scholarly journals Molecular weight, tertiary structure, water binding and colon behaviour of ispaghula husk fibre

2003 ◽  
Vol 62 (1) ◽  
pp. 211-216 ◽  
Author(s):  
Saphwan Al-Assaf ◽  
Glyn O. Phillips ◽  
Peter A. Williams ◽  
Shoji Takigami ◽  
Peter Dettmar ◽  
...  
Keyword(s):  
Molecular Weight ◽  
Water Content ◽  
Tertiary Structure ◽  
Free Water ◽  
Gel Permeation Chromatography ◽  
State Matrix ◽  
Scanning Calorimetry ◽  
Water Binding ◽  
Mechanism Of Interaction ◽  
A Chain

Molecular variables, using aqueous and alkaline extracts, of the polysaccharide from ispaghula husk (IH) were examined using gel-permeation chromatography linked to multi-angle laser light scattering. Progressive extraction can yield a component with a molecular weight (MW) value up to about 7×106 Da, and gels, which accompany the extraction, have MW ranging from 10–20× 106 Da. To mimic the polysaccharide degradation, particularly in the colon, the solid IH was degraded progressively using ionising radiation. A chain break occurs every 7.5 kGy in NaOH and every 15 kGy in water. The solid-state matrix is opened by the radiation to yield increased visco-elasticity of the aqueous extracts at critical radiation doses, before further degradation occurs after about 12 kGy. Differential scanning calorimetry is used to study the mechanism of interaction of water with IH. The first water to be taken up is non-freezing water and represents about twelve water molecules/disaccharide unit of the polysaccharide. As the water content is increased, the water becomes bound to the polysaccharide and freezes and melts at a temperature different from free water. This water is thermodynamically distinguishable from free water. It forms amorphous ice on cooling which crystallises exothermically and subsequently melts endothermically. Saturation occurs at a water content of 2–3 g water/g polymer, showing that about 60% of the water in the system is ‘bound’. The most surprising conclusion is that despite the fact that the IH swells in water to form a solid and stiff gel, the greater part of that water in the gel is still free and behaves like liquid water.

scholarly journals Temperature- and pH-sensitive hydrogels of sequential Ti-containing interpenetrating polymer networks

2021 ◽  
pp. 42-49
Author(s):  
Т.Т. Аlekseeva ◽  
◽  
N.V. Iarova ◽  
Keyword(s):  
Molecular Weight ◽  
Water Content ◽  
Average Molecular Weight ◽  
Polymer Networks ◽  
Bound Water ◽  
Free Water ◽  
Interpenetrating Polymer Networks ◽  
Hydroxyethyl Methacrylate ◽  
Scanning Calorimetry ◽  
Polymer Component

Hydrogels of sequential Ti-containing interpenetrating polymer networks based on hydrophilic cross-linked polyurethanes with different molecular weight of polyethylene glycols and Ti-containing copolymer were synthesized based on 2-hydroxyethyl methacrylate and titanium isopropoxide. The composition of sequential interpenetrating polymer networks was determined by the degree of equilibrium swelling of the polyurethane networks in 2-hydroxyethyl methacrylate and Ti-containing comonomer. It was established that the content of the second component of the interpenetrating polymer networks increases with increasing the average molecular weight value of the polyurethane network. It was shown that the obtained highly sensitive hydrogels of Ti-containing interpenetrating polymer networks react to the changes in the temperature and pH. These factors significantly change the equilibrium water content in the hydrogels. Differential scanning calorimetry allowed determining the phase transitions that are characteristic of bound and free water, which is a part of the hydrogel of polyurethanes, interpenetrating polymer networks and Ti-containing interpenetrating polymer networks. The results showed that the content of bound water and the degree of its binding to the components of the interpenetrating polymer networks depend on the chemical structure of the network, the nature of a second polymer component (which is a part of the interpenetrating polymer networks), the polarity and hydrophilicity of macromolecules, and the size of hydrogel cells. Regardless of the nature of the second polymer component, there is a general trend for all interpenetrating polymer networks: the total water content increases with increasing the average molecular weight of the polyurethane matrix networks.

