Oxidation Level and Glycidyl Ether Structure Determine Thermal Processability and Thermomechanical Properties of Arabinoxylan-Derived Thermoplastics

Herein we present arabinoxylan (AX)-based thermoplastics obtained by ring opening oxidation and subsequent reduction (dA-AX) combined with hydrophobization with three different glycidyl ethers [n-butyl (BuGE), isopropyl (iPrGE) and 2-ethylhexyl (EtHGE) glycidyl ether]. We also present the relationship of structural composition, thermal processing and thermomechanical properties. The BuGE and iPrGE etherified dA-AXs showed glass transition temperatures (Tg) far below their degradation temperatures and gave thermoplastic materials when compression-molded at 140˚C. The BuGE (3 mole) etherified dA-AX films at 19 and 31 % oxidation levels exclusively exhibit 244 % (±42) and 267 % (±72) elongation. In contrast, iPrGE-dA-AX samples with shorter and branched terminals in the side chains had maximum 60 % (±19) elongation. The dramatic difference in elongation is assumed to be due to the presence of longer alkoxide chains, higher molar substitution and dual Tg for the BuGE samples. Such superior elongation of AX thermoplastic films and its relationship with molar substitution and Tg has not been reported before.

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Ring-opening polymerization of monosubstituted oxiranes in the presence of potassium hydride: determination of initiation course and structure of macromolecules by MALDI-TOF mass spectrometry

Journal of Polymer Research ◽

10.1007/s10965-019-1943-x ◽

2019 ◽

Vol 26 (12) ◽

Cited By ~ 2

Author(s):

Zbigniew Grobelny ◽

Justyna Jurek-Suliga ◽

Sylwia Golba

Keyword(s):

Mass Spectrometry ◽

Ring Opening ◽

Glycidyl Ether ◽

Ring Opening Polymerization ◽

Size Exclusion ◽

Oxirane Ring ◽

Maldi Tof ◽

Glycidyl Ethers ◽

Initiation Step ◽

Potassium Hydride

AbstractSeveral monosubstituted oxiranes were polymerized with suspension of potassium hydride (KH) in tetrahydrofuran (THF) at room temperature. This heterogeneous process resulted in polyethers with various starting groups depending on the kind of monomer. The macromolecules formed in ring-opening polymerization of monosubstituted oxiranes were analyzed by Matrix Assisted Laser Desorption/Ionization - Time of Flight Mass Spectrometry (MALDI-TOF MS). It was stated, that initiation of propylene oxide (PO) polymerization with KH proceeded via three ways, i.e. cleavage of oxirane ring in the β-position, monomer deprotonation and deoxygenation. Potassium isopropoxide, potassium allyloxide and potassium hydroxide were the real initiators. The main reactions, which occur in the initiation step, depend on the type of monomer used. In the case of allyl glycidyl ether (AGE) and phenyl glycidyl ether (PGE) deprotonation of the monomer did not occur. During initiation of glycidyl ethers oxirane ring was opened and also linear ether bond between glycidyl group and oxygen atom was cleaved under influence of KH. Interestingly, formation of new kinds of macromolecules was observed in the systems containing glycidyl ethers, which do not possess mers of the monomers used. Mechanisms of the studied processes were presented and discussed. Carbon-13 Nuclear Magnetic Resonance (13C NMR) was used as supporting technique for analysis of the obtained polymers. Number average molar masses of the polymers (Mn) determined by Size Exclusion Chromatography (SEC) were about two times higher than calculated ones. It indicated that half of used KH did not take part in the initiation step.

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The relationship of red meat with cancer: Effects of thermal processing and related physiological mechanisms

Critical Reviews in Food Science and Nutrition ◽

10.1080/10408398.2014.967833 ◽

2015 ◽

Vol 57 (6) ◽

pp. 1153-1173 ◽

Cited By ~ 18

Author(s):

Vic Shao-Chih Chiang ◽

Siew-Young Quek

Keyword(s):

Thermal Processing ◽

Red Meat ◽

Physiological Mechanisms ◽

Relationship Of ◽

The Relationship

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Photo- and thermoinduced ring opening reaction of 2[(1,3,3-trimethylindoline-2(1H)-yliden)propen-1-yl]-3,3-dimethylindolino[1,2-b]-oxazolidine in polymer films

Open Chemistry ◽

10.2478/bf02475574 ◽

2004 ◽

Vol 2 (2) ◽

pp. 290-301

Author(s):

I. Petkov ◽

F. Charra ◽

J Nunzi ◽

T. Deligeorgiev

Keyword(s):

Polymer Films ◽

Ring Opening ◽

Uv Light ◽

Absorption Peak ◽

Ring Opening Reaction ◽

Radiation Induced ◽

Relationship Of ◽

The Relationship

AbstractThe influence of UV light and temperature on poly(methylmethacrylate) (PMMA) and poly(vinylchloride) (PVC) films, doped with 2[(1,3,3-trimethylindoline-2(1H)-yliden)propen-1-yl]-3,3-dimethylindolino[1,2-b]-oxazolidine has been investigated. The radiation-induced colour was analyzed spectrophotometrically at the maximum of the absorption peak at 560 nm. The effect of the temperature on unirradiated and irradiated films was studied. The results demonstrate a strong photochromic and a weak thermochromic behaviour of the PMMA and PVC films. The relationship of photocolouration-thermal decolouration is discussed based on the spectral results reported here.

