Egg-box Model Research Articles

3D Printable Alginate-Chitosan Hydrogel Loaded With Ketoconazole Exhibits Anticryptococcal Activity.

Natural polymers have recently been investigated for various applications, such as 3D printing and healthcare, including treating infections. Among microbial infections, fungal diseases remain overlooked, with limited therapeutic options and high recurrence. Cutaneous cryptococcosis is an opportunistic fungal infection triggered by mechanical inoculation or hematogenous dissemination of the yeast that causes cryptococcal pneumonia and meningitis. Every year, Cryptococcus neoformans endanger the lives of immunosuppressed hosts, resulting in 180,000 deaths per year. Nonetheless, healthy individuals can also be affected by this fungal infection. Cryptococcosis has a restricted and expensive therapeutic regimen with no topical approach to skin manifestations. This study sought to create a 3D printable biodegradable polymeric hydrogel carrying ketoconazole, a low-cost antifungal drug with reported anticryptococcal activity. The developed hydrogel exhibited good 3D printability and rheological properties, including a pseudoplastic behavior. The FTIR spectra of cross-linked hydrogels revealed interactions between alginate and Ca+2, referred to as the egg-box model, indicated by the decrease in peaks at 1600 and 1410 cm-1. Furthermore, the hydrogel loaded with ketoconazole showed remarkable antifungal activity against C. neoformans strains indicated by inhibition zones, which cross-linking did not seem to affect its antifungal performance. The developed material remained structurally stable for up to 12 days (288 h) in swelling studies, and preliminary cytotoxicity performed with V79 cells indicates potential for invivo studies and topical application.

Electro-coagulation pretreatment for improving nanofiltration membrane performance during reclamation of microplastic-contaminated secondary effluent: unexpectedly enhanced membrane fouling and mechanism analysis by MD-DFT simulation

The residue of microplastic in secondary effluent was inevitable with continuous aggravation on nanofiltration membrane fouling. Thus, this study aimed to further evaluate the applicability of electro-coagulation as pretreatment for improving the performance of a nanofiltration-oriented hybrid process during the reclamation of microplastic-contaminated secondary effluent. The electro-coagulation parameters were skillfully optimized and designed for following dynamic nanofiltration experiments. The potential influence of coagulants in different forms as well as their combined effects of microplastics on membrane fouling behaviors and pollutant rejection efficiency was distinguished. Specifically, terminal membrane permeability was reduced by 19% after 0.05 A electro-coagulation, while 0.2 A electro-coagulation almost eliminated the negative effects of microplastics. Mass transfer model analysis excluded the dominance of organic accumulation in the concentration polarization layer on membrane fouling development. Molecular dynamic (MD) simulation and egg-box model demonstrated that humic-Fe network possessed stronger bridging effects and greater porosity. This structure favored the co-deposition of other unlinked bacteria metabolites, which secretion was also facilitated by microplastics as immobilized carriers, on membrane surface. Additionally, density functional theory (DFT) calculation further confirmed that the greater demand for dehydration energy for ferric ions (1124 kcal/mol) inspired the formation of stronger humic-Fe complexes. Besides, residual microplastics in electro-coagulation effluent had different impacts on membrane rejection towards organic and inorganic pollutants, and it depended on the influenced cake-enhanced concentration polarization (CECP) by microplastic affinity with different pollutants.

Assessment of calcium alginate gels as wall materials for encapsulation systems.

Calcium alginate gels are widely used to encapsulate active compounds. Some characteristic parameters of these gels are necessary to describe the release of active compounds through mechanistic mathematical models. In this work, transport and kinetics properties of calcium alginate gels were determined through simple experimental techniques. The weight-average molecular weight ( = 192 × 103 Da) and the fraction of residues of α-l-guluronic acid ( = 0.356) of sodium alginate were determined by capillary viscometry and 1 H-nuclear magnetic resonance at 25 °C, respectively. Considering the half egg-box model, both values were used to estimate the molecular weight of calcium alginate as = 2.02 × 105 Da. An effective diffusion coefficient of water ( = 2.256 × 10-9 m2 s-1 ) in calcium alginate was determined using a diffusion cell at 37 °C. Finally, a kinetics constant of depolymerization ( = 9.72 × 10-9 m3 mol-1 s-1 ) of calcium alginate was obtained considering dissolution of calcium to a medium under intestinal conditions. The experimental techniques used are simple and easily reproducible. The obtained values may be useful in the design, production, and optimization of the alginate-based delivery systems that require specific release kinetics of the encapsulated active compounds. © 2023 Society of Chemical Industry.

