Changes to fine structure, size and mechanical modulus of phytoglycogen nanoparticles subjected to high-shear extrusion

Román, Laura; Baylis, Benjamin; Klinger, Karl; Jong, Jondavid de; Dutcher, John; Martínez, Mario M.

doi:10.1016/j.carbpol.2022.120080

Cited by 16 publications

(15 citation statements)

References 37 publications

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“…The best-fit value corresponds to surface chains with R g = 1.59 ± 0.04 nm, grafting density of 0.296 ± 0.005 chains/nm 2 , and degree of polymerization (DP) = 5.9 ± 0.2, which are comparable to the values R g = 1.5 nm, 0.125 ± 0.008 chains/nm 2 , and DP = 20 obtained by Simmons et al (2020) (see Table S2 in Supporting Information). Dividing the total particle volume by the AGU volume with its associated water (0.760 nm 3 ) yields a molecular weight of 7.63 × 10 6 g/mol, which is within an order of magnitude to recent more accurately measured values for PG. ,, To extend the modeling to low x EtOH values, wherein the assumption of Gaussian statistics of the surface chains under poor solvent conditions does not likely hold, we employed the raspberry model that constitutes a sphere with smaller hemispherical asperities embedded on its surface to model the excess high- q scattering region. We find a decreasing best-fit surface asperity size with increasing x EtOH ; however, between 0.071 ≤ x EtOH ≤ 0.129 the maximum permitted DP of fully dehydrated chains that the surface asperity features can contain is less than the DP of chains at x EtOH = 0 (see Table S3 in Supporting Information).…”

Section: Resultsmentioning

confidence: 99%

“…The influence of branching degree on PG stability in water points to the importance of end-groups to the colloidal stability of PG . Similarly, the core-chain SAXS model of PG has been physically motivated at the single-particle level due to its many exposed oligosaccharide chains. , Considering the average internal chain length of PG as 9.6, the polymeric corona of the dangling oligosaccharide chains of comparable length on the PG nanoparticle surface provides either stability or instability depending on the relative strength of chain–chain and chain–solvent interactions.…”

Section: Resultsmentioning

confidence: 99%

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Tuning the Phytoglycogen Size and Aggregate Structure with Solvent Quality: Influence of Water–Ethanol Mixtures Revealed by X-ray and Light Scattering Techniques

et al. 2022

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Phytoglycogen (PG) is a hyperbranched polysaccharide with promising properties for biomedical and pharmaceutical applications. Herein, we explore the size and structure of sweet corn PG nanoparticles and their aggregation in water–ethanol mixtures up to the ethanol mole fraction x EtOH = 0.364 in dilute concentrations using small-angle X-ray scattering (SAXS) and dynamic light scattering (DLS) measurements. Between 0 ≤ x EtOH ≤ 0.129, the conformation of PG contracts gradually decreasing up to ca. 80% in hydrodynamic volume, when measured shortly after ethanol addition. For equilibrated PG dispersions, SAXS suggests a lower PG volume decrease between 19 and 67% at the corresponding x EtOH range; however, the inflection point of the DLS volume contraction coincides with the onset of reduced colloidal stability observed with SAXS. Up to x EtOH = 0.201, the water–ethanol mixtures yield labile fractal and globular aggregates, as evidenced by their partial breakup under mild ultrasonic treatment, demonstrated by the decrease in their hydrodynamic size. Between 0.235 ≤ x EtOH ≤ 0.364, PG nanoparticles form larger, more cohesive globular aggregates that are less affected by ultrasonic shear forces.

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Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

Tuning the Phytoglycogen Size and Aggregate Structure with Solvent Quality: Influence of Water–Ethanol Mixtures Revealed by X-ray and Light Scattering Techniques

et al. 2022

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“…Fluorophore‐assisted capillary electrophoresis, high‐performance anion‐exchange chromatography, SEC with multi‐angle laser light scattering detection, and asymmetric‐flow field‐flow fractionation have proved useful for analysis of the size distribution and average molecular weight of dendritic glucan (Ciric et al., 2014; Matsui‐Yatsuhashi et al., 2017; Wang, Liu, et al., 2019). The recent work showed the unit and internal chain length distributions of phytoglycogen using high‐performance anion‐exchange chromatography and β‐amylolysis, which indicated that phytoglycogen had a lower A‐chain:B‐chain ratio (0.7), a lower number of chains per B‐chain (1.7), and a much higher number of A fingerprint chains (19.4%) compared to amylopectin (Roman et al., 2022).…”

