Conformation Of Chitosan Research Articles

Effect of free radicals on rheological properties, antioxidant activity, and molecular conformation of chitosan under solution pulsed plasma process based on radical scavengers

Radical scavengers were employed to evaluate the influence of various active species (•OH, •O, and H2O2) on the rheological properties, antioxidant activity, and molecular conformation of chitosan under solution plasma process (SPP) degradation. ESR analysis showed that •OH and •O radicals played important roles in SPP degradation. The results of rheological properties and antioxidant activity indicated that the •OH scavenger (tert-butanol), •O scavenger (1, 4-benzoquinone), and H2O2 scavenger (MnO2) remarkably inhibited the decrease of G' and G" of the degraded chitosan, the formation of gel structure, and the increase of antioxidant activity. The analysis of molecular conformation of the chitosan by particle size analysis, atomic force microscopy (AFM), and high performance size exclusion chromatography coupled with multi-angle laser light scattering (HPSEC-MALLS) revealed that the decrease of particle size, molecular aggregation, and molecular weight of chitosan was inhibited after the addition of radical scavengers. An evident effect of radical scavengers on the hard sphere conformation of chitosan was observed. It was found that the above effects were strongly dependent on the scavenger concentration. These results proved that •OH, •O, and H2O2 played important roles in SPP treatment. For the rheological properties and molecular conformation, H2O2 exhibited the greatest impact. For the antioxidant activity and molecular weight, •OH presented the biggest influence. Besides, •O expressed the weakest effect. This study will be beneficial to reveal the action mechanisms of SPP technology to the degradation of chitosan.

Structural and conformational changes on chitosan after green heterogeneous synthesis of phenyl derivatives

Four aromatic acid compounds: benzoic acid (Bz), 4-hydroxyphenylpropionic acid (HPPA), gallic acid (GA) and 4-aminobenzoic acid (PABA) were covalently bonded to chitosan in order to improve water solubility at neutral pH. The synthesis was performed via a radical redox reaction in heterogeneous phase by employing ascorbic acid and hydrogen peroxide (AA/H2O2) as radical initiators in ethanol. The analysis of chemical structure and conformational changes on acetylated chitosan was also the focus of this research. Grafted samples exhibited as high as 0.46 M degree of substitution (MS) and excellent solubility in water at neutral pH. Results showed a correlation between the disruption of C3-C5 (O3…O5) hydrogen bonds with increasing solubility in grafted samples. Spectroscopic techniques such as FT-IR and 1H and 13C NMR showed modifications in both glucosamine and N-Acetyl-glucosamine units by ester and amide linkage at C2, C3 and C6 position, respectively. Finally, loss of crystalline structure of 2-helical conformation of chitosan after grafting was observed by XRD and correlated with 13C CP-MAS-NMR analyses.

Conformation and persistence length of chitosan in aqueous solutions of different ionic strengths via asymmetric flow field-flow fractionation

Conformation of chitosan in acidic aqueous solutions is strongly influenced by ionic strength, but the conventional employed size exclusion chromatography is limited to high ionic strength. Here we show that conformation of chitosan in acetate buffer down to millimolar ionic strength can be studied via asymmetric flow field-flow fractionation (AF4), where the separation is governed by the diffusion properties of the chitosan molecules and assisted by the electrostatic repulsion of the polyelectrolyte from the channel membrane. The size of chitosan decreases with ionic strength due to increasing screening of the polyelectrolyte effect. The persistence length of chitosan in the solutions, obtained by fitting the conformation plot by the wormlike chain model, decreases linearly with the Debye screening length from 44.5 nm at a salt concentration of 1.25 mM dominated by the electrostatic contribution to 8.6 nm in 800 mM acetate buffer close to its intrinsic persistence length of 7.7 nm.

Chitosan-covered liposomes as a promising drug transporter: nanoscale investigations.

