Effect of chain extender length and molecular architecture on phase separation and rheological properties of ether-based polyurethanes

2021 ◽  
Author(s):  
Mohammadali Pourmohammadi-Mahunaki ◽  
Vahid Haddadi-Asl ◽  
Hossein Roghani-Mamaqani ◽  
Mojtaba Koosha ◽  
Mohammad Yazdi
2021 ◽  
Author(s):  
Ibraheem Alshareedah ◽  
Mahdi Muhammad Moosa ◽  
Priya R. Banerjee

The rheological properties of biological matters play a fundamental role in many cell processes. At the organelle level, liquid-liquid phase separation of multivalent proteins and RNAs drives the formation of biomolecular condensates that facilitate dynamic compartmentalization of cellular biochemistry1. With recent advances, it is becoming increasingly clear that the structure and rheological properties of these condensates are critical to their cellular functions2,3. Meanwhile, aberrant liquid-to-solid transitions in some cellular condensates are implicated in neurodegenerative disorders4. Within the limits of two extreme material states, viz., viscous liquid and amorphous or fibrillar solid, there lies a spectrum of materials known as viscoelastic fluids. Viscoelastic fluids behave as an elastic solid at time-scales shorter than their network reconfiguration time but as a viscous fluid at longer time-scales. Viscoelasticity of biomolecular condensates may constitute an adaptive mechanism for sensing mechanical stress and regulating biochemical processes5. From an engineering standpoint, viscoelastic fluids hold great potential for designing soft biomaterials with programmable mechanosensitivity6,7. Here, employing microrheology with optical tweezers, we demonstrate how multivalent disordered sticker-spacer8,9 polypeptides undergoing associative phase separation with RNA can be designed to control the frequency-dependent viscoelastic behavior of their condensates. Utilizing linear repeat polypeptides inspired by natural RNA-binding sequences, we show that polypeptide-RNA condensates behave as Maxwell fluids, with viscoelastic behavior that can be fine-tuned by the identity of the sticker and spacer residues. The sequence heuristics that we uncovered allowed us to create biomolecular condensates spanning two orders of magnitude in their viscous and elastic responses to the applied mechanical stress. This sequence-encoded regulation of viscoelasticity in disordered polypeptide-RNA condensates establishes a link between the molecular architecture of the polypeptide chains and the rheological properties of the resulting condensates at the mesoscale, enabling a route to engineer soft biomaterials with programmable mechanics.


Polymer Korea ◽  
2018 ◽  
Vol 42 (3) ◽  
pp. 394-399
Author(s):  
Jae O Park ◽  
Woo Jin Choi ◽  
Kwang Je Kim ◽  
Jae Heung Lee ◽  
Jae Sup Shin

2010 ◽  
Vol 49 (8) ◽  
pp. 827-836 ◽  
Author(s):  
V. F. Shumsky ◽  
I. Getmanchuk ◽  
T. Ignatova ◽  
Yu. Maslak ◽  
P. Cassagnau ◽  
...  

2021 ◽  
Vol 13 (19) ◽  
pp. 10582
Author(s):  
Peng Wang ◽  
Hong-Rui Wei ◽  
Xi-Yin Liu ◽  
Rui-Bo Ren ◽  
Li-Zhi Wang

The thermal storage stability of styrene–butadiene–styrene tri-block copolymer modified bitumen (SBSPMB) is the key to avoid performance attenuation during storage and transportation in pavement engineering. However, existing evaluation index softening point difference within 48 h (ΔSP48) cannot effectively distinguish this attenuation of SBSPMB. Thus, conventional physical indexes, rheological properties, and micro-structure characteristics of SBSPMB during a 10-day storage were investigated in this research. Results showed that during long-term thermal storage under 163 °C for 10 days, penetration, ductility, softening point, recovery rate (R%), and anti-rutting factor (G*/sinδ) were decayed with storage time increasing. This outcome was ascribed to the phase separation of SBS, which mainly occurred after a 4-day storage. However, ΔSP48 after a 6-day storage met the specification requirements (i.e., below 2.5 °C). Thus, the attenuation degree of asphalt performance in field storage was not effectively characterized by ΔSP48 alone. Results from network strength (I) and SBS swelling degree tests revealed that the primary cause was SBS degradation and base asphalt aging. Moreover, conventional indexes, including penetration, ductility, and softening point, were used to build a prediction model for rheological properties after long-term storage using partial least squares regression model, which can effectively predict I, R, Jnr, G*/sinδ, and SBS amount. Correlation coefficient is above 0.8. G*/sinδ and I at the top and bottom storage locations had high coefficient with SBS amount. Thus, phase separation of SBSPMB should be evaluated during thermal storage.


