Dissociation of Phenolic Groups in Kraft Lignin at Elevated Temperatures

Holzforschung ◽  
2000 ◽  
Vol 54 (5) ◽  
pp. 519-527 ◽  
Author(s):  
Magnus Norgren ◽  
Birger Lindström
Keyword(s):  
Molecular Weight ◽  
Elevated Temperatures ◽  
Kraft Lignin ◽  
Degree Of Dissociation ◽  
Molecular Weights ◽  
Kraft Process ◽  
Poisson Boltzmann ◽  
Dissociation Curves ◽  
Complete Dissociation ◽  
Good Agreement

Summary The dissociation of the phenolic groups in a polydisperse, low molecular weight kraft lignin (Indulin AT) was studied in alkaline aqueous solutions in the temperature interval 21–70 °C, using a UV-spectrophotometric method. It was found that at a constant concentration of hydroxide ions, the degree of dissociation was decreasing when the temperature was elevated. Dissociation curves and apparent pΚ 0 values were also calculated for the polydisperse sample at the same conditions, using the van't Hoff and the Poisson-Boltzmann equations. At degrees of dissociation exceeding α ≈ 0.4, the outcome of the theoretical approach showed to be in good agreement with the experimentally obtained results. Furthermore, calculations were performed for different molecular weights of kraft lignin and from this it was found that the apparent pΚ 0 is shifted to higher values by increasing molecular weight, due to an increased electrostatic attraction of the hydrogen ions, which is arising from a less curved surface. Predictions of the dissociation behavior at temperatures reached in the kraft process were performed and under these conditions, higher molecular weight lignin fragments seem never to reach the point of complete dissociation. It was also found that an increase in temperature results in phase separation in kraft lignin solutions with high ionic strengths and pH values close to the pΚ a of the phenolic groups.

Evaluation of polydispersity index Mw/Mn by quasielastic light scattering

1987 ◽  
Vol 52 (5) ◽  
pp. 1235-1245 ◽  
Author(s):  
Petr Štěpánek ◽  
Zdeněk Tuzar ◽  
Čestmír Koňák
Keyword(s):  
Molecular Weight ◽  
Light Scattering ◽  
Decay Time ◽  
Sampling Time ◽  
Polydispersity Index ◽  
New Method ◽  
Molecular Weights ◽  
Quasielastic Light Scattering ◽  
Good Agreement

The response of quasielastic light scattering to the polydispersity of scattering objects has been investigated. A new method of the polydispersity index determination has been suggested, suitable for the range 1.02 ⪬ Mw/Mn ⪬ 2.0 and consisting in the measurement of the dependence of the apparent decay time on the correlator sampling time. The polydispersity index can be determined by comparing these dependences with the theoretical ones obtained using correlation curves simulated for various values of the polydispersity index, assuming lognormal and Schulz-Zimm distributions of molecular weights. The test measurements on polystyrene standards having molecular weights in the range 9 103 – 20.6 106 give polydispersity index values Mw/Mn that are in a good agreement with those given by the manufacturer. The polydispersity index for polystyrene having the molecular weight Mw = 20.6 106 thus determined was Mw/Mn = 1.35.

Measurement of the Isothermal Volume Dilation Accompanying the Unilateral Extension of Rubber

1959 ◽  
Vol 32 (2) ◽  
pp. 428-433
Author(s):  
Fred G. Hewitt ◽  
Robert L. Anthony
Keyword(s):  
Molecular Weight ◽  
Young’S Modulus ◽  
Experimental Results ◽  
Molecular Weights ◽  
Rubber Specimen ◽  
A Value ◽  
Fractional Increase ◽  
Internal Agreement ◽  
Good Agreement

Abstract The fractional increase in volume accompanying the isothermal extension of soft gum rubber was measured for four rubber samples at mean extensions of 14, 33, and 51%. The chain molecular weights Mc of the four samples were 5500, 5100, 4400, and 3000, with an estimated uncertainty of about 10% in each value of Mc. The observed fractional increase in volume ranged from 3.2×10−5 to 142×10−5, the latter value being observed for the sample of lowest chain molecular weight and at the extension of 51%. The experimental results for each sample have been represented by theoretical curves based on Gee's expression for the fractional increase in volume as a function of the sample extension. The theoretical curves exhibit good agreement with those of Gee, Stern, and Treloar. The process of fitting the theoretical curves to the experimental points constituted a determination of Young's modulus E for each rubber specimen. As a check on the experimental results, and also on the theory employed, determinations of E were also made by two additional methods, namely, from rough stess-strain curves, and from the relation E=3γρRT/Mc. With one exception, the internal agreement between the three determinations of E for the four different samples was satisfactory. The exception noted can probably be ascribed to the use of too small a value of Mc for the sample of lowest chain molecular weight.

