Biomedical subjects

Marguerite Rinaudo

Publications and source records attributed to Marguerite Rinaudo.

12 recordsLinked to original sources

PubMed2006

Non-covalent interactions in polysaccharide systems.

[Chemical structure: see text] This paper describes the behavior of some polysaccharides with well-known chemical structures and in which the influence of cooperative secondary interactions play an important role. The roles played by hydrophobic and ionic interactions (including ionic selectivity) on polysaccharide conformation and gelation are discussed. Electrostatic attractions are also important in the complexes formed between surfactants and polyelectrolytes of opposite charge. Finally, van der Waals dipolar interactions and particularly hydrogen-bond formation are examined. The role of hydrogen bonds in solubility, conformation, and especially the local stiffness of polysaccharides, but also in polymer-polymer complexes frequently obtained with polysaccharides, is developed. Repeat unit for a number polysaccharides.

Carbohydrate Conformation↗

PubMed2006

Controlled synthesis and inclusion ability of a hyaluronic acid derivative bearing beta-cyclodextrin molecules.

A new synthetic route to beta-cyclodextrin-linked hyaluronic acid (HA-CD) was developed. This was based on the preparation of a HA derivative selectively modified with adipic dihydrazide (HA-ADH) and a beta-cyclodextrin derivative possessing an aldehyde function on the primary face, followed by their coupling by a reductive amination-type reaction. The CD-polysaccharide was fully characterized in terms of chemical integrity and purity by high-resolution NMR spectroscopy. The complexation ability of the grafted CD was further demonstrated by isothermal titration calorimetry using sodium adamantane acetate (ADAc) and Ibuprofen as model guest molecules. The thermodynamic parameters for the complexation of these negatively charged guest molecules by the beta-CD grafted on negatively charged HA were shown to be largely influenced by the ionic strength of the aqueous medium.

Acetates↗

PubMed2006

High-level production and purification of a fully active recombinant dextransucrase from Leuconostoc mesenteroides NRRL B-512F.

Recombinant expression of the dextransucrase dsrS gene by Escherichia coli was optimized to produce 5850 U L(-1) (culture) of DSR-S, corresponding to a 30-fold increase compared with previous studies. Rational deletions of the signal peptide, the beginning of the variable region and the last four repeats of the C-terminal end caused no loss of activity. This new variant successfully purified was remarkably stable. With a k(cat) of 584 s(-1), it is the most efficient recombinant glucansucrase described to date. The synthesized polymer possesses more than 95% of alpha-1,6 links, like the dextran produced by the native enzyme, and innovative gel properties were obtained.

Blotting, Western↗

PubMed2005

Assembly of the full-length recombinant mouse prion protein I. Formation of soluble oligomers.

The conversion of a monomeric alpha-helix-rich isoform to multimeric beta-sheet-rich isoforms is a prominent feature of the conversion between PrP(C) and PrP(SC). We mimicked this process in vitro by exposing an unglycosylated recombinant form of the full-length mouse prion protein ((Mo)PrP(23-231)) to an acidic pH, at 37 degrees C, and we monitored the kinetics of conformational change and assembly. In these conditions, monomeric (Mo)PrP(23-231) converts slowly to two ensembles of soluble oligomers that are separated by size exclusion chromatography. The larger oligomers (I) are unstable, and their formation involves almost no change in secondary structure content. The smaller oligomers (II) form stable spherical or annular particles containing between 8 and 15 monomers as determined by multi-angle laser light scattering (MALLS). Their formation is concomitant with the main, thought limited, change in the secondary structure content (10%) seen by Fourier Transform Infrared (FTIR) spectroscopy. Even if these oligomers conserve a large part of the secondary structure of monomeric PrP, they exhibit amyloid features with the appearance of intermolecular beta-structure as revealed by the appearance of an IR band below 1620 cm(-1).

Animals↗

PubMed2004

Macromolecular dimensions and mechanical properties of monolayer films of Sonorean mesquite gum.

Mesquite gum sourced from Prosopis velutina trees and gum arabic (Acacia spp.) were characterized using light scattering and Langmuir isotherms. Both gum materials were fractionated by hydrophobic interaction chromatography, yielding four fractions for both gums: FI, FIIa, FIIb and FIII in mesquite gum and FI, FII, FIIIa and FIIIb in gum arabic. In mesquite gum, the obtained fractions had different protein content (7.18-38.60 wt.-%) and macromolecular dimensions (M approximately 3.89 x 10(5)-8.06 x 10(5) g.mol(-1), RG approximately 48.83-71.11 nm, RH approximately 9.61-24.06 nm) and architecture given by the structure factor (RG/RH ratio approximately 2.96-5.27). The mechanical properties of Langmuir monolayers at the air-water interface were very different on each gum and their fractions. For mesquite gum, the most active species at the interface were those comprised in Fractions IIa and IIb and III, while Fraction I the pi/A isotherm lied below that of the whole gum. In gum arabic only Fraction III developed greater surface pressure at the same surface per milligram of material than whole gum. This is rationalized in terms of structural differences in both materials. Mesquite gum tertiary structure seems to fit best with an elongated polydisperse macrocoil in agreement with the "twisted hairy rope" proposal for arabinogalactan proteoglycans.

Carbohydrates↗

PubMed2003

Synthesis of starch derivatives with labile cationic groups.