Processing and characterization of poly(lactic acid) blended with polycarbonate and chain extender

2014 ◽  
Vol 34 (7) ◽  
pp. 665-672 ◽  
Author(s):  
Yottha Srithep ◽  
Wuttipong Rungseesantivanon ◽  
Bongkot Hararak ◽  
Krisda Suchiva
Keyword(s):  
Molecular Weight ◽  
Lactic Acid ◽  
Gel Permeation Chromatography ◽  
Chain Extender ◽  
Chain Extension ◽  
Morphological Properties ◽  
Poly Lactic Acid ◽  
Scanning Calorimetry ◽  
Commercial Applications ◽  
A Chain

Abstract Currently, use of poly(lactic acid) (PLA) is limited for commercial applications because it has a low heat resistance. In this research, an increase of over 40°C heat distortion temperature (HDT) of PLA alloy was obtained by blending PLA with polycarbonate (PC) and a chain extender (CE). Molecular weight, thermal, mechanical and morphological properties of PLA and PC blend with different CE contents were investigated. Gel permeation chromatography (GPC) results showed that some PLA-PC copolymers were produced and the compatibility of the PLA phase and in the PC phase was improved via the chain extension reaction. In addition, the reaction induced by CE also affected the crystallization behaviors of PLA, as observed from differential scanning calorimetry (DSC) results and the enthalpy of melting of PLA decreased with increasing CE content. The combined effects of the CE increasing molecular weight, improving compatibility and limiting the crystallization behavior of PLA/PC alloy greatly improved the HDT.

scholarly journals Poly(lactic acid) polymer stars built from early generation dendritic polyols

2013 ◽  
Vol 91 (6) ◽  
pp. 392-397 ◽  
Author(s):  
Genny E. Keefe ◽  
Jean-d'Amour K. Twibanire ◽  
T. Bruce Grindley ◽  
Michael P. Shaver
Keyword(s):  
Molecular Weight ◽  
Ring Opening ◽  
Gel Permeation Chromatography ◽  
Poly Lactic Acid ◽  
Reactive Site ◽  
Scanning Calorimetry ◽  
Early Generation ◽  
Sequential Reaction ◽  
Cyclic Esters ◽  
Total Molecular Weight

A family of polymer stars has been prepared from early generation dendritic cores with four, six, and eight arms. Four dendritic cores were prepared from the sequential reaction of a multifunctional alcohol with a protected anhydride, followed by deprotection to afford two or three new alcohol functionalities per reactive site. These cores were used as initiators for the tin-catalyzed ring-opening polymerization of l-lactide and rac-lactide to afford isotactic and atactic degradable stars, respectively. Two series of stars were prepared for each monomer, either maintaining total molecular weight or number of monomer units per arm. The polymers were characterized by NMR spectroscopy, light-scattering gel-permeation chromatography, differential scanning calorimetry, and thermogravimetric analysis. Our results support previous work that suggests that the length of the arms dictates thermal properties rather than the total molecular weight of the star. Little effect was noted between aromatic and aliphatic cores, presumably due to the flexibility of the rest of the core molecule. We have shown that early generation dendrimers can serve as excellent core structures for building core-first polymer stars via the ring-opening of cyclic esters.

scholarly journals Methylene-Bridged Tridentate Salicylaldiminato Binuclear Titanium Complexes as Copolymerization Catalysts for the Preparation of LLDPE through [Fe]/[Ti] Tandem Catalysis

Polymers ◽  
2019 ◽  
Vol 11 (7) ◽  
pp. 1114 ◽  
Author(s):  
Yani Luo ◽  
Jian Li ◽  
Derong Luo ◽  
Qingliang You ◽  
Zifeng Yang ◽  
...  
Keyword(s):  
Molecular Weight ◽  
High Temperature ◽  
Gel Permeation Chromatography ◽  
13C Nmr Spectroscopy ◽  
Molar Ratio ◽  
Tandem Catalysis ◽  
Titanium Complexes ◽  
Scanning Calorimetry ◽  
Molecular Weights ◽  
Branching Degree

A novel tandem catalysis system consisted of salicylaldiminato binuclear/mononuclear titanium and 2,6-bis(imino)pyridyl iron complexes was developed to catalyze ethylene in-situ copolymerization. Linear low-density polyethylene (LLDPE) with varying molecular weight and branching degree was successfully prepared with ethylene as the sole monomer feed. The polymerization conditions, including the reaction temperature, the Fi/Ti molar ratio, and the structures of bi- or mononuclear Ti complexes were found to greatly influence the catalytic performances and the properties of obtained polymers. The polymers were characterized by differential scanning calorimetry (DSC), high temperature gel permeation chromatography (GPC) and high temperature 13C NMR spectroscopy, and found to contain ethyl, butyl, as well as some longer branches. The binuclear titanium complexes demonstrated excellent catalytic activity (up to 8.95 × 106 g/molTi·h·atm) and showed a strong positive comonomer effect when combined with the bisiminopyridyl Fe complex. The branching degree can be tuned from 2.53 to 22.89/1000C by changing the reaction conditions or using different copolymerization pre-catalysts. The melting points, crystallinity and molecular weights of the products can also be modified accordingly. The binuclear complex Ti2L1 with methylthio sidearm showed higher capability for comonomer incorporation and produced polymers with higher branching degree and much higher molecular weight compared with the mononuclear analogue.