The Structure of Neoprene. I. The Molecular-Weight Distribution of Neoprene Type GN

1949 ◽  
Vol 22 (3) ◽  
pp. 680-689
Author(s):  
W. E. Mochel ◽  
J. B. Nichols ◽  
C. J. Mighton
Keyword(s):  
Molecular Weight ◽  
Natural Rubber ◽  
Osmotic Pressure ◽  
Molecular Weight Distribution ◽  
Weight Distribution ◽  
Distribution Curve ◽  
Pressure Measurements ◽  
Dilute Solution ◽  
Molecular Weights ◽  
Good Agreement

Abstract Polychloroprene rubber (Neoprene Type GN) was fractionated by partial precipitation from dilute solution in benzene and the fractions were examined both osmotically and viscometrically in benzene solutions. The molecular-weight distribution curve for Neoprene Type GN based on osmotic pressure measurements shows a pronounced maximum at 100,000, but has a long extension to molecular weights of over one million, indicating the presence of branched or cross-linked material which is still soluble. The uniformity is somewhat less than that of sol natural rubber, while in shape the Neoprene distribution curve resembles more closely that of peptized natural rubber than fresh sol rubber. Observed variations in the slopes of the π/c vs. c and the ηsp/c vs. c curves also indicate the presence in solution of complex, branched and (or) cross-linked molecules. Calibration of the intrinsic viscosity-molecular weight relationship by osmotic pressure measurements gave good agreement with the equation: [η]=KMa, where K=1.46×10−4 and a=0.73.

MOLECULAR WEIGHT AND HYDRODYNAMIC PROPERTIES OF SODIUM ALGINATE

1954 ◽  
Vol 32 (3) ◽  
pp. 227-239 ◽  
Author(s):  
W. H. Cook ◽  
David B. Smith
Keyword(s):  
Molecular Weight ◽  
Sodium Alginate ◽  
Intrinsic Viscosity ◽  
Diffusion Coefficients ◽  
Linear Relation ◽  
Hydrodynamic Properties ◽  
Viscosity Measurements ◽  
Molecular Weights ◽  
Extension Ratio ◽  
Good Agreement

Sedimentation, diffusion, and viscosity measurements were made on five unfractionated samples of sodium alginate ranging in intrinsic viscosity from 3.1 to 17.5. Diffusion coefficients were subject to large errors and are believed to be overestimated.Though the molecular weights obtained from sedimentation–diffusion (Svedberg equation) and sedimentation – intrinsic viscosity (Perrin–Simha equations) showed good agreement and yielded values of 3 to 21 × 104, higher values (4.6 to 37 × 104) from sedimentation–viscosity (Mandelkern–Flory equation) appear to be the better estimates. A linear relation between intrinsic viscosity and molecular weight was found with a slope (Mandelkern–Flory equation values) equivalent to Km = 13.9 × 10−3. The results indicate that sodium alginate has a relatively high extension ratio.

MOLECULAR WEIGHT AND HYDRODYNAMIC PROPERTIES OF SODIUM ALGINATE

1954 ◽  
Vol 32 (1) ◽  
pp. 227-239 ◽  
Author(s):  
W. H. Cook ◽  
David B. Smith
Keyword(s):  
Molecular Weight ◽  
Sodium Alginate ◽  
Intrinsic Viscosity ◽  
Diffusion Coefficients ◽  
Linear Relation ◽  
Hydrodynamic Properties ◽  
Viscosity Measurements ◽  
Molecular Weights ◽  
Extension Ratio ◽  
Good Agreement

