Enzymic hydrolysis of the bacterial polysaccharide xanthan by cellulase

In this paper the mechanism of enzymic hydrolysis by a cellulase on xanthan is investigated. It is demonstrated that in salt free solution there is a random breakdown of the main chain when the polysaccharide is in the unordered conformation. The apparent rate of hydrolysis followed by the decrease of the solution viscosity depends on the quality of the solution. In addition, the rate of hydrolysis may be directly correlated with the degree of local order expressed by its specific rotary power. It is shown that there is no hydrolysis on the ordered helical conformation.     

Hydration of hyaluronan polysaccharide observed by IR spectrometry. II. Definition and quantitative analysis of elementary hydration spectra and water uptake

We recorded a series of spectra of sodium hyaluronan (HA) films that were in equilibrium with their surrounding humid atmosphere. The hygrometry of this atmosphere extended from 0 to 0.97% relative humidity. We performed a quantitative analysis of the corresponding series of hydration spectra that are the difference spectra of the film at a defined hygrometry minus the spectrum of the dried film (hygrometry = 0). The principle of this analysis is to use this series of hydration spectra to define a limited number (four) of "elementary hydration spectra" over which we can decompose all hydration spectra with good accuracy. This decomposition, combined with the measurements of the numbers of H(2)O molecules at the origin in these elementary hydration spectra of the three characteristic vibrational bands of H(2)O, allowed us to calculate the hydration number under different relative humidity conditions. This number compares well with that determined by thermogravimetry. Furthermore, the decomposition defines for each hygrometry value which chemical mechanisms represented by elementary hydration spectra are active. This analysis is pursued by determining for the elementary hydration spectra the number of hydrogen bonds established by each of the four alcohol groups found in each disaccharide repeat unit before performing the same analysis for amide and carboxylate groups. These results are later utilized to discuss the structure of HA at various stages of hydration.     

Comparative rheological behavior of hyaluronan from bacterial and animal sources with cross-linked hyaluronan (hylan) in aqueous solution

Using a variety of rheological techniques, the behavior of hyaluronan (M(w) 0.8-2.2 x 10(6)), cross-linked hyaluronan (hylan) (M(w) 1.8-12.5 x 10(6)), and Healon (M(w) approximately 5 x 10(6)) (a proprietary hyaluronan) was studied over a large range of molecular weights. The object was to study the effect of the cross-links in hylan on the various rheological parameters, in comparison with linear hyaluronan. There are significant differences. The Huggins constant and the critical overlap parameter C*[eta] are considerably lower for hylan and an increase in moduli at low frequencies was observed for hylan compared with the hyaluronan samples at all molecular weights studied. The results point to a difference in structure in dilute solution for hylan due to the ability to form networks, which can be removed by pressure filtration. In contrast, we do not find an increase of the steady shear viscosity and elastic modulus at higher concentrations when a homogeneous entangled network is reached. We attribute this behavior to the semirigid character of the hyaluronan chain and to the predominance of entanglements over the cross-link points present in hylan in the semidilute domain. Due to the higher apparent molecular weights that are possible with hylan structures but not with the hyaluronans currently available, a wider range of applications can be achieved with hylans when viscoelasticity is required, particularly for the viscosupplementation of synovial fluid damaged by osteoarthritis.     

Dermatoglyphic analysis in bipolar affective disorder and schizophrenia--"continuum of psychosis" hypothesis corroborated?

Dermatoglyphic features are thought to be indicators of events in the early embryonal stages. They might also be associated with the developmental disorders of the central nervous system (CNS) including schizophrenia. Dermatoglyphic features of 92 male patients with bipolar affective disorder (BPAD) (unipolar depression and schizoaffective psychosis were excluded from the study) were compared with those of 195 males with schizophrenia (SCH) and both with those of 200 male controls (control group-CG). DSM-III-R criteria were used for the diagnostic evaluation. Quantitative analysis showed only one statistically significant difference between BPAD and SCH patients groups, regarding the c-d ridge count of the left hand. The canonical discriminant analysis did not permit correct classification (only 59.23% of cases were correctly classified) between BPAD and SCH. Numerous quantitative dermatoglyphic features of both BPAD and SCH differed significantly from those of the control subjects. Finger ridge counts as well as palmar ridge counts were markedly lower in BPAD and SCH as compared to the controls. These findings are not in contradiction with the hypothesis claiming that psychoses are a set of diverse expressions (due also to noninherited factors) of a single underlying entity.     

Structure and properties of a bacterial polysaccharide named Fucogel

The chemical structure of a polysaccharide named Fucogel was characterized and the position of acetylation was identified by NMR. A conformational analysis was performed on this 3-sugar repeating unit. From this, the persistence length, characterizing the stiffness of the polysaccharide, was determined and the role of the presence of acetyl group, reducing the stiffness, was pointed out. The helical conformations were also predicted, one of these being in agreement with X-ray data obtained on a similar polysaccharide. Experimental characterization of the native and deacetylated polysaccharides was developed. SEC experiments allowed us to determine the molar mass and the persistence length on the deacetylated polysaccharide. The value is in good agreement with that predicted from the molecular modeling. Microcalorimetry, rheology, and fluorescence spectroscopy demonstrated respectively that no helical conformation exists in solution but that loose interchain interactions due to the acetyl substituents exist in dilute solutions.     

Polyelectrolyte behavior of carrageenans in aqueous solutions

Osmotic coefficients of sodium, potassium, and calcium counterions have been determined in aqueous solutions on kappa-, iota-, and lambda-carrageenans at 25°C. The experimental results are correlated with the calculated ones from the limiting law of Manning. An orderd secondary structure exists in kappa- and iota-carrageenans. Its stability is discussed as a function of temperature, ionic strength, and the nature of the counterions.     

Sodium and calcium counterion activity in the presence of xanthan polysaccharide

This work concerns the activity coefficient determination for sodium and calcium ions in a semi-dilute solution of xanthan when they are mixed in various ratios, and their correlation with the conformational structures. From these values we show that the conformation can be related to the dissociation of the polymer carboxylic acid sites. Below an apparent dissociation coefficient of about 0.29, the conformation is ordered and above 0.55 the xanthan conformation is entirely disordered. The value of the counterion activity coefficient in pure solution of sodium or calcium xanthan salts agrees fairly well with the theoretical ones derived from Manning's and Lifson-Katchalsky's theories if we make the assumption that the Na form is a stretched coil and the Ca form a single fivefold helix.     

Order-disorder conformational transition in succinoglycan: calorimetric measurements

Differential scanning microcalorimetry was performed on succinoglycan samples from different sources in order to better understand the thermally induced order-disorder conformational transition of the polysaccharide. The shape of thermograms, as well as the melting temperature, were related to the content or distribution of the succinate groups at least in salt-free solution. With increasing polysaccharide and/or salt concentration, the change in the shape of the thermogram was attributed to a progressive screening of the succinate contribution to the order-disorder conformational transition instead of a change in the transition mechanism. In the presence of salt, contrary to the rheological behavior, the calorimetric results were found to be independent of the thermal history of the samples. This suggests a very low enthalpic contribution of the interchain interactions present in succinoglycan solutions. Possible contributions that could explain some discrepancies with results already published in the literature are discussed.