DFT, ab initio, NMR, and NBO analyses of N-substituted hydrazino acetamides: Experimental vs theoretical values

We studied the DFT (B3LYP) and HF at 6-31+G/6-31+G^∗∗ levels of theory in order to throw light on the conformation, structure, intramolecular hydrogen bond network, as well as proton and nitrogen NMR (GIAO method) of a series of model primary amides in the gas phase and/or in solution (chloroform, methanol, water, dimethyl sulfoxide, and heptane). In this manner, it was possible to show that the amidic group of these model compounds acts as the H-bond donor and interacts with two different H-bond acceptors, thus stabilizing the C₈ pseudocycle. The study was conducted to gain a better understanding of the conformation (both experimentally and theoretically) adopted by hydrazino acetamides (model compounds for aza-β³-peptides). In the light of this, we were able to explain why aza-β³-peptides develop a different H-bond network in comparison to their isosteric β³-peptide analogues (an extension of the β-peptide concept).     

Sound propagation in a monodisperse bubble cloud: From the crystal to the glass

We present a theoretical study of the propagation of a monochromatic pressure wave in an unbounded monodisperse bubbly liquid. We begin with the case of a regular bubble array --a bubble crystal-- for which we derive a dispersion relation. In order to interpret the different branches of this relation, we introduce a formalism, the radiative picture, which is the adaptation to acoustics of the standard splitting of the electric field in an electrostatic and a radiative part in Coulomb gauge. In the case of an irregular or completely random array --a bubble glass-- and at wavelengths large compared to the size of the bubble array spatial inhomogeneities, the difference between order and disorder is not felt by the pressure wave: a dispersion relation still holds, coinciding with that of a bubble crystal with the same bubble size and air volume fraction at the centre of its first Brillouin zone. This relation is discussed and compared to that obtained by Foldy in the framework of his multiscattering approach.     

Interaction of sodium and potassium ions with sandwiched cytosine-, guanine-, thymine-, and uracil-base tetrads

Nucleic acid tetraplexes and lipophilic self-assembling G-quadruplexes contain stacked base tetrads with intercalated metal ions as basic building blocks. Thus far, quantum-chemical studies have been used to explore the geometric and energetic properties of base tetrads with and without metal ions. Recently, for the first time, work on a sandwiched G-tetrad complex has been studied. We report here results of a systematic B3LYP density functional study on sandwiched G-, C-, U-, and T-tetrads with Na+ and K+ at different symmetries that substantially extend the recent work. The results include detailed information on total energies as well as on metal ion tetrad and base-base interaction energies. The geometrical parameters of the sandwiched metal ion complexes are compared to both experimental structures and to calculated geometries of complexes of single tetrads with metal ions. A microsolvation model explains the ion selectivity preference of K+ over Na+ in a qualitative sense.     

Exploring the melting of a semirigid-chain polymer with temperature-resolved small-angle <Emphasis Type="Italic">X</Emphasis>-ray scattering

The thermal behavior of semirigid semicrystalline polymers differs significantly from that of flexible-chain polymers. The origin of the differences is believed to lie in the higher energy expenditure associated with the formation of adjacent re-entry folds at the crystalline surface in the case of semirigid chains. The effect of constraints imposed by the interlamellar amorphous regions on the neighboring crystals was studied with temperature-resolved synchrotron radiation small-angle X-ray scattering (SAXS). The analysis of SAXS patterns with a generalized paracrystalline lamellar stack model indicates that melting of a semirigid-chain polymer is not a random process but that the crystals grown in the smallest amorphous gaps melt first. This suggests that the hitherto largely neglected geometrical confinement effects may play an important role in determining the thermodynamic stability of semirigid-chain polymer crystals.Received: 5 March 2004, Published online: 4 May 2004PACS: 61.41. + e Polymers, elastomers, and plastics - 64.70.Dv Solid-liquid transitions - 81.10.Aj Theory and models of crystal growth; physics of crystal growth, crystal morphology and orientation     

ePTFE functionalization for medical applications

Polytetrafluoroethylene (PTFE) is a ubiquitous material used in implants and medical devices in general due to its high biocompatibility and inertness; blood vessels, heart, jawbone, nose, eyes, or abdominal wall can benefit from its properties in the case of disease or injury. Its expanded version, ePTFE, is an improved version of PTFE with better mechanical properties, which extend its medical applications. However, ePTFE implants often lack improvement in properties such as antibacterial, antistenosis, or tissue integration properties. Improvements in these properties by several strategies of functionalization for medical purposes are discussed in this review. Covalent and non-covalent bonding are reviewed, including more specifically chemical impregnation, chemical surface modification, autologous vascularization, and cell seeding, which are strategies mainly used for improving the properties of ePTFE and are described in this review.     

The bubble cloud as an N-degree of freedom harmonic oscillator

The dynamics of a two-dimensional N-bubble static cloud is investigated and shown to be well described by an N-degree of freedom harmonic oscillator model, at least at low enough frequencies. Eigenmodes and eigenfrequencies are calculated and compared with experimental results obtained with an assembly of bubbles caught up under a net in a water tank. Accordance is found to be excellent in the frequency range of validity of the model, the limits of which are discussed. An interpretation of the low-frequency branch of Foldy’s dispersion relation in bubbly liquids is suggested in terms of “bubble waves” in a quasi-incompressible medium.