Sedimentation, diffusion, and viscosity measurements were made on five unfractionated samples of sodium alginate ranging in intrinsic viscosity from 3.1 to 17.5. Diffusion coefficients were subject to large errors and are believed to be overestimated.Though the molecular weights obtained from sedimentation–diffusion (Svedberg equation) and sedimentation – intrinsic viscosity (Perrin–Simha equations) showed good agreement and yielded values of 3 to 21 × 104, higher values (4.6 to 37 × 104) from sedimentation–viscosity (Mandelkern–Flory equation) appear to be the better estimates. A linear relation between intrinsic viscosity and molecular weight was found with a slope (Mandelkern–Flory equation values) equivalent to Km = 13.9 × 10−3. The results indicate that sodium alginate has a relatively high extension ratio.

Application possibilities of preparative size exclusion chromatography to analytical problems in polymer science

e-Polymers ◽  
2007 ◽  
Vol 7 (1) ◽  
Author(s):  
Hanneke M. L. Thijs ◽  
Michael A. R. Meier ◽  
Ulrich S. Schubert
Keyword(s):  
Molecular Weight ◽  
Size Exclusion Chromatography ◽  
Size Exclusion ◽  
Molecular Weight Determination ◽  
Polymer Science ◽  
Polymer Architecture ◽  
Molecular Weights ◽  
Star Shaped Polymer ◽  
Exclusion Chromatography ◽  
Good Agreement

AbstractThe application possibilities of preparative size exclusion chromatography for the detailed analysis of polymer analytes are discussed. Using the example of star-shaped polymer architecture, the possibilities of utilizing fractions obtained from preparative size exclusion chromatography and their subsequent off-line characterization with a variety of hyphenated analytic techniques are discussed and compared to one another. It was, for instance, possible to obtain an absolute SEC calibration for the investigated star-shaped polymers that showed very good agreement with theoretical expected values and values obtained by absolute molecular weight determination techniques by analyzing fractions of different molecular weights of this polymer architecture by MALDI-TOFMS in order obtain the Mp values required for SEC calibrations. Moreover, the star-shaped polymers were investigated by SEC-viscometry in order to obtain their absolute molecular weight. All analytical results are compared to each other and possibilities as well as limitations are discussed.

THE MOLECULAR WEIGHT OF POLYETHYLENE AND OF OTHER HIGH-MOLECULAR-WEIGHT ORGANIC COMPOUNDS

1958 ◽  
Vol 36 (5) ◽  
pp. 725-730 ◽  
Author(s):  
R. Tremblay ◽  
A. F. Sirianni ◽  
I. E. Puddington
Keyword(s):  
Molecular Weight ◽  
Vapor Pressure ◽  
High Molecular Weight ◽  
Organic Compounds ◽  
Molecular Weight Range ◽  
Weight Range ◽  
Temperature Range ◽  
Molecular Weights ◽  
Pressure Lowering ◽  
Good Agreement

The temperature range of the measurement of vapor-pressure depression using a sensitive differential mercury micromanometer has been extended, and the behavior of a series of polyethylene samples having a molecular-weight range of 2500 to 24,000 was examined in toluene solutions at 75 °C. Good agreement was obtained between vapor-pressure lowering and other means of determining number-average molecular weights of several special compounds.

Investigation by HPLC of the Catabolism of Recombinant Tissue Plasminogen Activator in the Rat

1988 ◽  
Vol 60 (01) ◽  
pp. 107-112 ◽  
Author(s):  
Roy Harris ◽  
Louis Garcia Frade ◽  
Lesley J Creighton ◽  
Paul S Gascoine ◽  
Maher M Alexandroni ◽  
...  
Keyword(s):  
Molecular Weight ◽  
Plasminogen Activator ◽  
Tissue Plasminogen Activator ◽  
Half Life ◽  
Recombinant Tissue Plasminogen Activator ◽  
Rat Plasma ◽  
High Molecular Weight Complex ◽  
Molecular Weights ◽  
Major Activity ◽  
Tissue Plasminogen

