Macromolecular hydration phenomena

Dehabadi, Leila; Udoetok, Inimfon A.; Wilson, Lee D.

doi:10.1007/s10973-016-5673-6

Cited by 11 publications

(12 citation statements)

References 122 publications

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“…Table 2) relates to its variable HLB character, arising due to its unique quaternary fibril structure. 44 The properties of CE are contrasted with starch biopolymers that possess greater hydrophile character and conformational lability. The narrow DSC endotherms at higher temperatures (for AP and CE) are in agreement with the greater stability of the bound water, in accordance with the microporous structure and apolar domains of these biopolymers.…”

Section: Discussionmentioning

confidence: 99%

Spectroscopic and Thermodynamic Study of Biopolymer Adsorption Phenomena in Heterogeneous Solid–Liquid Systems

2018

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Molecular selective adsorption processes at the solid surface of biopolymers in mixed solvent systems are poorly understood due to manifold interactions. However, the ability to achieve adsorptive fractionation of liquid mixtures is posited to relate to the role of specific solid–liquid interactions at the adsorbent interface. The hydration of solid biopolymers (amylose, amylopectin, cellulose) in binary aqueous systems is partly governed by the relative solvent binding affinities with the biopolymer surface sites, in accordance with the role of textural and surface chemical properties. While molecular models that account for the surface area and solvent effects provide reliable estimates of hydration energy and binding affinity parameters, spectroscopic and thermal methods offer a facile alternative experimental approach to account for detailed aspects of solvation phenomena at biopolymer interfaces that involve solid−liquid adsorption. In this report, thermal and spectroscopic methods were used to understand the interaction of starch- and cellulose-based materials in water–ethanol (W–E) binary mixtures. Batch adsorption studies in binary W–E mixtures reveal the selective solvent uptake properties by the biomaterials, in agreement with their solvent swelling in pure water or ethanol. The nature, stability of the bound water, and the thermodynamic properties of the biopolymers in variable hydration states were probed via differential scanning calorimetry and Raman spectroscopy. The trends in biopolymer–solvent interactions are corroborated by dye adsorption and scanning electron microscopy, indicating that biopolymer adsorption properties in W–E mixtures strongly depend on the surface area, pore structure, and accessibility of the polar surface groups of the biopolymer systems, in agreement with the solvent-selective uptake results reported herein.

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Section: Discussionmentioning

confidence: 99%

Spectroscopic and Thermodynamic Study of Biopolymer Adsorption Phenomena in Heterogeneous Solid–Liquid Systems

2018

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“…In general, all the flax materials show very small SA (∼1 m 2 /g) that is characteristic of nonporous fibril materials, 23,24 with negligible pore volumes ranging ∼0.35 to 1.3 × 10 −4 cm 3 /g (cf. Table 1).…”

Section: Resultsmentioning

confidence: 99%

“…20,22 More recently, new insight into surface-mediated hydration processes was obtained using complementary material characterization studies: spectroscopy, thermal analyses, solvent uptake, and adsorption isotherm methods. Recent studies 23,24 on the hydration of starch-and cellulose-based materials in mixed solvent systems reveal that the relative biopolymer−solvent affinity depends on various physicochemical properties: (1) HLB of the biopolymer, (2) relative polarity of the biopolymer−solvent system, (3) textural [surface area (SA) and pore structure] properties, and (4) solvent properties such as relative polarity and molar volume. The ability of natural FFs to adsorb water relates to the presence of abundant polar functional groups (−OH and COOH) that characterize surface adsorption sites.…”

Section: Introductionmentioning

confidence: 99%

“…Biopolymer hydration is ubiquitous to many chemical processes and stabilization of biological structures. − Theoretical and experimental techniques have been employed to investigate the hydration properties of biopolymers. , For example, single-crystal X-ray diffraction techniques and high-resolution NMR spectroscopy have provided unique insight into biopolymer hydration phenomena. , More recently, new insight into surface-mediated hydration processes was obtained using complementary material characterization studies: spectroscopy, thermal analyses, solvent uptake, and adsorption isotherm methods. Recent studies , on the hydration of starch- and cellulose-based materials in mixed solvent systems reveal that the relative biopolymer–solvent affinity depends on various physicochemical properties: (1) HLB of the biopolymer, (2) relative polarity of the biopolymer–solvent system, (3) textural [surface area (SA) and pore structure] properties, and (4) solvent properties such as relative polarity and molar volume. The ability of natural FFs to adsorb water relates to the presence of abundant polar functional groups (−OH and COOH) that characterize surface adsorption sites.…”