Liposomes are small artificial vesicles spherical shaped of 50–1000 nm in diameter. They are created from natural non-toxic phospholipids membranes. Externally, they are decorated with biocompatible polymers. Chitosan, a natural polymer, demonstrates exceptional advantages in drug delivery, in particular, as liposome cover. In this paper, Molecular Dynamics simulations (MD) are performed in the coupled NPT-NPH and NVT-NVE statistical ensembles to study the static and dynamic properties of DPPC membrane-bilayer with grafted cationic chitosan chains, with added Cl− anions to neutralize the environment, using the Martini coarse-grained force-field. From the NPT-NPH MD simulations we found a chitosan layer LDM ranging from 3.2 to 6.6 nm for graft chains of a degree of polymerization np = 45 and different grafting molar fractions Xp = 0.005, Xp = 0.014 and Xp = 0.1. Also, the chitosan chains showed three essential grafting regimes: mushroom, critic, and brush depending on Xp. The DPPC bilayer thickness DB and the area per lipid Al increased proportionally to Xp. From the NVT-NVE MD simulations, the analysis of the radial distribution function showed that the increase of Xp gives a more close-packed and rigid liposome. The analysis of the mean square displacement revealed that the diffusion of lipids is anomalous. In contrast, the diffusion of chitosan chains showed a normal diffusion, just after 100 ps. The diffusion regime of ions is found to be normal and independent of time. For the three identified regimes, the chitosan showed a tendency to adhere to the membrane surface and therefore affect the properties of the liposomal membrane.

Influence of macromolecules conformation of chitosan on its graft polymerization with vinyl monomers and the copolymer properties

The conformational states of chitosan macromolecules in solutions and their influence on the "grafting from" polymerization of 2-hydroxyethyl methacrylate and N-vinylpyrrolidone on the polysaccharide and the properties of their copolymers are studied. The conformational transition of macromolecules coil-rigid rod and rigid rod-globule in aqueous acidic solution was established by spectrophotometric method. The coil-rigid rod conformation transition depends on pH, it is sensitive to temperature and doesn't depend on the molecular weight of chitosan. The effective size of chitosan macromolecules for the rigid rod conformation was larger than for the coil conformation. The yield of the graft copolymer was significantly higher in case of where chitosan macromolecules were in the coil conformation (96 %) than in the rigid rod conformation (81 %). In the first case, the product of synthesis is a homogeneous solution, in the second case it is a colloidal solution. The copolymers were characterized by FTIR spectroscopy and gel-permeation chromatography.

Analysis of pH and salt concentration on structural and model-drug delivery properties of polysaccharide-based multilayered films

This paper explores the influence of pH and ionic strength of polyelectrolyte solutions as a simple and chemically amenable strategy for tuning the structure and drug delivery properties of polyelectrolyte multilayers produced via layer-by-layer technique. Carboxymethylcellulose/chitosan films were buildup under different pH (4.0 and 6.0) and salt concentrations (0 or 0.2 M NaCl) conditions. Systematic data analyses using Design of Experiments indicate that high ionic strength favors the formation of thinner and rougher films. Higher pH led to the formation of thinner and rougher films, attributed to the substantial decrease in the degree of ionization of carboxymethylcellulose and the random coil conformation of chitosan at the outermost layer, respectively. The random coiled conformation of chitosan near to neutral pH also seems to be the major factor to increase the surface film roughness under wet conditions. Drug delivery tests performed with Rose Bengal (model drug) indicate a predominant non-Fickian release mechanism for most of the buildup conditions tested. Densely packed multilayered films obtained at pH 6.0 and 0.2 M NaCl resulted in a faster, Fickian release mechanism, with minimal changes in surface morphology under wet conditions. The total amount of drug released shows a significative influence of only the polyelectrolyte solution pH, associated with the higher amount of free amino groups of chitosan at the film surface at higher pH conditions. These findings shed light on a strategy to develop functional coatings with tailored structural and drug delivery properties by simply controlling film depositions conditions.

A Study of the Viscosity Characteristics of Chitosan Solutions in the Presence of Organic Cosolvents

The effect of organic cosolvents (ethanol and isopropanol) on the viscosity characteristics of acetic acid aqueous solutions of chitosan is studied. Sorption and deformation–strength properties, as well as resistance to the process of enzymatic degradation of materials obtained from solutions, are determined. It is shown that the introduction of cosolvents into the chitosan–1% acetic acid system is accompanied by a consistent decrease in the intrinsic viscosity of polymers. It is found that, in the presence of cosolvents, at concentrations below the crossover concentration, chitosan molecules exist as systems of interacting (aggregated) macromolecules rather than isolated macromolecular coils. A change in the conformation of chitosan and the type of macromolecular aggregates in acetic acid solutions in the presence of cosolvents leads to a number of consequences: polymer units become less accessible to an enzyme preparation, the rate of enzymatic degradation decreases, and mechanical characteristics of film materials change.