Doubling growth of egg-box structure during Calcium-mediated molecular assembly of alginate

Ca2+-mediated molecular assembly of alginate underpins its wide range of applications in foods, pharmaceutics, biomedicines, tissue engineering and environmental treatments. The mode of growth of egg-box structure of alginate in the presence of Ca2+ is a long-standing fundamental problem to be concluded. In this work, we investigate the Ca-induced structural evolution of alginate in dilute solution using atomic force microscopy and dilute solution viscometry. It is demonstrated that the structural evolution follows the three critical steps of monocomplexation, dimerization and multimerization, upon binding with Ca2+. Interestingly, the alginate single chains grow into dimers and multimers via a doubling mode, i.e., successive emerging of dimer, tetramer, octamer, and hexadecamer. Compared with lower guluronate (G) alginate, higher G alginate exhibits a more pronounced multimerization process occurring at a lower ratio of Ca/G. A mechanistic model depicting the evolution of egg-box structure is proposed. The results would add new knowledge to the current egg-box model regarding the molecular assembly and gelation of an important biopolymer alginate, and provide fundamental basis for molecular engineering of alginate for more advanced applications.

How Accurate Is the Egg-Box Model in Describing the Binding of Calcium to Polygalacturonate? A Molecular Dynamics Simulation Study.

We performed molecular dynamics (MD) simulations of octameric galacturonate, GalA8, chains in the presence of Ca2+ in a ratio of R = [Ca2+]/[GalA] = 0.25 in order to determine to which extent the popular "egg-box model" (EBM) is able to describe the association between Ca2+ cations and polygalacturonate (polyGalA) chains. To this aim, we slightly revised the empirical parameters for the interaction between Ca2+ and the carboxylate oxygen atoms of GalA units so as to reproduce the experimental Ca2+-GalA association constant. We also defined an ad hoc order parameter, referred to as the egg-box score (EBS), that quantifies any deviation of the local coordination geometry of calcium cations with respect to an "ideal" EBM coordination geometry. The results reveal that the local coordination geometry of Ca2+ cations bound to polyGalA chains differs from that of the EBM. Moreover, polyGalA chains exhibit significant conformational disorder, and the cross-link angles formed between polyGalA chain axes are broadly distributed. Overall, the present study suggests that the EBM fails to describe accurately the association modes between calcium and polyGalA chains at a molar ratio R of 0.25.

Electroactive calcium-alginate/polycaprolactone/reduced graphene oxide nanohybrid hydrogels for skeletal muscle tissue engineering

Graphene derivatives such as reduced graphene oxide (rGO) are used as components of novel biomaterials for their unique electrical properties. Electrical conductivity is a crucial factor for muscle cells, which are electrically active. This study reports the development of a new type of semi-interpenetrated polymer network based on two biodegradable FDA-approved biomaterials, sodium alginate (SA) and polycaprolactone (PCL), with Ca2+ ions as SA crosslinker. Several drawbacks such as the low cell adhesion of SA and weak structural stability can be improved with the incorporation of PCL. Furthermore, this study demonstrates how this semi-IPN can be engineered with rGO nanosheets (0.5% and 2% wt/wt rGO nanosheets) to produce electroactive nanohybrid composite biomaterials. The study focuses on the microstructure and the enhancement of physical and biological properties of these advanced materials, including water sorption, surface wettability, thermal behavior and thermal degradation, mechanical properties, electrical conductivity, cell adhesion and myogenic differentiation. The results suggest the formation of a complex nano-network with different interactions between the components: bonds between SA chains induced by Ca2+ ions (egg-box model), links between rGO nanosheets and SA chains as well as between rGO nanosheets themselves through Ca2+ ions, and strong hydrogen bonding between rGO nanosheets and SA chains. The incorporation of rGO significantly increases the electrical conductivity of the nanohybrid hydrogels, with values in the range of muscle tissue. In vitro cultures with C2C12 murine myoblasts revealed that the conductive nanohybrid hydrogels are not cytotoxic and can greatly enhance myoblast adhesion and myogenic differentiation. These results indicate that these novel electroactive nanohybrid hydrogels have great potential for biomedical applications related to the regeneration of electroactive tissues, particularly in skeletal muscle tissue engineering.