Section: General Structurementioning

confidence: 99%

Advanced dendritic glucan‐derived biomaterials: From molecular structure to versatile applications

Chen

Zhao

McClements

et al. 2023

Comp Rev Food Sci Food Safe

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There is considerable interest in the development of advanced biomaterials with improved or novel functionality for diversified applications. Dendritic glucans, such as phytoglycogen and glycogen, are abundant biomaterials with highly branched three‐dimensional globular architectures, which endow them with unique structural and functional attributes, including small size, large specific surface area, high water solubility, low viscosity, high water retention, and the availability of numerous modifiable surface groups. Dendritic glucans can be synthesized by in vivo biocatalysis reactions using glucosyl‐1‐phosphate as a substrate, which can be obtained from plant, animal, or microbial sources. They can also be synthesized by in vitro methods using sucrose or starch as a substrate, which may be more suitable for large‐scale industrial production. The large numbers of hydroxyl groups on the surfaces of dendritic glucan provide a platform for diverse derivatizations, including nonreducing end, hydroxyl functionalization, molecular degradation, and conjugation modifications. Due to their unique physicochemical and functional attributes, dendritic glucans have been widely applied in the food, pharmaceutical, biomedical, cosmetic, and chemical industries. For instance, they have been used as delivery systems, adsorbents, tissue engineering scaffolds, biosensors, and bioelectronic components. This article reviews progress in the design, synthesis, and application of dendritic glucans over the past several decades.

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“…Many of these applications of PG rely on the binding or association of biomolecules with PG. The applications of PG can be further extended by modifying the particles, e.g., through covalent attachment of functional groups, partial digestion of the glycosidic bonds in the particles, , or by subjecting the particles to high shear . In the present study, we consider the effect of acid hydrolysis on the binding properties of PG.…”

Section: Introductionmentioning

confidence: 99%

“…The applications of PG can be further extended by modifying the particles, e.g., through covalent attachment of functional groups, partial digestion of the glycosidic bonds in the particles, 18,19 or by subjecting the particles to high shear. 20 In the present study, we consider the effect of acid hydrolysis on the binding properties of PG. Recently, we showed that acid hydrolysis results in not only a decrease in the particle radius but also a significant decrease in the mechanical stiffness of the particles.…”

Section: ■ Introductionmentioning

confidence: 99%

Binding Affinity of Concanavalin A to Native and Acid-Hydrolyzed Phytoglycogen Nanoparticles

et al. 2022

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Phytoglycogen (PG) is a polysaccharide produced in the kernels of sweet corn as soft, highly branched, compact nanoparticles. Its tree-like or dendritic architecture, combined with a high-safety profile, makes PG nanoparticles attractive for use in biological applications, many of which rely on the association or binding of small biomolecules. We have developed a methodology to functionalize surface plasmon resonance (SPR) sensor surfaces with PG nanoparticles, and we demonstrate the utility of the PG-functionalized SPR sensor by measuring the binding affinity of the tetrameric concanavalin A (ConA) protein to both native PG nanoparticles and smaller, softer acid-hydrolyzed PG nanoparticles. We measure comparable values of the equilibrium association constant K for native and acid-hydrolyzed PG, with a slightly smaller value for the acid-hydrolyzed particles that we attribute to unfavorable lateral interactions between the tetrameric subunits of ConA due to the increase in surface curvature of the smaller acid-hydrolyzed PG particles. We also use infrared reflection-absorption spectroscopy (IRRAS) to show that ConA maintains a large fraction of its native conformation, and thus its bioactivity, upon binding to PG, representing an important step toward the realization of PG as a novel bioactive delivery vehicle.

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Changes to fine structure, size and mechanical modulus of phytoglycogen nanoparticles subjected to high-shear extrusion

Cited by 16 publications

References 37 publications

Tuning the Phytoglycogen Size and Aggregate Structure with Solvent Quality: Influence of Water–Ethanol Mixtures Revealed by X-ray and Light Scattering Techniques

Tuning the Phytoglycogen Size and Aggregate Structure with Solvent Quality: Influence of Water–Ethanol Mixtures Revealed by X-ray and Light Scattering Techniques

Advanced dendritic glucan‐derived biomaterials: From molecular structure to versatile applications

Binding Affinity of Concanavalin A to Native and Acid-Hydrolyzed Phytoglycogen Nanoparticles

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