Dissolution behavior and conformation change of chitosan in concentrated chitosan hydrochloric acid solution and comparison with dilute and semidilute solutions

Viscosity, pH and electrolytic conductivity of dilute, semidilute and concentrated chitosan solution with hydrochloric acid adding were compared and the change in conformation of chitosan in concentrated solution was discussed. The dissolution behavior of chitosan in concentrated chitosan hydrochloric acid solution was investigated through determination of solution turbidity, microstate and size of chitosan particle. It was found that the concentration, degree of deacetylation (DD) of chitosan and content of hydrochloric acid in solution showed significant effects on the changes in viscosity, pH, and electrolytic conductivity of chitosan solution as hydrochloric acid added. And the transforms of above properties of chitosan solution during dissolution were corresponding to the proportion of hydrochloric acid to chitosan from which we could deduced that the confirmation of chitosan changed from entangling with each other to becoming compact coils due to electrostatic screen of Cl− and hydrophobic aggregation of chitosan with high concentration. In concentrated suspension solution, chitosan particles agglomerated first and then expended before disintegrating and dissolving with hydrochloric acid adding, resulting in solution turbidity, size and microstate of chitosan particle changed obviously during dissolution.

Chitosan-carboxymethylcellulose based microcapsules formulation for controlled release of active ingredients from cosmeto textile

Chitosan-based emulsions were prepared at pH from 4.0 to 6.0. The zeta potential and droplet size were monitored at different pH. Double emulsions (wateroil- water) were observed due to the stiff conformation of chitosan at pH 4.0. At pH 5.0, the emulsion droplets were the smallest (2.9 μm) of the experimental pH range. The emulsion droplets were well dispersed due to high surface charge of chitosan (for example, +50 mV at pH 5.5) in entire pH range. The emulsion was treated with carboxymethyl cellulose (CMC) for neutralizing the charged chitosan on the surface of emulsion droplets. Above 10×10−2 mg/ml of CMC, no change in zeta potential was observed indicating no more free chitosan existed after neutralization with CMC. The emulsion was then crosslinked with different amount of glutaraldehyde. Upon increasing the amount of glutaraldehyde, the amount of core content inside the microcapsule and encapsulation efficiency of shell materials decreased gradually. The Dynamic Scanning Calorimetry data confirmed no interaction between core and shell material in the microencapsulation process. The thermal degradation of the microcapsules was examined by thermogravimetric analysis and a gradual decrease in the degradation temperature upon increasing glutaraldehyde concentration was found. The tuning of CMC concentration can provide valuable information regarding stable emulsion and efficient microcapsule formulation via coacervation.

Effect of Protonation State and N-Acetylation of Chitosan on Its Interaction with Xanthan Gum: A Molecular Dynamics Simulation Study.

Hydrophilic matrices composed of chitosan (CS) and xanthan gum (XG) complexes are of pharmaceutical interest in relation to drug delivery due to their ability to control the release of active ingredients. Molecular dynamics simulations (MDs) have been performed in order to obtain information pertaining to the effect of the state of protonation and degree of N-acetylation (DA) on the molecular conformation of chitosan and its ability to interact with xanthan gum in aqueous solutions. The conformational flexibility of CS was found to be highly dependent on its state of protonation. Upon complexation with XG, a substantial restriction in free rotation around the glycosidic bond was noticed in protonated CS dimers regardless of their DA, whereas deprotonated molecules preserved their free mobility. Calculated values for the free energy of binding between CS and XG revealed the dominant contribution of electrostatic forces on the formation of complexes and that the most stable complexes were formed when CS was at least half-protonated and the DA was ≤50%. The results obtained provide an insight into the main factors governing the interaction between CS and XG, such that they can be manipulated accordingly to produce complexes with the desired controlled-release effect.