Section: Introductionmentioning

confidence: 99%

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Hydration and Sorption Properties of Raw and Milled Flax Fibers

Karoyo

Dehabadi²,

Alabi

et al. 2020

ACS Omega

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The physicochemical and hydration properties of mechanically modified flax fibers (FFs) were investigated herein. Raw flax fibers (FF-R) were ball-milled and sieved through mesh with various aperture sizes (420, 210, and 125 μm) to achieve modified samples, denoted as FF-420, FF-210, and FF-125, respectively. The physicochemical and hydration properties of FF-R with variable particle sizes were characterized using several complementary techniques: microscopy (SEM), spectroscopy (FT-IR, XRD, and XPS), thermoanalytical methods (DSC and TGA), adsorption isotherms using gas/dye probes, and solvent swelling studies in liquid H 2 O. The hydration of FF biomass is governed by the micropore structure and availability of active surface sites, as revealed by the adsorption isotherm results and the TGA/DSC profiles of the hydrated samples. Gravimetric water swelling, water retention values, and vapor adsorption results provide further support that particle size reduction of FF-R upon milling parallels the changes in surface chemical and physicochemical properties relevant to adsorption/hydration in the modified FF materials. This study outlines a facile strategy for the valorization and tuning of the physicochemical properties of agricultural FF biomass via mechanical treatment for diverse applications in biomedicine, energy recovery, food, and biosorbents for environmental remediation.

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“…For the higher MC concentrations, the polymeric chains were closer to each other and it was feasible to form hydrophobic interactions. Denser packed MC chains tended to make bridges with water molecules [30]. In a partially cross-linked network, aggregation occurred at sufficiently high temperatures, when it was easier to break down water cages at higher concentrations.…”

Section: Resultsmentioning

confidence: 99%

Crosslinking Kinetics of Methylcellulose Aqueous Solution and Its Potential as a Scaffold for Tissue Engineering

et al. 2019

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Thermosensitive, physically crosslinked injectable hydrogels are in the area of interests of various scientific fields. One of the representatives of this materials group is an aqueous solution of methylcellulose. At ambient conditions, methylcellulose (MC) is a sol while on heating up to 37 °C, MC undergoes physical crosslinking and transforms into a gel. Injectability at room temperature, and crosslinkability during subsequent heating to physiological temperature raises hopes, especially for tissue engineering applications. This research work aimed at studying crosslinking kinetics, thermal, viscoelastic, and biological properties of MC aqueous solution in a broad range of MC concentrations. It was evidenced by Differential Scanning Calorimetry (DSC) that crosslinking of MC is a reversible two-stage process, manifested by the appearance of two endothermic effects, related to the destruction of water cages around methoxy groups, followed by crosslinking via the formation of hydrophobic interactions between methoxy groups in the polymeric chains. The DSC results also allowed the determination of MC crosslinking kinetics. Complementary measurements of MC crosslinking kinetics performed by dynamic mechanical analysis (DMA) provided information on the final storage modulus, which was important from the perspective of tissue engineering applications. Cytotoxicity tests were performed using mouse fibroblasts and showed that MC at low concentration did not cause cytotoxicity. All these efforts allowed to assess MC hydrogel relevance for tissue engineering applications.

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Macromolecular hydration phenomena

Cited by 11 publications

References 122 publications

Spectroscopic and Thermodynamic Study of Biopolymer Adsorption Phenomena in Heterogeneous Solid–Liquid Systems

Spectroscopic and Thermodynamic Study of Biopolymer Adsorption Phenomena in Heterogeneous Solid–Liquid Systems

Hydration and Sorption Properties of Raw and Milled Flax Fibers

Crosslinking Kinetics of Methylcellulose Aqueous Solution and Its Potential as a Scaffold for Tissue Engineering

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