Structural Characterization and Rheological and Antioxidant Properties of Novel Polysaccharide from Calcareous Red Seaweed.

A novel sulfated xylogalactan (JASX) was extracted and purified from the rhodophyceae Jania adhaerens. JASX was characterized by chromatography (GC/MS-EI and SEC/MALLS) and spectroscopy (ATR-FTIR and 1H/13C NMR) techniques. Results showed that JASX was constituted by repeating units of (→3)-ß-d-Galp-(1,4)-3,6-α-l-AnGalp-(1→)n and (→3)-ß-d-Galp-(1,4)-α-l-Galp-(1→)n substituted on O-2 and O-3 of the α-(1,4)-l-Galp units by methoxy and/or sulfate groups but also on O-6 of the ß-(1,3)-d-Galp mainly by ß-xylosyl side chains and less by methoxy and/or sulfate groups. The Mw, Mn, D, [η] and C* of JASX were respectively 600 and 160 kDa, 3.7, 102 mL.g-1 and 7.0 g.L-1. JASX exhibited pseudoplastic behavior influenced by temperature and monovalent salts and highly correlated to the power-law model and the Arrhenius relationship. JASX presented thixotropic characteristics, a gel-like viscoelastic behavior and a great viscoelasticity character. JASX showed important antioxidant activities, outlining its potential as a natural additive to produce functional foods.

The Benefits of Smart Nanoparticles in Dental Applications.

Dentistry, as a branch of medicine, has undergone continuous evolution over time. The scientific world has focused its attention on the development of new methods and materials with improved properties that meet the needs of patients. For this purpose, the replacement of so-called "passive" dental materials that do not interact with the oral environment with "smart/intelligent" materials that have the capability to change their shape, color, or size in response to an externally stimulus, such as the temperature, pH, light, moisture, stress, electric or magnetic fields, and chemical compounds, has received much attention in recent years. A strong trend in dental applications is to apply nanotechnology and smart nanomaterials such as nanoclays, nanofibers, nanocomposites, nanobubbles, nanocapsules, solid-lipid nanoparticles, nanospheres, metallic nanoparticles, nanotubes, and nanocrystals. Among the nanomaterials, the smart nanoparticles present several advantages compared to other materials, creating the possibility to use them in various dental applications, including preventive dentistry, endodontics, restoration, and periodontal diseases. This review is focused on the recent developments and dental applications (drug delivery systems and restoration materials) of smart nanoparticles.

Immobilization and Release Studies of Triazole Derivatives from Grafted Copolymer Based on Gellan-Carrying Betaine Units.

New polymer-bioactive compound systems were obtained by immobilization of triazole derivatives onto grafted copolymers and grafted copolymers carrying betaine units based on gellan and N-vinylimidazole. For preparation of bioactive compound, two new types of heterocyclic thio-derivatives with different substituents were combined in a single molecule to increase the selectivity of the biological action. The 5-aryl-amino-1,3,4 thiadiazole and 5-mercapto-1,2,4-triazole derivatives, each containing 2-mercapto-benzoxazole nucleus, were prepared by an intramolecular cyclization of thiosemicarbazides-1,4 disubstituted in acidic and basic medium. The structures of the new bioactive compounds were confirmed by elemental and spectral analysis (FT-IR and 1H-NMR). The antimicrobial activity of 1,3,4 thiadiazoles and 1,2,4 triazoles was tested on gram-positive and gram-negative bacteria. The triazole compound was chosen to be immobilized onto polymeric particles by adsorption. The Langmuir, Freundlich, and Dubinin-Radushkevich adsorption isotherm were used to describe the adsorption equilibrium. Also, the pseudo-first and pseudo-second models were used to elucidate the adsorption mechanism of triazole onto grafted copolymer based on N-vinylimidazole and gellan (PG copolymer) and grafted copolymers carrying betaine units (PGB1 copolymer). In vitro release studies have shown that the release mechanism of triazole from PG and PGB1 copolymers is characteristic of an anomalous transport mechanism.

New Grafted Copolymers Carrying Betaine Units Based on Gellan and N-Vinylimidazole as Precursors for Design of Drug Delivery Systems.