Preparation and Properties of Urea Slow-Release Fertilizer Hydrogel by Sodium Alginate-Gelatin Biopolymer

Urea is high solubility nitrogen fertilizer. There is major nitrogen pollution in ecosystem. Slow-release nitrogen fertilizer the way to decrease nitrogen form agriculture. Slow-release nitrogen fertilizer the way to decrease nitrogen in agriculture. Slow-release formulations of nitrogen fertilizer were developed based on alginate-gelatin by using calcium chloride as the cross-linker in the egg-box model as hydrogels. Water-retaining ratio, loading behavior, and the release kinetics were examined. The release kinetic rates were investigated by Zero-order kinetic, First-order kinetic, Higuchi, Korsmeyer-Peppas, Weibull, and Hixson-Crowell models. The results showed that the S1G0.5 sample (alginate 1 g and gelatin 0.5 g) was the optimum condition for application as urea slow-release fertilizers because it was a minimal release kinetic rate for 12 hrs. These results indicate that the alginate-gelatin hydrogel can be a slow-release nutrient to plant an environmentally friendly fertilizer.

AgNP/Alginate Nanocomposite hydrogel for antimicrobial and antibiofilm applications

The synthesis and specific surface functionalization of antimicrobial silver nanoparticles (AgNPs) and their incorporation into an alginate hydrogel is described. Divalent cation-mediated ionic crosslinking was used to disperse the AgNPs throughout the gel, made possible by –COO- cross-linking sites provided by the surface-enhanced nanoparticles, inspired by the classic egg-box model crosslinking of calcium alginate. An AgNP concentration, 10-20 μg g-1 increased hygrogel elasticity, viscosity, and shear resistance by 45, 30, and 31% respectively. Cryo-TEM revealed evenly distributed AgNP assemblies of discrete AgNPs throughout the gel matrices. FTIR-ATR indicated AgNPs were involved in alginate carboxylate-Ca2+-COO-AgNP crossbridging, which was not achieved through mixing of AgNPs into preformed gels. Live/dead fluorometric assays determined a minimal bactericidal concentration of 25 μg g-1 Ag for 6 microorganisms. Anti-biofilm assays showed species-dependent cell death of 44 -61%, with limited silver ion release of 0.41% and 1.1% after 7 days for Gram positive and negative bacteria, respectively.

Regulation mechanisms of humic acid on Pb stress in tea plant (Camellia sinensis L.)

Though the interaction between humic acid (HA) and heavy metals has been widely reported, the effects of HA on the toxicity of heavy metals to plants are still in debate. In this study, the regulation mechanisms of HA on Pb stress in tea plant (Camellia sinensis L.) was investigated through hydroponic experiments, and the experimental results were explained by using transmission electron microscope (TEM), scanning transmission X-ray microscopes (STXM) and isobaric tags for relative and absolute quantitation (iTRAQ) differential proteomics. Significant alleviation of Pb stress was found with HA coexistence. TEM results showed that HA greatly mitigated the damage of cells caused by Pb stress. Compared with sole Pb treatment, the addition of HA increased the contents of pectin and pectic acid in the cell wall by 10.5% and 30.5%, while arabinose (Ara) and galactose (Gal) decreased by 20.5% and 15.9%, respectively, which were beneficial for increasing Pb adsorption capacity of the cell wall and promoting cell elongation. Moreover, iTRAQ differential proteomics analysis proved that HA strengthened the antioxidant system, promoted the synthesis of cell wall, and stabilized protein and sulfur-containing substance metabolism in molecular level. Notably, the concentration of calcium (Ca) in the cell wall of HA coexistence treatment was 47.4% higher than Pb treatment. STXM results also indicated that the distribution of Ca in the cell wall was restored with the presence of HA. This might promote the formation of the egg-box model, thus alleviating Pb stress in cells. Our results reveal the regulation mechanisms of HA on Pb detoxification in plants and provide useful information for improving the safety of agricultural products.

Evidence for an egg-box-like structure in iron(ii)-polygalacturonate hydrogels: a combined EXAFS and molecular dynamics simulation study.

