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Hydrodynamic Study of Linear Pullulan Standards in DMF Solutions and Metrology Aspects of Transport Methods

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Submitted:

06 December 2024

Posted:

09 December 2024

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Abstract
Due to the great demand of pullulan in macromolecular characterization area and its attractive capabilities for chemical engineering towards bio-, farmo-, medical composite materials in DMF solutions we have conducted the classical molecular hydrodynamic study with pullulan standards in dilute DMF solutions. The hydrodynamic characteristics were acquired through viscometry, velocity sedimentation, isothermal diffusion and DLS. The self-consistency check of the obtained values was performed within the concept of hydrodynamic invariant and then the absolute values of molar masses were determined by Svedberg equation. The canonical Kuhn-Mark-Houwink-Sakurada scaling relationships were determined: η, cm^3/g=0.058*M^0.60, s0*10^13, s=0.020*M^0.48 and D_0*10^7,cm^2/s=1300*M^(-0.52) for intrinsic viscosity, sedimentation and diffusion coefficients, correspondingly, within broad molar mass range 7.2≤M_(sD)10^(-3),g/mol≤640. The most sophisticated Gray-Bloomfield-Hearst theory based on implementation of wormlike necklace model resulted in equilibrium rigidity A=(2.4±0.2) nm and transversal polymer chain diameter d=(0.5±0.3) nm. The conformational parameters were also assesed with computer simulations within modern Multi-HYDFIT suite and leaded to close enough data: A_MHF=(3.7±0.3) nm and d_MHF=(2.2±0.2) nm, showing great convergence of classical hydrodynamic theory with computer simulations. The inhere obtained data for pullulan in DMF solutions were also compared with earlier reported results obtained in water revealing nearly identical conformational parameters. Within metrology aspect the acqusiotion of the hydrodynamic characteristics with differenr experimental techniques and their interrelation is discussed in detail.
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Subject: Chemistry and Materials Science  -   Biomaterials
Copyright: This open access article is published under a Creative Commons CC BY 4.0 license, which permit the free download, distribution, and reuse, provided that the author and preprint are cited in any reuse.
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