New grafted copolymers possessing structural units of 1-vinyl-3-(1-carboxymethyl) imidazolium betaine were obtained by graft copolymerization of N-vinylimidazole onto gellan gum followed by the polymer-analogous reactions on grafted polymer with the highest grafting percentage using sodium chloroacetate as the betainization agent. The grafted copolymers were prepared using ammonium persulfate/N,N,N',N' tetramethylethylenediamine in a nitrogen atmosphere. The grafting reaction conditions were optimized by changing one of the following reaction parameters: initiator concentration, monomer concentration, polymer concentration, reaction time or temperature, while the other parameters remained constant. The highest grafting yield was obtained under the following reaction conditions: ci = 0.08 mol/L, cm = 0.8 mol/L, cp = 8 g/L, tr = 4 h and T = 50 °C. The kinetics of the graft copolymerization of N-vinylimidazole onto gellan was discussed and a suitable reaction mechanism was proposed. The evidence of the grafting reaction was confirmed through FTIR spectroscopy, X-ray diffraction, 1H-NMR spectroscopy and scanning electron microscopy. The grafted copolymer with betaine structure was obtained by a nucleophilic substitution reaction where the betainization agent was sodium chloroacetate. Preliminary results prove the ability of the grafted copolymers to bind amphoteric drugs (cefotaxime) and, therefore, the possibility of developing the new sustained drug release systems.

Alkyl-Chitosan-Based Adhesive: Water Resistance Improvement.

A chemical modification by grafting alkyl chains using an octanal (C8) on chitosan was conducted with the aim to improve its water resistance for bonding applications. The chemical structure of the modified polymers was determined by NMR analyses revealing two alkylation degrees (10 and 15%). In this study, the flow properties of alkyl-chitosans were also evaluated. An increase in the viscosity was observed in alkyl-chitosan solutions compared with solutions of the same concentration based on native chitosan. Moreover, the evaluation of the adhesive strength (bond strength and shear stress) of both native and alkyl-chitosans was performed on two different double-lap adherends (aluminum and wood). Alkyl-chitosans (10 and 15%) maintain sufficient adhesive properties on wood and exhibit better water resistance compared to native chitosan.

The extracellular matrix of the oleolytic biofilms of Marinobacter hydrocarbonoclasticus comprises cytoplasmic proteins and T2SS effectors that promote growth on hydrocarbons and lipids.

The assimilation of the nearly water insoluble substrates hydrocarbons and lipids by bacteria entails specific adaptations such as the formation of oleolytic biofilms. The present article reports that the extracellular matrix of an oleolytic biofilm formed by Marinobacter hydrocarbonoclasticus at n-hexadecane-water interfaces is largely composed of proteins typically cytoplasmic such as translation factors and chaperones, and a lesser amount of proteins of unknown function that are predicted extra-cytoplasmic. Matrix proteins appear to form a structured film on hydrophobic interfaces and were found mandatory for the development of biofilms on lipids, alkanes and polystyrene. Exo-proteins secreted through the type-2 secretion system (T2SS) were shown to be essential for the formation of oleolytic biofilms on both alkanes and triglycerides. The T2SS effector involved in biofilm formation on triglycerides was identified as a lipase. In the case of biofilm formation on n-hexadecane, the T2SS effector is likely involved in the mass transfer, capture or transport of alkanes. We propose that M. hydrocarbonoclasticus uses cytoplasmic proteins released by cell lysis to form a proteinaceous matrix and dedicated proteins secreted through the T2SS to act specifically in the assimilation pathways of hydrophobic substrates.

The evolution of the global COVID-19 epidemic in Morocco and understanding the different therapeutic approaches of chitosan in the control of the pandemic.

In 2020, Coronavirus disease (COVID-19), a new viral respiratory disease caused by a virus that belongs to Coronaviridae family, has been identified. It is a very severe flu that negatively affects the functions of the lung and other respiratory organs. COVID-19 virus can be transmitted between people either by touching an infected person or by direct contact with their respiratory droplets. Therefore, the COVID-19 virus has become a global concern due to its rapid spread and severity. Based on the World Health Organization report from 2 March 2020 to 24 October 2022, the total infected cases and deaths in Morocco are around 1,265,389 (3.46%) and 16,280 (0.04%), respectively. Recently, some scientists have found that chitosan, a polymer existed in nature, can inhibit COVID-19 infection and repair damaged tissue. Therefore, understanding chitosan mechanisms in controlling COVID-19, might lead to innovative strategies in the medical field, such as developing drugs against SARS-CoV-2, and replacing vaccines, which have negative side effects. This review aims to show the evolution of the COVID-19 pandemic worldwide, specifically in Morocco, its pathophysiology, and its ability to silence the immune system. This review also provides an overview of the treatments and measures applied to protect human beings and how chitosan acts and controls COVID-19.

Structural features and rheological behavior of a water-soluble polysaccharide extracted from the seeds of Plantago ciliata Desf.