scholarly journals Analysis of the Degradation During Melt Processing of PLA/Biosilicate® Composites

2019 ◽  
Vol 3 (2) ◽  
pp. 52 ◽  
Author(s):  
Eduardo H. Backes ◽  
Laís de N. Pires ◽  
Lidiane C. Costa ◽  
Fabio R. Passador ◽  
Luiz A. Pessan
Keyword(s):  
Molecular Weight ◽  
Gel Permeation Chromatography ◽  
Melt Processing ◽  
Poly Lactic Acid ◽  
Processing Route ◽  
Mechanical Resistance ◽  
Scanning Calorimetry ◽  
Oxidative Reactions ◽  
Bioactive Composites ◽  
Internal Mixer

Poly (lactic acid) (PLA)/bioactive composites are emerging as new biomaterials since it is possible to combine stiffness, mechanical resistance, and bioactive character of the bioglasses with conformability and bioabsorption of the PLA. In this study, PLA/Biosilicate® composites were prepared using a melt-processing route. The processability and properties were evaluated aiming to produce composites with bioactive properties. Two different PLA (PLA 2003D and PLA 4043D) were tested with the addition of 1 wt. % of Biosilicate®. Both materials presented a huge reduction in melt viscosity after internal mixer processing. The degradation effects of the addition of Biosilicate® in the PLAs matrices were evaluated using zeta potential tests that showed a very high liberation of ions, which catalyzes PLA thermo-oxidative reactions. To understand the extension of degradation effects during the processing, the composites were characterized using thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), gel permeation chromatography (GPC), and rheological tests. GPC results showed that PLA with the lowest residual acid content (RAC), PLA 2003D, presented higher thermal stability, higher molecular weight, and viscosity baseline compared to PLA 4043D. The composites showed a significant decrease in molecular weight for both PLA with the addition of Biosilicate®. TGA results showed that Biosilicate® might have reduced the activation energy to initiate thermodegradation reactions in PLAs and it occasioned a reduction in the Tonset by almost 40 °C. The DSC results showed that severe matrix degradation and the presence of bioglass did not significantly affect glass transition temperature (Tg), melting temperature (Tm) and crystallinity of PLAs, but it influenced cold crystallization peak (Tcc). In this way, the type of PLA used influences the processability of this material, which can make the production of filaments of this material for 3D printing unfeasible.

scholarly journals A Greener Enzymatic Oligoesterification of Biobased Renewable Synthons

2021 ◽  
Author(s):  
Juan Villavicencio ◽  
Ferley Orozco ◽  
Ricardo Benitez ◽  
Jaime Martin ◽  
Giovanni Rojas
Keyword(s):  
Molecular Weight ◽  
Molar Mass ◽  
Gel Permeation Chromatography ◽  
Scanning Calorimetry ◽  
Reaction Conditions ◽  
Step Process ◽  
Gel Permeation ◽  
One Step ◽  
First Time ◽  
Temperature Time

Polyesters of xylitol and succinic acid were prepared yielding from 70 to 75% by enzymecatalyzed esterification using a molar mass from 1:1 to 2:5 at 120 and 140 °C employing from 1 to 10% m/m of enzyme. Control over branching degree was achieved by tuning the reaction conditions (temperature, time, comonomer ratio, enzyme content). This one-step process from renewable starting materials avoids protection-deprotection techniques, as well as the use of toxic solvents by introducing limonene as solvent for polyesterification for the first time. All materials were structurally characterized by infrared (IR) and nuclear magnetic resonance (NMR)spectroscopy, their thermal properties were studied by differential scanning calorimetry (DSC)and thermogravimetric analysis (TGA), and the molecular weight of samples were obtained by gel-permeation chromatography (GPC).

