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A fucoidan (CCF) and a sodium alginate (CCSA) were extracted and purified from the Tunisian brown seaweed Cystoseira compressa. CCF was a highly sulfated heterogalactofucan composed of α-(1→3), α-(1→4)-linked l-Fucp as main backbone which could be highly branched (31.84%) at O-3 and O-4 positions of α-(1→4)-l-Fucp and α-(1→3)-l-Fucp by terminal monosaccharides and side chains such as terminal α-l-Fucp, terminal β-d-Galp, β-d-Galp-(1→3)-α-l-Fucp and β-d-Galp-(1→4)-α-l-Fucp. The ratio of α-(1→3)/α-(1→4) linkages was estimated at 3.86:1. CCSA was characterized by HPAEC-PAD, GC/MS-EI, ATR-FTIR, and 1 H-NMR. The M/G ratio was M/G = 0.77, indicating that CCSA respectively contained 44% and 56% of mannuronic and guluronic acids. The values of F GG , F MM , F GM (or F MG ) blocks as well as the parameter η were estimated. The two polysaccharides exhibited effective antioxidant activities by ferrous ion chelation, ferric ion reduction and DPPH radical-scavenging, outlining their potentials as natural additives., (Copyright © 2018 Elsevier Ltd. All rights reserved.)

Several thermo-sensitive polyelectrolyte complexes were prepared by ionic self-association between an anionic polysaccharide (alginate) and a monocationic copolymer (polyether amine, Jeffamine®-M2005) with a 'Low Critical Solubility Temperature' (LCST). We show that electro-association must be established below the aggregation temperature of the free Jeffamine®, after which the organization of the system is controlled by the thermo-association of Jeffamine® that was previously electro-associated with the alginate. Evidence for this comes primarily from the rheology in the semi-dilute region. Electro- and thermo-associative behaviours are optimal at a pH corresponding to maximum ionization of both compounds (around pH 7). High ionic strength could prevent the electro-association. The reversibility of the transition is possible only at temperatures lower than the LCST of Jeffamine®. Similar behaviour has been obtained with carboxymethyl cellulose (CMC), which suggests that this behaviour can be observed using a range of anionic polyelectrolytes. In contrast, no specific properties have been found for pullulan, which is a neutral polysaccharide., (Copyright © 2015 Elsevier Ltd. All rights reserved.)

The immobilization of pullulanase from Klebsiella pneumoniae by grafting was investigated. Pullulanase was linked after activation of alginate via a covalent bond between the amine groups of the enzyme and the carboxylic acid groups of alginate. The immobilization yield was 60%. The activity of free pullulanase and immobilized pullulanase was followed by the quantification of reducing ends by colorimetric assay and the determination of the molar masses of the hydrolyzed pullulan by SEC/MALS/DRI. Compared to free pullulanase, the kinetics is largely slowed. The evolution of the weight average molar mass of pullulan leading to high production of shorter oligosaccharides during hydrolysis is not the same as that obtained with free enzyme. Immobilized pullulanase retained 75% and 30% of its initial activity after 24 h and 14 days of incubation at 60°C, respectively while free pullulanase lost its activity after 5 h of hydrolysis at the same temperature. The kinetic parameters of immobilized pullulanase were also investigated by isothermal titration calorimetry (ITC). The affinity of immobilized enzyme to its substrate was reduced compared to the free pullulanase due to steric hindrance and chemical links., (© 2015 American Institute of Chemical Engineers.)

Pullulanase from Klebsiella pneumoniae was entrapped into calcium alginate beads. Its activity was estimated by the determination of number-average molar masses using two different methods: a colorimetric assay of reducing ends (REs) and a size-exclusion chromatography/multiangle light scattering/differential refractive index. The second method also provided weight-average molar masses of hydrolyzed pullulan and the quantity of maltotriose (DP3) and its multiples (DP6 and DP9) produced by the enzymatic treatment. The alginate beads showed a good retention of the loaded pullulanase (30%), and the system showed a downturn of hydrolysis kinetics in comparison with free pullulanase due to the limiting access of substrate-enzyme. On the contrary with the results obtained from free enzyme hydrolysis, for which a large distribution of pullulan fragments is observed during the treatment, the immobilized enzyme system has evidenced, during the enzymatic treatment, the coexistence of native or only slightly degraded pullulan chains together with maltotriose units. Complete hydrolysis of pullulan chains was achieved once diffused into the gel., (© 2014 Wiley Periodicals, Inc.)