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The relationship of the scleractinian corals to the rugose corals

Paleobiology ◽

10.1017/s0094837300025707 ◽

1980 ◽

Vol 6 (02) ◽

pp. 146-160 ◽

Cited By ~ 29

Author(s):

William A. Oliver

Keyword(s):

Critical Points ◽

Scleractinian Corals ◽

Convincing Evidence ◽

Early Triassic ◽

Rugose Corals ◽

History Of ◽

The Subject ◽

Relationship Of ◽

The Relationship ◽

Biologic Factors

The Mesozoic-Cenozoic coral Order Scleractinia has been suggested to have originated or evolved (1) by direct descent from the Paleozoic Order Rugosa or (2) by the development of a skeleton in members of one of the anemone groups that probably have existed throughout Phanerozoic time. In spite of much work on the subject, advocates of the direct descent hypothesis have failed to find convincing evidence of this relationship. Critical points are:(1) Rugosan septal insertion is serial; Scleractinian insertion is cyclic; no intermediate stages have been demonstrated. Apparent intermediates are Scleractinia having bilateral cyclic insertion or teratological Rugosa.(2) There is convincing evidence that the skeletons of many Rugosa were calcitic and none are known to be or to have been aragonitic. In contrast, the skeletons of all living Scleractinia are aragonitic and there is evidence that fossil Scleractinia were aragonitic also. The mineralogic difference is almost certainly due to intrinsic biologic factors.(3) No early Triassic corals of either group are known. This fact is not compelling (by itself) but is important in connection with points 1 and 2, because, given direct descent, both changes took place during this only stage in the history of the two groups in which there are no known corals.

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Skeletal elements of crinoid echinoderms: High-resolution structural and microanalytical results

Proceedings, annual meeting, Electron Microscopy Society of America ◽

10.1017/s0424820100074768 ◽

1983 ◽

Vol 41 ◽

pp. 194-195

Author(s):

D. F. Blake ◽

L. F. Allard ◽

D. R. Peacor

Keyword(s):

High Resolution ◽

Marine Invertebrates ◽

Sea Urchins ◽

Structural Features ◽

Sea Stars ◽

High Resolution Tem ◽

Relationship Of ◽

The Relationship ◽

Insight Into

Echinodermata is a phylum of marine invertebrates which has been extant since Cambrian time (c.a. 500 m.y. before the present). Modern examples of echinoderms include sea urchins, sea stars, and sea lilies (crinoids). The endoskeletons of echinoderms are composed of plates or ossicles (Fig. 1) which are with few exceptions, porous, single crystals of high-magnesian calcite. Despite their single crystal nature, fracture surfaces do not exhibit the near-perfect {10.4} cleavage characteristic of inorganic calcite. This paradoxical mix of biogenic and inorganic features has prompted much recent work on echinoderm skeletal crystallography. Furthermore, fossil echinoderm hard parts comprise a volumetrically significant portion of some marine limestones sequences. The ultrastructural and microchemical characterization of modern skeletal material should lend insight into: 1). The nature of the biogenic processes involved, for example, the relationship of Mg heterogeneity to morphological and structural features in modern echinoderm material, and 2). The nature of the diagenetic changes undergone by their ancient, fossilized counterparts. In this study, high resolution TEM (HRTEM), high voltage TEM (HVTEM), and STEM microanalysis are used to characterize tha ultrastructural and microchemical composition of skeletal elements of the modern crinoid Neocrinus blakei.

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Studies on Leukemogenic and Sarcomagenic Viruses

Proceedings, annual meeting, Electron Microscopy Society of America ◽

10.1017/s0424820100067777 ◽

1970 ◽

Vol 28 ◽

pp. 156-157

Author(s):

Leon Dmochowski

Keyword(s):

Electron Microscopy ◽

Electron Microscope ◽

Morphological Properties ◽

Mode Of Development ◽

Relationship Of ◽

The Relationship

Electron microscopy has proved to be an invaluable discipline in studies on the relationship of viruses to the origin of leukemia, sarcoma, and other types of tumors in animals and man. The successful cell-free transmission of leukemia and sarcoma in mice, rats, hamsters, and cats, interpreted as due to a virus or viruses, was proved to be due to a virus on the basis of electron microscope studies. These studies demonstrated that all the types of neoplasia in animals of the species examined are produced by a virus of certain characteristic morphological properties similar, if not identical, in the mode of development in all types of neoplasia in animals, as shown in Fig. 1.

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The relationship of IGE receptor topography to signaling activity in RBL-2H3 mast cells

Proceedings, annual meeting, Electron Microscopy Society of America ◽

10.1017/s0424820100085484 ◽

1991 ◽

Vol 49 ◽

pp. 236-237

Author(s):

J.R. Pfeiffer ◽

J.C. Seagrave ◽

C. Wofsy ◽

J.M. Oliver

Keyword(s):

Mast Cells ◽

Protein A ◽

Scattered Electron ◽

Ige Receptor ◽

Receptor Complexes ◽

Ige Binding ◽

Electron Imaging ◽

Small Clusters ◽

Relationship Of ◽

The Relationship

In RBL-2H3 rat leukemic mast cells, crosslinking IgE-receptor complexes with anti-IgE antibody leads to degranulation. Receptor crosslinking also stimulates the redistribution of receptors on the cell surface, a process that can be observed by labeling the anti-IgE with 15 nm protein A-gold particles as described in Stump et al. (1989), followed by back-scattered electron imaging (BEI) in the scanning electron microscope. We report that anti-IgE binding stimulates the redistribution of IgE-receptor complexes at 37“C from a dispersed topography (singlets and doublets; S/D) to distributions dominated sequentially by short chains, small clusters and large aggregates of crosslinked receptors. These patterns can be observed (Figure 1), quantified (Figure 2) and analyzed statistically. Cells incubated with 1 μg/ml anti-IgE, a concentration that stimulates maximum net secretion, redistribute receptors as far as chains and small clusters during a 15 min incubation period. At 3 and 10 μg/ml anti-IgE, net secretion is reduced and the majority of receptors redistribute rapidly into clusters and large aggregates.

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