Binary molybdenum-based catalyst for coordination polymerization of styrene

2016 ◽  
Vol 49 (5) ◽  
pp. 408-421 ◽  
Author(s):  
Jieting Geng ◽  
Youguo Shao ◽  
Feng Song ◽  
Feng Li ◽  
Jing Hua
Keyword(s):  
Molecular Weight ◽  
Catalyst Activity ◽  
Average Molecular Weight ◽  
Gel Permeation Chromatography ◽  
Catalyst System ◽  
Bulk Polymerization ◽  
Molar Ratio ◽  
Scanning Calorimetry ◽  
Coordination Polymerization ◽  
Co Catalyst

Coordination polymerization of styrene (St) using molybdenum pentachloride supported by phosphite ligand in the presence of metal organic compound was studied for the first time. The types of phosphite and co-catalysts significantly affected the catalytic activity of the molybdenum (V) (Mo(V)) active center and the number-average molecular weight ( Mn) of the resultant polymer. Among the examined catalysts, tri(nonylphenyl)phosphite (TNPP) ligand and AlOPhCH3( i-Bu)2 as co-catalyst provided the polymer with highest yield (up to 87.1%), metallocene as co-catalyst provided the polymer with highest Mn (up to 5.32 × 105). The effect of [P]/[Mo] molar ratio on catalyst activity of the polymerization was discussed and the structures of Mo·TNPP complexes were preliminarily studied by infrared (IR) and ultraviolet spectroscopies. Besides, the polystyrene (PS) samples synthesized through bulk polymerization and solution polymerization were characterized by gel permeation chromatography, IR, carbon 13 nuclear magnetic resonance, and differential scanning calorimetry, respectively, and the results indicated both of the PS had high molecular weight (approximately 105) and atactic structure. All these results demonstrated that Mo(V) catalyst system was very effective for St polymerization.

On the structure alteration of crosslinkable gelatin coupled with methacrylic acid and its hydrogel

e-Polymers ◽  
2012 ◽  
Vol 12 (1) ◽  
Author(s):  
Xiaohong Hu ◽  
Dan Li ◽  
Feng Zhou ◽  
Changyou Gao
Keyword(s):  
Molecular Weight ◽  
Triple Helix ◽  
Sol Gel ◽  
Average Molecular Weight ◽  
Gel Permeation Chromatography ◽  
Apparent Molecular Weight ◽  
Small Range ◽  
Scanning Calorimetry ◽  
Physical Chemical ◽  
Substitution Degree

AbstractPhysical structures of a crosslinkable gelatin derivative (GM) were studied in terms of alteration of apparent molecular weight, triple helix content and mechanical strength. The GM with a substitution degree (DS) of 49% and 79% was prepared by grafting mechacrylic acid (MA), which was able to form injectable hydrogel by photoinitiating polymerization. The zeta potential was increased along the increase of DS. After modification, the apparent number-average molecular weight (Mn) detected by gel permeation chromatography was decreased to about 2/3 of gelatin, while the apparent weight-average molecular weight (Mw) was changed within a small range. Differential scanning calorimetry and circular dichroism (CD) revealed that ability of triple-helix formation of GM was decreased along with the increase of DS and decrease of GM concentration. After photocrosslinking, the sol-gel transition of GM49 physical-chemical hydrogel still existed, but completely disappeared for its chemical hydrogel. The physical-chemical hydrogel showed a larger storage modulus at 20°C than at 37°C as a result of additional physical crosslinking.

First GPC results of terpyridine based chain extended supramolecular polymers: comparison with viscosity and analytical ultracentrifugation

e-Polymers ◽  
2006 ◽  
Vol 6 (1) ◽  
Author(s):  
Michael A. R. Meier ◽  
Harald Hofmeier ◽  
Caroline H. Abeln ◽  
Christos Tziatzios ◽  
Mircea Rasa ◽  
...  
Keyword(s):  
Molecular Weight ◽  
Analytical Ultracentrifugation ◽  
Average Molecular Weight ◽  
Gel Permeation Chromatography ◽  
Supramolecular Polymers ◽  
Supramolecular Polymer ◽  
Poly Ethylene ◽  
A Chain ◽  
First Time ◽  
Good Agreement

AbstractThe molecular weight of an extended metallo-supramolecular polymer, based on a α,ω-bis-terpyridine-poly(ethylene glycol) polymer linked via ruthenium(II) ions, was determined by gel permeation chromatography, viscosimetry as well as analytical ultracentrifugation. An optimized GPC method was applied for the first time to this kind of chain extended supramolecular polymers and the obtained results showed a good agreement with viscosimetry and analytical ultracentrifugation. A chain extended polymer with an average molecular weight of around 140 000 was found. These results clearly demonstrate that well-soluble high-molecular-weight metal-containing coordination polymers that are based on well-defined telechelics can be synthesized and fully characterized.

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