bands in ⁴⁰Ca. We observe positive- and negative-parity bands. The negative-parity band is proposed to be a partner of an inversion doublet with the positive-parity states being based on 4p-4h configurations. The properties of the positive-parity states are discussed on the basis of the shell model and the parity doublet on the basis of a cluster model with intrinsic reflection asymmetric shapes.Received: 2 May 2003, Revised: 23 September 2003, Published online: 20 January 2004PACS: 21.10.-k Properties of nuclei; nuclear energy levels - 21.60.Gx Cluster models     

Detaching thiolates from copper and gold clusters: which bonds to break?

The interaction of alkanethiolates with small coinage metal clusters of copper and gold was studied based on density functional theory with a focus on the metal-thiolate junction. Calculation of fragmentation energies indicate that for Cu(n)-thiolate (n = 1,3,5,7, and 9) there is a progressive lowering in energy for the fragmentation of the S-C bond in the thiolate from a value of 2.9 eV for n = 1 to 1.4 eV for n = 9. The detailed electronic origins of this specific weakening are attributed to a polarization of electron density in the S-C bond as induced by bonding with the Cu(n) cluster. For the gold analogues, this effect is not observed and fragmentation at the S-C bond experiences only a slight 10% destabilization as n increases from 3 to 9. The relativistic origin of this difference between Cu and Au is discussed, and an analysis of bonding considerations is presented.     

Investigating the history of prehistoric glues by gas chromatography-mass spectrometry

Although organic materials are very sensitive to biochemical alteration processes, they may be preserved for millennia in various archaeological contexts. Remains of adhesives made during prehistory were discovered at different sites, in the form of residues adhering to flint tools and ceramic vessels or as free lumps in sediment. To characterise the natural substances exploited for adhesive production during late prehistory, we undertook GC and GC/MS analysis of 90 samples from 8 sites dating from the Neolithic to Iron Age periods. This paper discusses our approach to the study of organic adhesives preserved in archaeological contexts, with a particular focus on the presentation of the various categories of organic adhesives that we analysed and the choice of chromatographic conditions adapted to the specificity of such samples. The results obtained show that birch bark tar, a triterpenoid adhesive made by destructive distillation of white birch bark, was predominantly used during the neolithic period even though other materials such as various barks or organic fossil substance were also used. During the Bronze and Iron ages, which follow the Neolithic period, adhesive production is evolving through the expansion of the range of the natural substances used (identification of diterpenoid pine resin) and the addition of beeswax as a plasticiser to birch bark tar. By combining chromatographic analysis and archaeological data, it was thus possible to follow the evolution of adhesive making at the end of prehistory, testifying to the inventiveness of the craftsmen whatever the period considered.     

Comparison of the (17)O NMR spectra of zeolites LTA and LSX

¹⁷O NMR studies of various cation-exchanged LTA and LSX zeolites have shown similarities between the two systems. LSX samples containing divalent cations contain resonances with similar chemical shifts to those previously assigned to ‘bare’ framework oxygen atoms in Ca-LTA and Sr-LTA. The assignments are consistent with the trends seen in the spectra of monovalent cation-containing LSX and LTA zeolites, which show an increase in the average chemical shift with increasing cationic radius. The spectrum of Li-LSX, like Na-LSX, can be assigned based on the T–O–T bond angles. Gas sorption studies on Li-LSX are used to help identify the framework oxygen atoms that form the β-cages and demonstrate the sensitivity of the ¹⁷O shifts to gas loading.     

Numerical predictions and experiments on the free-plate edge mode

In this paper, te edge mode variation is studied with three different methods: the reciprocal work method, already used by Torvik [J. Acoust. Soc. Am. 41 (1967) 346] to model this phenomenon, the S-parameter method and a finite element model that are applied for the first time to the study of the edge resonance. Moreover, laser probe measurements of the edge mode have also been performed and compared to the numerical predictions. The good agreement between the numerical predictions and the experimental data allows full understanding of the resonant phenomenon. The edge resonance is linked to the strong increase in amplitude of two complex Lamb waves, and the edge mode is proved to radiate into the plate as the first symmetrical Lamb mode S(0). Displacements at the edge and away from the edge have been computed and measured to evaluate the spatial and temporal behaviour of the edge mode. The dependence of the edge resonance frequency and amplitude on the Poisson coefficient has also been studied.     

The structure of a self-assembled calixarene aqua-channel system

The crystal structure of the complex 12.calix-[4]-arene dihydroxyphosphonic acid, 12.propane diammonium, 12.ethanol and 40.water molecules is based on dimeric units of the calix, assembled via trigonal units into a hexameric tube of 15 A radius and 16 A depth, further assemby via spanning propane diammonium cations and ethanol molecules forms a channel (40 A), selectively containing all the water molecules.     

Some remarks on half-factorial orders

In questo articolo, si dimostra il legame fra la semi-fattorialità e la fattorialità debole nel contesto degli ordini algebrici. In particolare, si ottiene che un ordine semi-fattoriale ha il stesso numero di classi che su chiusura integrale.