The behavior of a hydrolytic enzyme (pullulanase) toward its substrate (pullulan) in the presence of a nonsubstrate (alginate), both below and above the critical entanglement concentration (C*), was studied. The hydrolysis kinetics were studied with the enzyme and alginate concentrations varied using two main methods: a colorimetric assay of the reducing extremities (RE), which allowed the number-average molar masses (Mn) of the oligosaccharides to be determined, and size exclusion chromatography with on-line, multiangle light scattering, viscometer, and differential refractive index detectors, which allowed the average molar masses, Mn and Mw, of the oligosaccharides during hydrolysis to be determined. Free pullulanase acts via an "endo" process. The presence of alginate slows the hydrolysis kinetics, particularly when the alginate concentration is greater than the C*. These results were confirmed by the evolution of the kinetic parameters (KM, Vmax) obtained via isothermal titration calorimetry (ITC). The amount of oligosaccharides produced is not dependent on the alginate concentration, and the endo enzyme behavior is not modified by the entanglement in the medium. These observations were also confirmed by ITC analysis in the presence of degraded alginate (without entanglement). Our results correlated with the substrate diffusion in entangled media. The pullulanase reaction in the presence of alginate is shown to be diffusion-dependent.

This paper presents the development of new pH-sensitive, amphiphilic and biocompatible hydrogels based on alginate-g-PCL, cross-linked with calcium ions to form beads, prepared for controlled delivery of poorly water-soluble drug. We have focused our study on the effect of the length of PCL chains (530 and 1250 g mol(-1)). Swelling profiles obtained clearly indicated that these hydrogels swell slightly (10-14%) in a simulated gastric fluid (pH 1.2), and strongly (700-1300% before disintegration) in a simulated intestinal fluid (pH 6.8). In both media, rates of swelling were lower for beads based on amphiphilic derivatives than for alginate/Ca2+ ones due to the hydrophobic PCL grafts, and decreased when hydrophobic character increased. A model drug, theophylline, was entrapped into these hydrogels and release studies were carried out. The drug was protected in acidic fluid (only 14-20% of release for alginate-g-PCL hydrogel against 35% of release for alginate hydrogel during 350 min). The drug is released completely in neutral fluid due to ion exchanges and disintegration of the hydrogel. PCL leads to decrease in the release kinetics in SIF (2h for alginate-g-PCL/Ca2+ beads against 1h for alginate/Ca2+ beads). It was demonstrated that the establishment of clusters inside beads by intramolecular interactions between PCL grafts of 530 g mol(-1) in salt media allowed to retain the drug and to slow down its release considerably.

The release of sodium polystyrene sulfonate (SPS) from calcium alginate hydrogel beads has been studied. It has been shown that the structure of the cross-linked calcium alginate network is of primary importance in the retention and/or release of the SPS. This has been evidenced by studying the influence of Ca2+ concentration, molar masses (Mn) and the ratio of mannuronic acid/guluronic acid components. A minimum in the SPS release is observed in relation with the organization of the network structure. Conditions inducing the organization of a strong gel (e.g. high Ca2+ concentration for example) are not always related to a low release. A good control of release is found when a compromise between a well-structured hydrogel and sterical consideration of SPS is reached. [Copyright &y& Elsevier]

Abstract: New amphiphilic polysaccharides based on alginate-grafted-Poly (ε-caprolactone) or alg-g-PCL bearing two kinds of PCL chains with different molar masses (1250 and 530gmol−1) with various amounts from 3% to 15% were prepared. Rheological properties in aqueous solutions of such systems have been investigated as a function of polymer concentration, added salt and temperature in semi-dilute regime. Strong hydrophobic intermolecular associations were clearly demonstrated in pure water whatever the PCL chain length and extend of modification. Increasing polymer concentration, grafting rate and/or PCL chains length can lead to a structured liquid behaviour. Rheological properties of the most organized system have been found independent to the temperature (until 60°C). In salt media, a strong dependence of hydrophobic interactions to the length of PCL chains was observed. For M PCL =1250g.mol−1 the screening of charges promotes the establishment of intermolecular interactions and leads to a strong physical gel for the highest grafting rates. For M PCL =530gmol−1, ionic strength leads to a decrease of rheological properties when increasing grafting rate. This result may indicate an increase of hydrophobic clusters even in the entangled regime. This unusual behaviour opens the ways for the preparation of suitable hydrogels for drug release. [Copyright &y& Elsevier]

Abstract: New water soluble and amphiphilic PCL-grafted-alginates with two different molar masses of PCL (530 and 1250gmol−1) and molar hydrophobe contents from 3.5 to 15% have been prepared by new aqueous micellar grafting technique. Physico-chemical behaviour in aqueous solution (pure water and NaCl 0.1M) has been studied by means of viscosity measurements and on-line Flow field flow fractionation/Multi-angle laser light scattering/Quasi-elastic light scattering/Differential refractive index analyses. Expected associative behaviour has been evidenced in pure water whatever the length of the PCL chains. In salt media, the associative behaviour strongly depends on the length of PCL chains. For PCL chains of 530gmol−1, intramolecular hydrophobic interactions are predominant, even in semi-dilute regime. This non-classical behaviour for an associative polyelectrolyte opens the way to the conception of amphiphilic matrices with hydrophobic clusters for controlled release applications. [Copyright &y& Elsevier]