A new route to starch derivatives bearing hydrolyzable cationic groups was developed. This was based on reacting starch compounds with betaine derivatives in the presence of diisopropylcarbodiimide and 4-dimethylaminopyridine as coupling reagents in an aprotic polar solvent. Water-soluble starches with a perfectly controlled degree of substitution were thus obtained which were fully characterized by infrared, 1H and 13C spectroscopy and viscosity measurements. The cationic groups grafted on the polysaccharides are shown to hydrolyze slowly upon storage at room temperature.

4-Aminopyridine↗

PubMed2002

Characterization of white wine mannoproteins.

Mannoproteins, Saccharomyces cerevisiae yeast polysaccharides, play a major role in wine processing and characteristics. A systematic characterization of these polymers in terms of chemical composition and molecular structure is addressed in this study. Mannoproteins were isolated from white wine through a sequence of operations that consisted of nanofiltration for concentration of macromolecules, polysaccharide precipitation with ethanol, and affinity chromatography on concanavalin A. The whole wine mannoproteins present a very broad molecular mass distribution with several populations. Two major populations with very different compositions were separated by size exclusion chromatography. The mannoproteins with higher molecular mass are a mannose homopolymer containing 10.3% protein. The mannoproteins with lower molecular mass consisted of 87.5% of mannose and some other residues and a protein content of 2.5%. The highest molecular weight mannoprotein structure was examined by (1)H and (13)C NMR spectroscopic techniques such as 1-D TOCSY, 2-D COSY, and 2-D HMQC.

Chemical Precipitation↗

PubMed2002

Disentangling alpha from beta mechanical relaxations in the rubber-to-glass transition of high-sugar-chitosan mixtures.

The occurrence of molecular motions in addition to those of the glass-transition region (alpha mechanism) were investigated in chitosan and a branched derivative substituted with alkyl chains having eight carbon atoms. Once hydrophobic interactions of the alkyl groups in aqueous solution were demonstrated, polymers were mixed with glucose syrup at high levels of solids. The real (G') and imaginary (G") components of the complex dynamic modulus in high-solid mixtures were measured between 0.1 and 100 rad s(-1) in the temperature range from -55 to 50 degrees C. The method of reduced variables gave superposed curves of G' and G", which unveiled an anomaly in the dispersion of the alkylated derivative both in terms of higher modulus values and dominant elastic component of the polymeric network, as compared with the glass-transition region of chitosan. It was proposed that the new mechanical feature was due to beta mechanism, and master curves of viscoelastic functions and relaxation processes were constructed to rationalize it.

Alkylation↗

PubMed2002

Molecular structure of the rhamsan-like exocellular polysaccharide RMDP17 from Sphingomonas paucimobilis.

X-Ray diffraction analysis of the sodium salt of the polysaccharide RMDP17, a 2-deoxy rhamsan analog, reveals that it adopts a gellan-like, half-staggered, threefold, left handed, double helix of pitch 57.4 A. The side chain of the branched polymer is hydrogen bonded to the main chain. Sodium ions, linked to the carboxylate groups, promote the association of helices via water molecules. Two helices of opposite polarity occupy a trigonal unit cell of dimensions a=17.6 and c=28.7 A. The packing arrangement displays a series of hydrogen bonds involving main chain and side chain atoms, as well as some water bridges, between the helices.

Hydrogen Bonding↗

PubMedDate not supplied

Galactosylated N-vinylpyrrolidone-maleic acid copolymers: synthesis, characterization, and interaction with lectins.

Water-soluble artificial glycoconjugate polymers were synthesized from poly(N-vinylpyrrolidone-co-maleic anhydride) by amidation with an amine-containing galactose derivative. The glycopolymers having different galactose contents were fully characterized in terms of chemical structure by NMR and potentiometric titrations, and their aqueous behavior was studied by viscometric measurements. Their specific binding properties were examined by enzyme-linked lectin assays using RCA(120) lectin. Whatever the glycopolymer, the grafted galactoses were shown to behave similarly to free galactose.

Drug Delivery Systems↗

PubMedDate not supplied

Tailoring of bioresorbable polymers for elaboration of sugar-functionalized nanoparticles.

Maleic copolymers with different contents of galactose moieties and dodecyl chains were synthesized and used as both a stabilizer and a surface coating for the preparation of poly(epsilon-caprolactone) nanoparticles by the emulsification-diffusion technique. The size of the nanoparticles was controlled by varying the initial concentration of the modified maleic copolymers. As the concentration of the latter increased, the particle size decreased, indicating that the copolymers serve as a stabilizer. Moreover, surface modification of nanoparticles was confirmed by xi-potential measurements. Nanoparticles were also shown to be recognized by a galactose-specific lectin, demonstrating the presence of galactose units on the particle surface. This approach offers opportunities for the production of novel targeted drug delivery systems.

Biocompatible Materials↗

PubMedDate not supplied

Role of the pH on hyaluronan behavior in aqueous solution.

In this paper, we have examined the behavior of hyaluronan solutions at different pH values. A slight degradation is observed in acidic conditions (pH = 1.6) and basic medium (pH = 12.6) from molecular weight distribution analysis, but the rheological behavior is relatively not influenced much by the pH at the exclusion of two domains: around pH = 2.5, a gel-like behavior is shown and is attributed to cooperative interchain interactions due to the reduction of the polymer net charge and may be the protonation of the acetamido groups; for pH > 12, the decrease of viscosity is mainly attributed to a reduction of the stiffness of the polymeric backbone in alkaline conditions due to the partial breakage of the H-bond network.

Hyaluronic Acid↗