Tuning the formation and stability of microcapsules by environmental conditions and chitosan structure

The goal of this work is to tune the formation and stability of the alginate-chitosan (AC) polyelectrolyte complexes (PECs) and microcapsules. Particularly, we explore the role of the conformation of chitosan on its interaction with alginate to understand the mechanism underpinning their interactions at the molecular level. Reducing the charge density by increasing pH will increase the compactness of chitosan, the values of the enthalpy (H) and stoichiometry (N) of binding between chitosan and alginate. Consequently, chitosan has advantage in being adsorbed on alginate beads to form microcapsules, including the binding rate and binding amount. Though the total heat release remain similar in the range of ionic strength, chitosan diffuses much easier into alginate hydrogels when in higher ionic strength. Increasing pH and ionic strength both help AC microcapsules to have higher stability. The results indicate that the formation and stability of AC microcapsules are related to the rigidity and conformations of chitosan molecules. After increasing acetylation degree (DA) of chitosan, the binding rate of chitosan and mechanical strength of AC microcapsules are both reduced. This work demonstrates the versatility and feasibility of tuning the formation and stability of polysaccharide microcapsules by physical factors and chitosan chemical structures.

Effect of GO/CS/PbS nanocomposite films on tetraethyoxysilane sensing

In this work, a new method for generating highly fluorescent graphene oxide (GO)/chitosan (CS)/PbS nanocomposite films in a mild environment was developed via electrostatic interactions and in situ growth methods. The growth of PbS nanoparticles was initiated by ion complexation with –NH2 in the CS chain, followed by the thioacetamide treatment of S2− obtained from decomposed samples. Moreover, the distinct features of the nanocomposite films were characterized by Fourier transform infrared spectroscopy, differential scanning calorimetry, UV–vis, and scanning electron microscopy. Polymer molecules could control nucleation and PbS growth on the surface of GO/CS films to stabilize nanoparticles. The fluorescence spectral measurements clearly showed that the fluorescence of the nanocomposite film was gradually enhanced with tetraethyoxysilane addition. This enhancement was ascribed to the gradual decrease in solvent polarity. Moreover, the CS conformation changed in an extension state, which increased the distance between PbS and GO and reduced their quenching effect. The fluorescence results revealed that the GO/CS/PbS nanocomposite films were sensitive to tetraethoxysilane and could easily be recovered and reused for sensing. Therefore, the nanocomposite films may be specific sensor materials for tetraethoxysilane. Such a simple and efficient strategy would provide an opportunity for the large-scale production of various heterostructures with wide potential applications in the sensing field.

Insights into chitosan multiple functional properties: the role of chitosan conformation in the behavior of liposomal membrane.

Interactions between chitosan and the liposomal membrane are relevant to the physiological functionality of chitosan, including dietary fiber, antimicrobial action, and fabrication of a delivery system for bioactives. To elucidate the multiple functions of chitosan, the dependence of liposomal membrane properties on the biopolymer conformation was investigated. The concentration dependence of chitosan conformation in aqueous solution was quantified by fluorescence and viscosity measurements. As the concentration increased, the extended chains of chitosan (0-1.0 mg mL(-1)) partially crimped (1.0-1.5 mg mL(-1)), and then self-aggregated forming irregular coils (>1.5 mg mL(-1)). Adsorption of chitosan linear chains on the liposomal membrane surface tended to maintain the morphology of liposomes, decrease the membrane interior micropolarity and rigidify the liposomal membrane. However, these effects were negligible or even opposite in the case of chitosan coils. Analysis on the membrane fluidity revealed that the microviscosity of liposomes decorated by 1.5 mg mL(-1) concentration of chitosan decreased by 17% after being heated at 80 °C for 10 min, in contrast to the decreased percentage of 55 at 4 mg mL(-1). Additionally, compared with the poor oxidative stability of liposomes decorated by chitosan coils, those decorated by chitosan linear chains exhibited slight lipid peroxidation with the TBARS inhibition of around 10% and 6% against oxygen and ferric ions, respectively. These findings suggest that the conformational effects of chitosan on the liposomal membrane are responsible for its multiple functional properties.

Structure of chitosan determines its interactions with mucin.

