Polydimethylsiloxane-Based Polyurethanes: Phase-Separated Morphology and In Vitro Oxidative Biostability

2009 ◽  
Vol 62 (8) ◽  
pp. 794 ◽  
Author(s):  
Taeyi Choi ◽  
Jadwiga Weksler ◽  
Ajay Padsalgikar ◽  
Rebeca Hernéndez ◽  
James Runt

Three series of segmented polyurethane block copolymers were synthesized using 4,4′-methylenediphenyl diisocyanate (MDI) and 1,4-butanediol (BDO) or 1,3-bis(4-hydroxybutyl)tetramethyl disiloxane (BHTD) as the hard segments, and soft segments composed of poly(dimethyl siloxane) (PDMS)-based and poly(hexamethylene oxide) (PHMO) macrodiols. Copolymers synthesized with the PDMS macrodiol and PDMS and PHMO macrodiol mixtures consist of three microphases: a PDMS phase, hard domains, and a mixed phase of PHMO (when present), PDMS ether end-group segments and some dissolved hard segments. Degrees of phase separation were characterized using small-angle X-ray scattering by applying a pseudo two-phase model, and the morphology resulting from unlike segment demixing was found to be closely related to the in vitro oxidative biostability of these segmented polyurethanes.

1999 ◽  
Vol 14 (9) ◽  
pp. 3789-3798 ◽  
Author(s):  
Arata Korematsu ◽  
Yu-Jun Li ◽  
Takayuki Murakami ◽  
Tadao Nakaya

New segmented polyurethanes containing phospholipid moieties in the main chains and long-chain alkyl groups in the side chains were synthesized. The soft segments used in this study were poly(butadiene), poly(isoprene), hydrogenated poly(isoprene), and poly(1,6-hexyl-1,2-ethylcarbonate) diol. The hard segments of these polyurethanes were 4,4′-methylenediphenyl diisocyanate, bis[2-(2-hydroxyethyldimethylammonio)ethyl]2-cetyl- 1,3-propanediphosphate, and 1,4-butanediol. The blood compatibilities of the new polymers were evaluated by platelet-rich plasma contact studies and viewed by scanning electron microscopy using medical grade BioSpan® and nonphospholipid polyurethane as references. These new materials have good surfaces in terms of platelet adhesion, and the morphology of adhered platelets undergoes a relatively low degree of variation.


1993 ◽  
Vol 328 ◽  
Author(s):  
Ken D. Zemach ◽  
M. F. Rubner

ABSTRACTSeveral diacetylene containing polyesters with thermochromic transitions at or around room temperature have been synthesized. Some of these polymers have been shown to be highly sensitive to body temperature, giving rise to either reversible or irreversible thermochromic changes, depending upon both the molecular structure and the processing conditions. By changing the structure and processing conditions, the thermochromic transition can be moved over a wide range of temperatures. Segmented polyurethanes using these diacetylene functionalized polyesters as soft segments and containing diacetylene groups in the hard segments have also been produced. Through a selective polymerization process, it is possible to selectively cross-polymerize the hard segment diacetylene groups or cross-polymerize both the hard and soft segments thereby making it possible to examine the effects of hard and soft segment crosslinking on mechanical properties.


Author(s):  
S. L. Goodman ◽  
C. Li ◽  
S. L. Cooper ◽  
R. M. Albrecht

Segmented polyurethanes (PUs) are composed of alternating blocks of crystalline or glassy urethane “hard segments” and rubbery “soft segments.” Chemical incompatability between hard segment (HS) and soft segment (SS) blocks produces a two-phase structure, which accounts for the elastomeric properties of these polymer systems. Polyurethanes are prepared with different HS and SS components, and HS:SS ratios, for various applications. Knowledge of the 3D morphology is necessary to understand polyurethane structure-property relationships. Although conventional transmission electron microscopy can image some polyurethanes, high voltage electron microscopy (HVEM) causes less radiation damage and images thicker samples at higher resolution, thus a sample region may be imaged at multiple tilt angles to provide 3D information. High resolution scanning electron microscopy (HR-SEM) provides complementary information, and at low accelerating voltages (1-3 keV), images near surface structures.Polyurethanes were examined with hard segments of methylene diphenylene diisocyanate (MDI) and 2000 MW soft segments of polytetramethylene oxide (PTMO), polybutadiene (PBD) and polydimethysiloxane (PDMS).