2022 ◽  
Vol 0 (0) ◽  
Author(s):  
Kai Yuan ◽  
Xiaofei Li ◽  
Xudong Yang ◽  
Shuai Luo ◽  
Xi Yang ◽  
...  

Abstract In this study, the effect of bacterial cellulose nanofibers (BCNF) incorporation on the structural and rheological properties of casein gels was investigated, where the mixed BCNF and casein gels were prepared by adding gluconic acid δ-lactone (GDL) to acidify the mixed polymer solutions at 3.0% casein concentration (w/v) and varying BCNF concentrations (0–0.5%, w/v). By changing the addition amount of GDL, the mechanical and structural properties of the mixed gels were studied at above, near and below the electric point (pI) of the casein. At pH above the pI of the casein, the introduction of BCNF initially increased the gel strength, but further addition of BCNF weakened the mixed gels. At near and below the pI of the casein, the incorporation of BCNF continuously increased the gel strength. Besides, all gels showed good structural homogeneity, without macroscopic phase separation occurring, which indicated good compatibility of BCNF with the casein gels.


2021 ◽  
Vol 43 (4) ◽  
pp. 280-286
Author(s):  
T.D. IGNATOVA ◽  
◽  
L.F. KOSYANCHUK ◽  

This article is devoted to the analysis of the results of the investigation of the process of forming mixtures of linear polymers formed simultaneously in situ according to different mechanisms. The first mechanism is polyaddition, the second mechanism is radical polymerization. This is one of the possible ways to obtain multicomponent polymer systems. The kinetics of chemical reactions of the formation of components and the phase separation which accompanies these reactions were studied for mixtures of poly(methyl methacrylate) (PMMA) with two polyurethanes (PU) of different chemical nature of both flexible and rigid blocks. PU-1 was synthesized from macrodiisocyanate based on oligo(tetramethylene glycol) with molecular mass 1000 g·mol–1 and hexamethylene diisocyanate taken in the molar ratio 1 : 2 using diethylene glycol as a chain extender. PU-2 was synthesized from macrodiisocyanate based on olygo(propylene glycol) with molecular mass 1000 g·mol–1 and toluylene diisocyanate taken in the molar ratio 1 : 2 using butanediol as a chain extender. The mixture of polystyrene (PS) with PU-2 was studied too. It is established that regardless of the chemical nature of the components, the process of in situ mixture formation is subject to general laws. In particular, the change in the chemical nature of the component formed by the mechanism of polyaddition (mixtures PMMA/PU-1 and PMMA/PU-2) or of the component formed by radical polymerization (mixtures PMMA/PU-2 and PS/PU-2) does not affect the nature of the dependence of the conversion degree of components and the fraction of formed polymers at the beginning of the phase separation on the composition of the initial reaction mixtures. Only the absolute values of these parameters change due to different reactivity and different thermodynamic compatibility of the mixed components.


2011 ◽  
Vol 331 ◽  
pp. 139-143 ◽  
Author(s):  
Heng Quan ◽  
Zhen Ya Gu

A series of hydrophilic polyether polyurethanes were prepared with two-steps technique from 4,4’- diphenylmethane diisocyanate (MDI), polytetramethylene glycol 1000 (PTMG1000) and polyethylene glycol 1000 (PEG1000) with 1,4-butanediol (BDO) as the chain extender. Further more, the relationships between structure and moisture permeability, water resistance, hydrophility and phase inversion temperature (PIT) of the polyurethanes was investigated. For polyether polyurethanes with nicer micro phase separation structure, the studies show that the hydrophilic ether bond content and mobility of soft segment chains have decisive effect on their water resistance, moisture permeability and hydrophility without reference to the soft segment content on the whole.


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