Predicted Influence of N-Acetyl Group Content on the Conformational Extension of Chitin and Chitosan Chains

ABSTRACT

Conformational analysis of chitosan molecules has been performed using the MM3(92) force field to investigate the role played by the acetamido groups on the stiffness of these chains. A high dielectric constant value was needed to model an aqueous environment and to reproduce the distribution of the N-acetyl glucosamine group orientation that is observed by NMR. Disaccharidic fragments, differently substituted at C2, were selected as models for chitin and chitosan chains. Their conformational space has been explored by means of adiabatic mapping of the glycosidic Φ,Ψ torsion angles. Although the overall features of all the potential energy surfaces created appear similar, the accessible conformational space of a glycosidic bond is affected by the nature of the substituent at C2 on the non-reducing residue of the disaccharide unit. This is illustrated by the differences in the calculated partition functions together with the predicted average homonuclear and heteronuclear coupling constants. Computed maps were used to predict polymeric unperturbed dimensions, characteristic ratio and persistence length of idealized chitin and chitosan chains, by Monte Carlo methods. Pure chitosan is predicted to be more coiled than pure chitin chains. At low N-acetyl group contents, chain extension appears to be dependent on the degree of substitution. Average chain dimensions increase monotonically for increases in content up to 60% of N-acetyl groups, but show no significant variation at higher contents. For molecules consisting of 50% amino and 50% N-acetylated residues, random, alternate and block patterns of substitution have been investigated. It has also been shown that the spatial extension of the polymer chains is dependent on the primary structure. Comparison with the literature experimental data is difficult because of the extreme diversity of the reported conformationally dependent values. However, such study provides a unique insight into the dependence of these two factors (degree of acetylation and distribution of acetyl groups) on the stiffness and flexibility of different chitin and chitosan chains.     

Measurement of Lamb wave polarization using a one-dimensional scanning laser vibrometer (L)

A single head scanning laser Doppler vibrometer is used for the estimation of the polarization of the first symmetric (S(0)) and antisymmetric (A(0)) Lamb wave modes. The measurements at two known incidence angles are performed in order to resolve the two components of motion. Filtering in the frequency/wavenumber domain of the response recorded along a scan line separates the contributions from each mode and allows the evaluation of the corresponding elliptical trajectories of particle motion. Comparison between measured and analytically estimated trajectories validates the measurement technique and suggests its application for the development of material characterization and diagnostics tools.     

Compressive matched-field processing

Source localization by matched-field processing (MFP) generally involves solving a number of computationally intensive partial differential equations. This paper introduces a technique that mitigates this computational workload by "compressing" these computations. Drawing on key concepts from the recently developed field of compressed sensing, it shows how a low-dimensional proxy for the Green's function can be constructed by backpropagating a small set of random receiver vectors. Then the source can be located by performing a number of "short" correlations between this proxy and the projection of the recorded acoustic data in the compressed space. Numerical experiments in a Pekeris ocean waveguide are presented that demonstrate that this compressed version of MFP is as effective as traditional MFP even when the compression is significant. The results are particularly promising in the broadband regime where using as few as two random backpropagations per frequency performs almost as well as the traditional broadband MFP but with the added benefit of generic applicability. That is, the computationally intensive backpropagations may be computed offline independently from the received signals, and may be reused to locate any source within the search grid area.     

Nonaffine deformation of inherent structure as a static signature of cooperativity in supercooled liquids

We unveil the existence of nonaffinely rearranging regions in the inherent structures (IS) of supercooled liquids by numerical simulations of model glass formers subject to static shear deformations combined with local energy minimizations. In the liquid state IS, we find a broad distribution of large rearrangements which are correlated only over small distances. At low temperatures, the onset of the cooperative dynamics corresponds to much smaller displacements correlated over larger distances. This finding indicates the presence of nonaffinely rearranging domains of relevant size in the IS deformation, which can be seen as the static counterpart of the cooperatively rearranging regions in the dynamics. This idea provides new insight into possible structural signatures of slow cooperative dynamics of supercooled liquids and supports the connections with elastic heterogeneities found in amorphous solids.     

A review of the dynamical susceptibility in different complex systems

The dynamical susceptibility has been introduced to characterize the dynamical heterogeneities in glass forming liquids. We have used it as a tool to investigate the slow dynamics of other disordered systems such as gels, granular media and spin glasses. We review here the results obtained via numerical simulations of different model systems. The comparative study of the behaviour of the dynamical susceptibility sheds some light on the significant differences in the complex slow dynamics of glasses, spin glasses, granular media, irreversible gels, and colloidal gels.     

A generalization of a theorem on biseparating maps

In J. Math. Anal. Appl. 12 (1995) 258–265, Araujo et al. proved that for any linear biseparating map  from C(X) onto C(Y), where X and Y are completely regular, there exist ω in C(Y) and an homeomorphism h from the realcompactification vX of X onto vY, such that

The compact version of this result was proved before by Jarosz in Bull. Canad. Math. Soc. 33 (1990) 139–144. In Contemp. Math., Vol. 253, 2000, pp. 125–144, Henriksen and Smith asked to what extent the result above can be generalized to a larger class of algebras. In the present paper, we give an answer to that question as follows. Let A and B be uniformly closed Φ-algebras. We first prove that every order bounded linear biseparating map from A onto B is automatically a weighted isomorphism, that is, there exist ω in B and a lattice and algebra isomorphism ψ between A and B such that

(a)=ωψ(a) for all aA.

We then assume that every universally σ-complete projection band in A is essentially one-dimensional. Under this extra condition and according to a result from Mem. Amer. Math. Soc. 143 (2000) 679 by Abramovich and Kitover, any linear biseparating map from A onto B is automatically order bounded and, by the above, a weighted isomorphism. It turns out that, indeed, the latter result is a generalization of the aforementioned theorem by Araujo et al. since we also prove that every universally σ-complete projection band in the uniformly closed Φ-algebra C(X) is essentially one-dimensional.     

Inclusive ϱ0,K *±(892) andf production in\bar p p Interactions at 12 GeV/c

Inclusive production of ?⁰,K ^*±(892), andf is studied in \(\bar p\) p interactions at 12 GeV/c. The inclusive cross sections for ?⁰,K ^*±(892), andf are found to be 6.7±0.3 mb, 1.0±0.2 mb, and 1.4±0.3 mb, respectively. The differential cross sections are presented as a function of c.m. rapidity, Feynmanx and square of the transverse momentump _T ² . Comparison with the correspondingpp data shows some interesting differences which can be attributed to the \(\bar p\) p annihilation. The results are compared with the predictions of the quark fusion model.