A water-soluble polysaccharide (PSPC) was extracted from the seeds of Plantago ciliata Desf., a spontaneous Algerian Saharan plant by a hot aqueous extraction then purified by successive ethanolic precipitations. The final extraction yield for PSPC was close to 18.6% (w/v). PSPC was then investigated regarding its global composition, structural features and rheological properties. PSPC is a neutral arabinoxylan, composed of a ß-(1,3)/ß-(1,4)-d-xylan backbone with side chains of Xylp, and Araf residues attached in O-2 and O-3 positions. The macromolecular characteristics of PSPC in water was determined by SEC/MALLS, with a high molecular weight (Mw) of 700 kDa, a low polydispersity index (PDI) of 1.47 and an intrinsic viscosity [η] close to 157 mL/g. PSPC showed a pseudoplastic behavior in semi-dilute media and the critical overlay concentration (C*) was estimated around 0.32-0.37% (w/v). This current research has supplied original structural information on a new arabinoxylan which could be particularly useful as a novel source of soluble fiber belonging to psyllium.

Stimuli-sensitive xanthan derivatives/N-isopropylacrylamide hydrogels: influence of cross-linking agent on interpenetrating polymer network properties.

This article first describes the preparation and characterization of a novel class of unsaturated polysaccharide derivatives/ß-cyclodextrin acrylate/N-isopropylacrylamide stimuli-responsive hydrogels synthesized by free radical polymerization. Xanthan gum was partially functionalized by esterification with maleic anhydride under various conditions. By copolymerization of these maleate polysaccharides with a known temperature sensitive precursor (N-isopropylacrylamide) water-swollen hydrogels with interpenetrating polymer networks (IPN) were obtained. The hydrogels were characterized for their temperature and pH-responsive behavior by equilibrium swelling experiments and differential scanning calorimetry. The investigation of these materials also includes solid-state (13)CP/MAS NMR, elemental analysis of the nitrogen content and thermogravimetric measurements. Morphology was visualized by scanning electron microscopy. Depending upon composition, the hydrogels showed different response rates to the external changes of temperature as well as pH. By changing the feed composition ratio of precursors and cross-linking agent (ß-cyclodextrin acrylate or N,N'-methylenebisacrylamide, respectively) the phase transition temperature (lower critical solution temperature) could also be adjusted near the body temperature for the potential applications in biomedical and biotechnology fields. The role of the cross-linking agent on these properties is more particularly discussed.

Synthesis and biological activity of some new 1,3,4-thiadiazole and 1,2,4-triazole compounds containing a phenylalanine moiety.

New 1,3,4-thiadiazole, 6, 7 and 1,2,4-triazole derivatives, 8, 9 containing a phenylalanine moiety have been synthesized by intramolecular cyclization of 1,4-disubstituted thiosemicarbazides, 4, 5, in acid and alkaline media, respectively; the thiosemicarbazides were obtained by reaction of hydrazide 3 with appropriate aromatic isothiocyanates. The toxicity of the synthesized compounds was evaluated and the anti-inflammatory study of the triazole compound 9 established an appreciable anti-inflammatory activity that is comparable with that of other nonsteroidal anti-inflammatory agents.

New highly-percolating alginate-PEI membranes for efficient recovery of chromium from aqueous solutions.

Highly percolating membranes are prepared by the interaction of polyethylenimine and alginate (with glutaraldehyde crosslinking). SEM illustrates the macroporous structure of the material. The material is characterized by FTIR before and after chromate anions sorption. Batch-simulated continuous sorption experiments revealed that the maximum sorption occurred at pH 2 and the flow rate has limited effect on sorption efficiency. Uptake kinetics and sorption isotherms are well fitted by the pseudo-second-order rate and Sips equations, respectively. Maximum sorption is found close to 314 mg g-1. Competition effects from Ca(II), Cu(II), Cl-, NO3-, and SO42- are investigated to evaluate sorbent selectivity. The membranes are applied to remediate a simulate of Cr(VI) contaminated electroplating wastewater. Successive cycles of sorption and desorption show that the membranes maintain sorption capacity higher than 200 mg Cr g-1 for both Cr(VI) and total chromium for the first two cycles. These new highly percolating membranes have promising performances for Cr(VI) removal.

Dilational viscoelasticity and relaxation properties of interfacial electrostatic complexes between oppositely charged hydrophobic and hydrophilic polyelectrolytes.