Author(s):  
Eva-Maria Mandelkow ◽  
Ron Milligan

Microtubules form part of the cytoskeleton of eukaryotic cells. They are hollow libers of about 25 nm diameter made up of 13 protofilaments, each of which consists of a chain of heterodimers of α-and β-tubulin. Microtubules can be assembled in vitro at 37°C in the presence of GTP which is hydrolyzed during the reaction, and they are disassembled at 4°C. In contrast to most other polymers microtubules show the behavior of “dynamic instability”, i.e. they can switch between phases of growth and phases of shrinkage, even at an overall steady state [1]. In certain conditions an entire solution can be synchronized, leading to autonomous oscillations in the degree of assembly which can be observed by X-ray scattering (Fig. 1), light scattering, or electron microscopy [2-5]. In addition such solutions are capable of generating spontaneous spatial patterns [6].In an earlier study we have analyzed the structure of microtubules and their cold-induced disassembly by cryo-EM [7]. One result was that disassembly takes place by loss of protofilament fragments (tubulin oligomers) which fray apart at the microtubule ends. We also looked at microtubule oscillations by time-resolved X-ray scattering and proposed a reaction scheme [4] which involves a cyclic interconversion of tubulin, microtubules, and oligomers (Fig. 2). The present study was undertaken to answer two questions: (a) What is the nature of the oscillations as seen by time-resolved cryo-EM? (b) Do microtubules disassemble by fraying protofilament fragments during oscillations at 37°C?


1981 ◽  
Vol 46 (7) ◽  
pp. 1675-1681 ◽  
Author(s):  
Josef Baldrian ◽  
Božena N. Kolarz ◽  
Henrik Galina

Porosity variations induced by swelling agent exchange were studied in a styrene-divinylbenzene copolymer. Standard methods were used in the characterization of copolymer porosity in the dry state and the results were compared with related structural parameters derived from small angle X-ray scattering (SAXS) measurements as developed for the characterization of two-phase systems. The SAXS method was also used for porosity determination in swollen samples. The differences in the porosity of dry samples were found to be an effect of the drying process, while in the swollen state the sample swells and deswells isotropically.


2021 ◽  
Vol 4 (1) ◽  
Author(s):  
Margret Paar ◽  
Vera H. Fengler ◽  
Daniel J. Rosenberg ◽  
Angelika Krebs ◽  
Rudolf E. Stauber ◽  
...  

AbstractHuman serum albumin (HSA) constitutes the primary transporter of fatty acids, bilirubin, and other plasma compounds. The binding, transport, and release of its cargos strongly depend on albumin conformation, which is affected by bound ligands induced by physiological and pathological conditions. HSA is both highly oxidized and heavily loaded with fatty acids and bilirubin in chronic liver disease. By employing small-angle X-ray scattering we show that HSA from the plasma of chronic liver disease patients undergoes a distinct opening compared to healthy donors. The extent of HSA opening correlates with clinically relevant variables, such as the model of end-stage liver disease score, bilirubin, and fatty acid levels. Although the mild oxidation of HSA in vitro does not alter overall structure, the alteration of patients’ HSA correlates with its redox state. This study connects clinical data with structural visualization of albumin dynamicity in solution and underlines the functional importance of albumin’s inherent flexibility.


Biomolecules ◽  
2019 ◽  
Vol 10 (1) ◽  
pp. 39 ◽  
Author(s):  
Roman Kamyshinsky ◽  
Yury Chesnokov ◽  
Liubov Dadinova ◽  
Andrey Mozhaev ◽  
Ivan Orlov ◽  
...  

Rapid increase of intracellular synthesis of specific histone-like Dps protein that binds DNA to protect the genome against deleterious factors leads to in cellulo crystallization—one of the most curious processes in the area of life science at the moment. However, the actual structure of the Dps–DNA co-crystals remained uncertain in the details for more than two decades. Cryo-electron tomography and small-angle X-ray scattering revealed polymorphous modifications of the co-crystals depending on the buffer parameters. Two different types of the Dps–DNA co-crystals are formed in vitro: triclinic and cubic. Three-dimensional reconstruction revealed DNA and Dps molecules in cubic co-crystals, and the unit cell parameters of cubic lattice were determined consistently by both methods.


FEBS Letters ◽  
2019 ◽  
Vol 593 (12) ◽  
pp. 1360-1371 ◽  
Author(s):  
Liubov A. Dadinova ◽  
Yurii M. Chesnokov ◽  
Roman A. Kamyshinsky ◽  
Ivan A. Orlov ◽  
Maxim V. Petoukhov ◽  
...  

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