The local structure of Fe2+ in Fe2+-polygalacturonic acid (polyGalA) hydrogels has been studied by coupling Extended X-ray Absorption Fine Structure (EXAFS) spectroscopy and molecular dynamics (MD) simulation. The EXAFS fitting results reveal an octahedral coordination geometry of Fe2+ both in aqueous solution and in the hydrogel, with similar Fe-O distances (2.09 ± 0.01 Å in the hydrogel and 2.11 ± 0.01 Å in aqueous solution). The MD simulations evidence that standard empirical force fields are unable to accurately reproduce the EXAFS spectra of Fe2+ in both aqueous solution and hydrogel. Based on the EXAFS distance determinations, we then performed restrained MD simulations of hypothetical octahedral coordination modes of Fe2+ with polyGalA chains. The best agreement between experimental and simulated EXAFS spectra was found when Fe2+ is monodentately coordinated to two carboxylate and two hydroxyl oxygens from a pair of polyGalA chains as well as to two water oxygens in an octahedral coordination geometry compatible with the "egg-box model".

Fouling mechanism of hydrophobic polytetrafluoroethylene (PTFE) membrane by differently charged organics during direct contact membrane distillation (DCMD) process: An especial interest in the feed properties

The growing attention to membrane distillation (MD) processes from various disciplines raises the demand for systematic research on MD membrane fouling. This study investigates the role of feed properties, such as feed compositions, charge properties, particle size, hydrophobicity/hydrophilcity, thermal stability and intermolecular interactions, in organic fouling of direct contact membrane distillation (DCMD). The differently charged lysozyme (LYS), sodium alginate (SA), and bovine serum albumin (BSA) were chosen as model organic foulants. The fouling data showed that the feed containing LYS and SA displayed a more severe flux decline compared to the BSA/SA solution, which was highly associated with the charge interaction. Additionally, the flux performance for the mixed foulants was partly affected by the proportion of protein (BSA or LYS) to polysaccharide (SA). It was found that the mixed feed containing less BSA caused a faster flux decline, whereas the feed containing higher amounts of LYS exhibited a more severe membrane fouling. Based on the membrane characterization analysis using FTIR, the BSA and SA showed significant conformational changes during the feed heating process, which largely aggravated the membrane fouling rate. Furthermore, the membrane fouling degree was proven to be distinctly affected by the sites where fouling occurred according to the SEM-EDX analysis. The results exhibited that SA was primarily deposited on the membrane surface, while the LYS largely penetrated into the pores, causing a more severe membrane fouling. Finally, two different fouling patterns including “egg-box model” and “multi-layer model” were suggested for the BSA/SA and LYS/SA feeds during the DCMD operation process, respectively.

An electrochemically active green synthesized polycrystalline NiO/MgO catalyst: Use in photo-catalytic applications

For many years, research scientists have aided communities in their tremendous efforts towards environmental remediation. Due to their high physical and chemical stability, metal oxide nanoparticles (NPs) have been used as metal catalysts to remedy this issue. This article reviews green approaches for the synthesis of metal oxide nanoparticles, in aqueous bio-reductive polyphenols from punica granatum peel extract and the degradation of organic pollutants. The bimetallic nanocomposite of face-centred cubic NiO/MgO pseudocapacitors were successfully prepared via the polyphenols of punica granatum peel extracts. X-ray diffraction spectroscopy (XRD) successfully provide evidence of polycrystalline face-centre cubic nanocomposite (high crystallinity index (Icry)>1) while revealing their interplanar distance. The spherical and irregular particle distribution of the binary NiO/MgO nanocomposite (at different calcination temperatures) was assessed by high resolution-TEM. FTIR, GC–MS and EDS provided evidence of the proposed mechanism during coordination between polyphenols and metal precursors. The popular “egg box model” is referred to in the case of polyphenols-metal interaction. The unique feature of two consecutive chelation site per repeat that provides a favourable entropic contribution to the inter-chain association is produced by this model governed by electrostatic interactions. Based on the obtained results, new structural models of Ni2+/Mg2+-polyphenols (punicalagin) complexes were proposed. UV–vis and Cyclic voltammetry confirmed the growth and band gap energies of the nanocomposite. NiO/MgO nanocomposite was found to be excellent photocatalysts for the degradation of methylene orange and methylene blue under the illumination of artificial light irradiation. The experiments demonstrated that MB in aqueous solution was more efficiently photo-degraded (87%) than MO (73%) using NiO/MgO nanocomposite as photocatalysts within 10min of exposure. Conclusively, the nanocomposite was found to be more efficient compared to other reported oxides.