Strongly adsorbing hydrophobic cationic polyelectrolyte, Eudragit RS, containing approximately 2.5 mol% of pendent hydrophilic trimethylammonium (TMA) groups irreversibly adsorbs from its methylene chloride (MCl) solution at the MCl/water interface and forms solid-like adsorption layers (ALs). Submitted to periodic dilational deformations with the standard radial frequency omega(0)=0.63 rad/s, these ALs exhibit relatively high dilational storage modulus E' approximately 20 mN/m and practically zero loss modulus E'' at the bulk concentration C(Eud)=4 x 10(-3)g/L. The frequency scanning of these ALs in the diapason omega=0.01-0.63rad/s and the approximation of the experimental dependences E'(omega) and E''(omega) by two relaxation times rheological model makes it possible to estimate the crossing frequency of these ALs determined from the condition E'(omega(c))=E''(omega(c)) as omega(c) approximately 5 x 10(-4)rad/s. Upon dissolving the hydrophilic anionic polyelectrolyte, chitosan sulfate (ChS), in the water phase (C(ChS)=3 x 10(-2)g/L) the electrostatic interpolyelectrolyte complexes form at the MCl/water interface. The elasticity moduli E' and E'' of these mixed AL did not undergo remarkable variations, but the crossing frequency is sharply increased by approximately 10 times becoming equal to omega(c) congruent with 3 x 10(-3)rad/s. The increase of omega(c) certifies for the liquefaction of mixed Eudragit RS/ChS adsorption layers. A remarkable decrease of the storage modulus down to E'=8 mN/m and simultaneous increase of the crossing frequency up to omega(c) congruent with 10(-2)rad/s occurs upon increasing the concentrations of both components, Eudragit RS and ChS, up to 0.1g/L. The liquefaction effect in the mixed ALs of oppositely charged polyelectrolytes was explained on the basis of the proposed relaxation mechanism. The effect of the liquefaction of adsorption layers of strongly adsorbing hydrophobic polyelectrolytes by formation of interpolyelectrolyte complexes with hydrophilic polyelectrolytes must be taken into account in the production of nano-capsules and nano-fibers.

New di-(beta-chloroethyl)-alpha-amides on N-(meta-acylamino-benzoyl)- D,L-aminoacid supports with antitumoral activity.

In order to obtain new compounds with antitumoural action the N-(meta-acylaminobenzoyl)-alpha-acylaminobenzoyl)-alpha-aminoacids 4-9 were prepared. These compounds were subsequently converted into the corresponding Delta(2)-oxazolin-5-ones 10-15, which in turn were submitted to a ring opening reaction with di-(beta-chloroethyl)amine to afford the peptide supported N-mustards 16-21, which showed low toxicity and cytostatic activity similar to that of sarcolisine against the Ehrlich ascite and Walker 253 carcinosarcoma.

Improvement of chitosan solubility and bactericidity by synthesis of N-benzimidazole-O-acetyl-chitosan and its electrodeposition.

Chitosan solubility and its antibacterial activity have been improved first of all with a chemical synthesis of N-benzimidazole-O-acetyl-chitosan in acetic medium and foremost through a potentiodynamic electrodeposition of this derivative. An association of one benzimidazole and three acetyl moieties per two units of the biopolymer chain was evidenced by FTIR and 1H NMR, pH-metric titration and TG analysis. Cyclic voltammetry study of the modified polymer in acetonitrile solution reveals its anodic oxidation at a platinum disk and a progressive growing of a thin film, through the cycling of potential. An enhancement of the solubility of the biopolymer as well as its antibacterial activity against Salmonella typhimurium, Escherichia coli, Staphylococcus aureus and Pseudomoenas aeruginosa bacteria have been observed with these chemical and after electrochemical modifications.

Extraction and characterization of an alginate from the Iranian brown seaweed Nizimuddinia zanardini.

Sodium alginate from Nizimuddinia zanardini (an Iranian brown algae) was extracted with acid and alkaline solutions, partially and totally hydrolyzed and analyzed for its biochemical composition. 1H NMR spectroscopy, SEC-MALLS, HPAEC and FT-IR were performed to determine its structure and its physico-chemical properties. This alginate has a M/G ratio of 1.1, a molecular weight of 103 kDa, a polydispersity index of 1.22, and an intrinsic viscosity of 342 mL/g. Its antioxidant activity was tested by DPPH radical scavenging showing its potential for food preservation. Rheological properties of solutions of this alginate with concentrations between 1 and 5% (w/v) in water and 0.5 M NaCl were investigated indicating a Newtonian fluid type behaviour in water and a shear thinning fluid type behaviour in NaCl solutions.

Structural characterization and antioxidant activity of water-soluble polysaccharides from the Tunisian brown seaweed Cystoseira compressa.