Synthetic and natural mucoadhesive biomaterials in optimized galenical formulations are potentially useful for the transmucosal delivery of active ingredients to improve their localized and prolonged effects. Chitosans (CS) have potent mucoadhesive characteristics, but the exact mechanisms underpinning such interactions at the molecular level and the role of the specific structural properties of CS remain elusive. In the present study we used a combination of microviscosimetry, zeta potential analysis, isothermal titration calorimetry (ITC) and fluorescence quenching to confirm that the soluble fraction of porcine stomach mucin interacts with CS in water or 0.1 M NaCl (at c < c*; relative viscosity, η(rel), ∼ 2.0 at pH 4.5 and 37 °C) via a heterotypic stoichiometric process significantly influenced by the degree of CS acetylation (DA). We propose that CS-mucin interactions are driven predominantly by electrostatic binding, supported by other forces (e.g., hydrogen bonds and hydrophobic association) and that the DA influences the overall conformation of CS and thus the nature of the resulting complexes. Although the conditions used in this model system are simpler than the typical in vivo environment, the resulting knowledge will enable the rational design of CS-based nanostructured materials for specific transmucosal drug delivery (e.g., for Helicobacter pylori stomach therapy).

Dual Effects of Chitosan Decoration on the Liposomal Membrane Physicochemical Properties As Affected by Chitosan Concentration and Molecular Conformation

This study was devoted to a further understanding of the dependence of liposomal membrane properties on chitosan conformation and proved the dual effects of chitosan. The concentration dependence of chitosan conformation in aqueous solution was illustrated by surface tension and fluorescence probe techniques. Fluorescence and Raman spectra were subsequently employed to investigate the dynamic and structural changes of the liposomal membrane resulting from chitosan decoration. Results showed that the unfolded and crimped chains of chitosan flatly adsorbed onto the membrane surface via electrostatic attraction and favored liposome stability. Furthermore, the adsorption of crimped chains seemed stronger due to the embedding of their hydrophobic moieties. However, the presence of chitosan coils induced the increase in membrane fluidity, the intrachain disorder in lipid molecules, and the gauche conformation change of choline group. Dynamic light scattering and lipid oxidation measurements demonstrated that this perturbation was correlated with the permeation of coils into the lipid bilayer.

PH/temperature sensitive chitosan-g-(PA-PEG) aqueous solutions as new thermogelling systems

As a new thermal gelling polymer aqueous solution, we are reporting a poly(ethylene glycol)-poly(alanine) grafted chitosan (CS-g-(PA-PEG)) system. The sol–gel transition temperature and the modulus of the in situ-formed thermal gel at 37 °C changed 17 → 27 →32 °C and 396 → 241 → 43 Pa, respectively, as the pH increased from 3.0 to 6.5 and to 9.0. The mechanism of such a pH/temperature sensitive behaviour of the CS-g-(PA-PEG) aqueous solution was investigated by studying changes in the conformation of chitosan, polyalanine and PEG of the CS-g-(PA-PEG). As the temperature increased, ammonium groups of the chitosan partially deprotonated to a neutral form, the α-helical content of the polyalanine increased and molecular motion of the PEG decreased. Such changes cooperatively increase the hydrophobicity and viscosity of CS-g-(PA-PEG), resulting in the sol–gel transition of the polymer aqueous solution with increasing temperature. As the pH increased, ammonium groups of the chitosan deprotonated to a neutral form and the α-helical content of polyalanine decreased, which induce a change in the nanoassembly of the polymer. CS-g-(PA-PEG) significantly increased the gel modulus of a previously reported PEG grafted chitosan (CS-g-PEG) thermal gel by incorporating the α-helical polyalanine moieties between CS and PEG. The CS-g-(PA-PEG) could be a promising biomaterial as a new robust thermogel with pH and temperature sensitivity.