<I>In Vitro</I> and <I>In Vivo</I> Evaluation of Pectin/Copper Exchanged Faujasite Composite Membranes

The biocompatibility and excellent ion exchange capacity make faujasites ideal candidates for tissue engineering applications. A novel pectin/copper exchanged faujasite hybrid membrane was synthesized by solvent casting technique, using calcium chloride as the crosslinking agent. AFM images revealed the egg-box model organization of calcium cross-linked pectin chains used as a matrix. The morphology of composite membranes was characterized by SEM and their elemental composition was determined using EDX. The higher contact angle of P (1%) when compared to that of native pectin figured out an enhanced hydrophobicity of hybrid material. The embedded faujasite particles maintained their crystalline structure as revealed by XRD and their interactions with the polymer matrix was evaluated by FTIR. The composite membrane with 1% (w/w) of copper exchanged faujasite, P(1%), exhibited better thermal stability, excellent antibacterial activity, controlled swelling and degradation. Finally, it displayed cell viability of 89% on NIH3T3 fibroblast cell lines and aided in improving wound healing and re-epithelialisation in Sprague Dawley rats. The obtained data suggested their potential as ideal matrices for efficient treatment of burn wounds.

Scaling law and microstructure of alginate hydrogel

The gelation of alginate in aqueous solution was studied as a function of Ca2+ concentration. At each given concentration of alginate, a critical gel concentration cg, Ca2+, was successfully determined for the first time using the Winter–Chambon criterion. The critical gel concentration cg, Ca2+ was found to increase linearly with alginate concentration. At the same time, the critical relaxation exponent n decreased and the critical gel strength Sg increased linearly with alginate concentration. An improved egg-box model was proposed to describe the change in gel junction and gel network. In the stable gel state, the plateau modulus Ge of alginate gel depended on Ca2+ concentration according to a power-law scaling, Ge=kɛ1.5, where ɛ is the relative distance of a gelling variable (Ca2+ concentration in this case) from the gel point (cg, Ca2+). The FESEM images verified the microstructure of alginate gel in which alginate chains associated into fibrils in the presence of Ca2+ ions. The fibrillar diameter and network density increased with increasing Ca2+ ion concentration while alginate concentration had a weak influence on fibrillar diameter.

Zeolites incorporated polymeric gel beads—Promising drug carriers

Novel hybrid gel beads comprising of pectin and copper exchanged zeolites were prepared using ionotropic gelation technique. The prepared beads were transparent and spherical. The egg-box model crosslinking of pectin was visualised on the surface of the bead. The embedded zeolites maintained their crystallinity inspite of their weak interactions with pectin. Their anti-bacterial properties were attributed due to the copper ions leached from the cavities of zeolites incorporated in polymer matrix. The obtained results proved their versatility as promising drug carriers.

Calcium-α-l-Guluronate Complexes: Ca2+ Binding Modes from DFT-MD Simulations

The interactions of divalent calcium ions with a single α-L-guluronate anion and oligo(α-L-guluronate) chain have been studied in terms of the 'hybrid' molecular dynamics technique in which the selected parts of the system are treated with different level of theory (DFT-MD). The simulations were focused on obtaining the free energy profiles designed to clarify the possible calcium binding modes. In all considered cases, the calcium ion is coordinated by carboxyl oxygen atoms and water molecules exclusively. The results allowed for (i) determining the dentacy of calcium binding; (ii) estimating the calcium binding/unbinding-related free energy profiles; and (iii) positive verification of the previously [J. Comput. Chem. 2011, 32, 2988] proposed modification of the egg-box model describing the calcium alginate/guluronate structure. Additionally, the findings indicate that the polarization of the carboxyl group induced by the presence of Ca(2+) ion causes the increase of the free energy barrier separating the 'free' and 'bound' states of Ca(2+), in comparison to the classical biomolecular force fields (GROMOS/SPC and GLYCAM/TIP3P).