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 ß-d-Galp, ß-d-Galp-(1→3)-α-l-Fucp and ß-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 1H-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 FGG, FMM, FGM (or FMG) 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.

Structural characterization and thermal behavior of a gum extracted from Ferula assa foetida L.

The gum asafoetida, an oleo-gum-resin from root of Ferula assa foetida, was extracted through alcoholic procedure followed by water extraction and then biochemically characterized using colorimetric assays, Fourier infrared spectroscopy, gas chromatography coupled to mass spectrometry, and 1D and 2D nuclear magnetic resonance. The gum was mainly composed of carbohydrates (67.39% w/w) with a monosaccharide distribution of 11.5: 5.9: 2.3: 1 between Gal, Ara, Rha and GlcA (molar ratio) and proteins (arabinogalactan protein). The polysaccharide consisted of a (1→3)-ß-d-galactan backbone ramified predominantly from O-6 but also from O-4 and O-4,6. Side chains included terminal-α-l-Araf, terminal-α-l-Rhap, (1→3)-α-l-Araf, (1→5)-α-l-Araf, terminal-ß-d-Galp, ß-d-GlcA and traces of (1→4)-ß-d-GlcA. X-ray diffraction pattern showed a semi crystalline microstructure. Thermal behavior of the gum was evaluated by thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC) revealed temperatures below and upper 200°C as dominant regions of weight loss.

Kinetic aspects, rheological properties and mechanoelectrical effects of hydrogels composed of polyacrylamide and polystyrene nanoparticles.

Snake-cage gels were prepared using monodisperse polystyrene (PS) nano-sized particles ( = 200 nm) in place of the more commonly used linear polymer. The kinetics of the formation of the complementary polyacrylamide (PAM) hydrogel was studied alone or in the presence of the PS nanoparticles by H-NMR. Without PS, the reactivity ratios of the acrylamide (Am) and the cross-linking agent ,'-methylene-bisacrylamide (BisAm) were computed using the initial kinetics of PAM gel at high cross-linker concentration ( = 0.52 and = 5.2 for Am and BisAm, respectively). In the presence of PS, during the formation of nanoparticle composite (NPC) gels, there was a decrease in the conversion rate with an increasing fraction of PS nanoparticles. This could be explained by steric effects, which induce an increase of the elastic modulus of the matrix with the increasing fraction of PS nanoparticles. There was a considerable increase in the rheological properties of the NPC gels ( tensile modulus), which was more pronounced at higher fractions of nanoparticles. We used particular mechanical properties to develop a stimulus-responsive ("smart") material, a mechanoelectrical effect, which may be used in the development of soft and wet tactile-sensing devices.

Interactions between quaternized chitosan and surfactant studied by diffusion NMR and conductivity.

Surfactant-polysaccharide complexes (SPEC) based on oppositely charged sodium 1-decanesulfonate and quaternized chitosan were studied using two techniques. The first one, the conductivity, is a very often used even when diffusion NMR (DOSY) technique was considered for the first time for such systems involving surfactant and chitosan derivatives and more generally polysaccharides. The physico-chemical characteristics of pure surfactant solutions as well as SPECs were determined and compared according to the considered experimental technique. Close results were obtained and the great advantage of DOSY technique is the capacity to study simultaneously the two components of the systems, allowing more information on the nature of interactions between the surfactant and the polysaccharide as well as the mechanism involved during these interactions. This may be of great interest to understand how these complexes can alter the properties of formulations in which these components are involved, which is one of the big challenges of the industrial research.

Dilational rheology of oil/water interfaces covered by amphiphilic polysaccharides derived from dextran.

This work studied the adsorption at dodecane/water interface of amphiphilic polysaccharides derived from dextran (a nonionic bacterial polysaccharide) by random attachment of phenoxy groups along the chains (between 10 and 20 attached phenoxy groups per 100 glucose repeat units). The long-time kinetics of interfacial tension decrease was satisfactorily described assuming diffusion-limited adsorption of hydrophobic units (over 4h). Dilational rheology of dodecane/water interface was studied for the first time with that kind of amphiphilic polysaccharides and evidenced a significant elastic component. For all dextran derivatives, experimental results were conveniently described using Lucassen-van den Tempel model which assumed diffusion-limited of surface active species. The characteristic frequency increased with the number of attached phenoxy groups and its order of magnitude (10-3-10-2rad.s-1) was consistent with estimations based on the previous model. Experimental results were compared to those obtained with commercial stabilizers like Pluronics (L64, P105, F68 and F127) and Tween 80.