SummaryThe catabolism of recombinant tissue plasminogen activator (rt-PA) was investigated after injection of radiolabelled material into rats. Both Iodogen and Chloramine T iodination procedures yielded similar biological activity loss in the resultant labelled rt-PA and had half lives in the rat circulation of 1 and 3 min respectively. Complex formation of rt-PA was investigated by HPLC gel exclusion (TSK G3000 SW) fractionation of rat plasma samples taken 1-2 min after 125I-rt-PA injection. A series of radiolabelled complexes of varying molecular weights were found. However, 60% of the counts were associated with a single large molecular weight complex (350–500 kDa) which was undetectable by immunologically based assays (ELISA and BIA) and showed only low activity with a functional promoter-type t-PA assay. Two major activity peaks in the HPLC fractions were associated with Tree t-PA and a complex having a molecular weight of ̴ 180 kDa. HPLC fractionation to produce these three peaks at various timed intervals after injection of 125I-rt-PA showed each to have a similar initial rate half life in the rat circulation of 4-5 min. The function of these complexes as yet is unclear but since a high proportion of rt-PA is associated with a high molecular weight complex with a short half life in the rat, we suggest that the formation of this complex may be a mechanism by which t-PA activity is initially regulated and finally cleared from the rat circulation.

Permeability Enhancing and Chemotactic Activities of Lower Molecular Weight Degradation Products of Human Fibrinogen

1981 ◽  
Vol 45 (01) ◽  
pp. 090-094 ◽  
Author(s):  
Katsuo Sueishi ◽  
Shigeru Nanno ◽  
Kenzo Tanaka
Keyword(s):  
Molecular Weight ◽  
Degradation Products ◽  
Electron Microscopic Observation ◽  
Chemotactic Activity ◽  
Lower Molecular Weight ◽  
Electron Microscopic ◽  
Human Fibrinogen ◽  
Rabbit Skin ◽  
Molecular Weights ◽  
Active Fragments

SummaryFibrinogen degradation products were investigated for leukocyte chemotactic activity and for enhancement of vascular permeability. Both activities increased progressively with plasmin digestion of fibrinogen. Active fragments were partially purified from 24 hr-plasmin digests. Molecular weights of the permeability increasing and chemotactic activity fractions were 25,000-15,000 and 25,000 respectively. Both fractions had much higher activities than the fragment X, Y, D or E. Electron microscopic observation of the small blood vessels in rabbit skin correlated increased permeability with the formation of characteristic gaps between adjoining endothelial cells and their contraction.These findings suggest that lower molecular weight degradation products of fibrinogen may be influential in contributing to granulocytic infiltration and enhanced permeability in lesions characterized by deposits of fibrin and/or fibrinogen.

Toxicity of Heparinoids, with Special Reference to the Precipitation of Fibrinogen

1964 ◽  
Vol 12 (01) ◽  
pp. 232-261 ◽  
Author(s):  
S Sasaki ◽  
T Takemoto ◽  
S Oka
Keyword(s):  
Molecular Weight ◽  
Dextran Sulfate ◽  
Anticoagulant Activity ◽  
Molecular Structures ◽  
Severe Reaction ◽  
Clinical Use ◽  
Molecular Weights ◽  
Close Relationship

SummaryTo demonstrate whether the intravascular precipitation of fibrinogen is responsible for the toxicity of heparinoid, the relation between the toxicity of heparinoid in vivo and the precipitation of fibrinogen in vitro was investigated, using dextran sulfate of various molecular weights and various heparinoids.1. There are close relationships between the molecular weight of dextran sulfate, its toxicity, and the quantity of fibrinogen precipitated.2. The close relationship between the toxicity and the precipitation of fibrinogen found for dextran sulfate holds good for other heparinoids regardless of their molecular structures.3. Histological findings suggest strongly that the pathological changes produced with dextran sulfate are caused primarily by the intravascular precipitates with occlusion of the capillaries.From these facts, it is concluded that the precipitates of fibrinogen with heparinoid may be the cause or at least the major cause of the toxicity of heparinoid.4. The most suitable molecular weight of dextran sulfate for clinical use was found to be 5,300 ~ 6,700, from the maximum value of the product (LD50 · Anticoagulant activity). This product (LD50 · Anticoagulant activity) can be employed generally to assess the comparative merits of various heparinoids.5. Clinical use of the dextran sulfate prepared on this basis gave satisfactory results. No severe reaction was observed. However, two delayed reactions, alopecia and thrombocytopenia, were observed. These two reactions seem to come from the cause other than intravascular precipitation.

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