Preparation of Ca-alginate biopolymer beads and investigation of their decorporation characteristics for 85Sr, 238U and 234Th by in vitro experiments

The aim of this work was to investigate whether Ca-alginate biopolymer beads (CaABBs) can be used to reduce the bioavailability of radionuclides in the gastrointestinal tract of humans. The uptake of strontium, uranium and thorium from a simulated gastrointestinal system was studied by in vitro techniques using CaABBs. This agent was prepared from Na-alginate through cross-linking with divalent calcium ions according to the egg-box model. The effects of process variables such as pH of the gastrointestinal juice, incubation time and solid-to-solution ratio for the removal of radionuclides from the gastrointestinal juice were investigated. The results suggest that CaABBs are a potent material for reducing the bioavailability of radionuclides with a high uptake efficiency in the gastrointestinal tract.

Biosorption of radiostrontium by alginate beads: application of isotherm models and thermodynamic studies

Radioactive strontium is one of the major radioactive contaminant and its contamination is a very serious concern. Therefore, there is a need for economic, effective, non-toxic, readily available and abundant adsorbent or biosorbent to remove strontium from solutions. In this study, biosorption of 85Sr as a surrogate for 90Sr onto alginate beads was investigated in a batch system. Alginate beads were prepared from Na-alginate via cross-linking with divalent calcium ions according to the egg box model. The effect of several parameters such as pH, initial strontium concentration, contact time, dosage of alginate beads and temperature were investigated. In order to optimize the design of biosorption system for the removal of strontium, it is important to establish the most appropriate correlation for equilibrium curves. The experimental isotherm data were described by 6 different biosorption isotherm models, namely Langmuir, Freundlich, Dubinin–Radushkevich, Temkin, Flory–Huggins and Brunauer, Emmer and Teller, with constants obtained from linear and non-linear regression methods. The thermodynamic parameters (∆H°, ∆S° and ∆G°) for strontium biosorption were also determined. The results indicate that these alginate beads have a good potential for the biosorption of strontium from solutions.

Mechanical properties of calcium alginate fibers produced with a microfluidic device

Fibers are important microstructural elements in many foods. The main objective of this research was to produce calcium alginate fibers with uniform diameters (about 300 and 550μm) using a microfluidic device (MFD) and to study the effect of concentration of sodium alginate [Alg] and calcium chloride [CaCl2] on their mechanical properties (MP). Moisture content (MO) and MP as maximum tensile stress (σmax), tensile strain at break (ΔL/L0) and apparent Young's modulus (E) of fibers were determined and a statistical model and surface responses were developed as a function of [Alg] and [CaCl2]. As [CaCl2] increased first a strengthening and then a weakening of fibers were observed. Furthermore, σmax increased with the addition of Ca2+ and a maximum of σmax was obtained for a [CaCl2] around 1.4% (exceeding several times the stoichiometric requirements of the carboxylate groups of the polymer). Such behavior prompted a molecular explanation of what happens during gelation based on the “egg-box model” and this model is tried to complete. Moreover, fibers with [Alg] ≥1.8% showed high extensibility (ΔL/L0 around 100%) and low values of MO. High values of E (∼0.5MPa) were obtained for [CaCl2] close to 1.4%. A greater understanding is needed of the interaction between cation-polysaccharide-water, taking into account [Alg] and [CaCl2] to predict the mechanical behavior of fibers. Calcium alginate fibers are important in food engineering as texture and microencapsulation agents.

Molecular basis of calcium binding by polyguluronate chains. Revising the egg‐box model

The egg-box model is the commonly accepted description of the calcium alginate/guluronate structure. It assumes that calcium ions are bound in the periodic chelation sites located between two polyuronate chains. This study was focused on elucidating the nature of interactions between calcium and polyuronates, responsible for the Ca(2+)-induced association of polyuronate chains in the aqueous solutions. Both molecular dynamics and semiempirical (ZINDO-1/Monte Carlo) methods were used for this purpose. Based on the obtained results, new structural models of Ca(2+)-polyguluronate complexes were proposed both for parallel and antiparallel pairing. Contrary to the classical egg-box model, Ca(2+) ions are coordinated by four carboxyl oxygens from two opposite carboxyl groups belonging to two different polyguluronate chains and, additionally, by four oxygen atoms belonging to water molecules. Such a coordination pattern can be interpreted as the result of competition between water molecules and carboxylic groups of polyguluronate for calcium ions. Other structural details (the network of hydrogen bonds, for instance) are close to those corresponding to the "shifted" egg-box model proposed by Braccini and Pérez (Biomacromolecules 2001, 2, 1089) and remain in agreement with the experimental data.