Macromolecular conformation of chitosan in dilute solution: A new global hydrodynamic approach

Chitosans of different molar masses were prepared by storing freshly prepared samples for up to 6 months at either 4, 25 or 40 °C. The weight-average molar masses, M w and intrinsic viscosities, [ η] were then measured using size exclusion chromatography coupled to multi-angle laser light scattering (SEC-MALLS) and a “rolling ball” viscometer, respectively. The solution conformation of chitosan was then estimated from: (a) the Mark–Houwink–Kuhn–Sakurada (MHKS) power law relationship [ η] = kM w a and (b) the persistence length, L p calculated from a new approach based on equivalent radii [Ortega, A., & Garcia de la Torre, J. (2007). Equivalent radii and ratios of radii from solution properties as indicators of macromolecular conformation, shape, and flexibility. Biomacromolecules, 8, 2464–2475]. Both the MHKS power law exponent ( a = 0.95 ± 0.01) and the persistence length ( L p = 16 ± 2 nm) are consistent with a semi-flexible rod type (or stiff coil) conformation for all 33 chitosans studied. A semi-flexible rod conformation was further supported by the Wales–van Holde ratio, the translational frictional ratio and sedimentation conformation zoning.

Physicochemical Behavior of Homogeneous Series of Acetylated Chitosans in Aqueous Solution: Role of Various Structural Parameters

Physicochemical properties of four different homogeneous series of chitosans with degrees of acetylation (DA) and weight-average degrees of polymerization (DP(w)) ranging from 0 to 70% and 650 to 2600, respectively, were characterized in an ammonium acetate buffer (pH 4.5). Then, the intrinsic viscosity ([eta](0)), the root-mean-square z-average of the gyration radius (R(G,z)), and the second virial coefficient (A(2)) were studied by viscometry and static light scattering. The conformation of chitosan, according to DA and DP(w), was highlighted through the variations of alpha and nu parameters, deduced from the scale laws [eta](0) = K(w)and R(G,z) = K', respectively, and the total persistence length (L(p,tot)). In relation with the different behaviors of chitosan in solution, the conformation varied according to two distinct domains versus DA with a transition range in between. Then, (i) for DA < 25%, chitosan exhibited a flexible conformation; (ii) a transition domain for 25 < DA < 50%, where the chitosan conformation became slightly stiffer and, (iii) for DA > 50%, on increasing DP(w) and DA, the participation of the excluded volume effect became preponderant and counterbalanced the depletion of the chains by steric effects and long-distance interactions. It was also highlighted that below and beyond a critical DP(w,c) (ranging from 1 300 to 1 800 for DAs from 70 to 0%, respectively) the flexibility of chitosan chains markedly increased then decreased (for DA > 50%) or became more or less constant (DA < 50%). All the conformations of chitosan with regards to DA and DP(w) were described in terms of short-distance interactions and excluded volume effect.

Three D structures of chitosan

Crystal structures of two polymorphs of chitosan, tendon (hydrated) and annealed (anhydrous) polymorphs, have been reported. In both crystals, chitosan molecule takes up similar conformation (Type I form) to each other, an extended two-fold helix stabilized by intramolecular O(3)O(5) hydrogen bond, which is also similar to the conformation of chitin or cellulose. Three chitosan conformations other than Type I form have been found in the crystals of chitosan-acid salts. In the salts with acetic and some other acids, called Type II salts, chitosan molecule takes up a relaxed two-fold helix composed of asymmetric unit of tetrasaccharide. This conformation seems to be unstable because no strong intramolecular hydrogen bond like Type I form. Type II crystal changes to the annealed polymorph of chitosan by a spontaneous water-removing action of the acid. Chitosan molecule in its hydrogen iodide salt prepared at low temperature takes a 4/1 helix with asymmetric unit of disaccharide. The fourth chitosan conformation was found to be a 5/3 helix in chitosan salts with medical organic acids having phenyl group such as salicylic or gentisic acids. Similar conformation of chitosan molecule in the aspirin (acetylsalicylic acid) salt was suggested by a solid-sate NMR measurement.

Two different molecular conformations found in chitosan type II salts

The type II structure of chitosan acidic salts prepared from crab tendon in solid state was studied using an X-ray fiber diffraction technique together with the linked-atom least-squares (LALS) technique. The cylindrical Patterson method was applied to confirm the molecular conformation of the chitosan. It was shown that there are two different helical conformations for type II salts. One is the relaxed twofold helix having a tetrasaccharide as an asymmetric unit as found in chitosan·HCl salt, which was previously reported as a conformation of chitosan·HCOOH salt. The other is the fourfold helix having a disaccharide as an asymmetric unit newly found in chitosan·HI salt.