Isoprene and Rubber. Part 20. The Colloidal Nature of Rubber, Gutta-Percha, and Balata

1930 ◽  
Vol 3 (4) ◽  
pp. 586-595
Author(s):  
H. Staudinger
Keyword(s):  
Molecular Weight ◽  
Characteristic Viscosity ◽  
Specific Viscosity ◽  
Decomposition Products ◽  
Molecular Weights ◽  
Gutta Percha ◽  
Viscosity Increase ◽  
Preceding Work ◽  
Rubber Part

Abstract I. The Molecular Weight of Rubber, Gutta-Percha, and Balata In the preceding work the molecular weight of rubber and balata was calculated on the basis of relations between specific viscosity ηsp and molecular weight which are shown by semi-colloidal decomposition products, on the assumption that this relation is also true for eucolloids. The value ηr−1 was taken as the specific viscosity, i. e., the characteristic viscosity increase of a substance of definite concentration and known solvent. The expression “specific viscosity” has already been used by J. Duclaux. In viscosity investigations of nitrocellulose solutions he represents this by a constant K which is calculated from the relations of the change of viscosity at various concentrations derived by Arrhenius: Based on these constants, nitrocelluloses show different average molecular weights for the increase in viscosity, that is, this constant K is greater with high molecular products than with low. In the following, this constant represents not the specific viscosity, but the viscosity-concentration constant Kc; the earlier constant Km which, on the basis of the formula: expressed the relation between the specific viscosity and the molecular weight, is called the viscosity-molecular weight constant.

Isoprene and Rubber. Part 29. High Molecular Hydrorubbers

1932 ◽  
Vol 5 (2) ◽  
pp. 136-140
Author(s):  
H. Staudinger ◽  
W. Feisst
Keyword(s):  
Molecular Weight ◽  
Catalytic Reduction ◽  
Molecular Form ◽  
Average Molecular Weight ◽  
Molecular Size ◽  
Decomposition Products ◽  
Molecular Weights ◽  
Rubber Part ◽  
Derivatives Of ◽  
Suitable Process

Abstract The molecular concept in organic chemistry is based upon the fact that the molecules, whose existence is proved by vapor density determinations, enter into chemical reactions as the smallest particles. If now it is assumed that organic molecular colloids like rubber are dissolved in dilute solution in molecular form then it must be proved that in the chemical transposition of macromolecules as well no change in the size of the macromolecules occurs. In the case of hemicolloids, therefore for molecular colloids with an average molecular weight of 1000 to 10,000, this has been proved by the reduction of polyindenes, especially of polysterenes, to hydroproducts with the same average molecular weight, and also by the fact that cyclorubbers do not change their molecular weight upon autoöxidation. The molecular weights of hemi-colloidal hydrocarbons are therefore invariable. This is much more difficult to prove in the case of rubber, although there are many more ways in which unsaturated rubber can be transposed than the stable polysterenes, polyindenes, and poly cyclorubbers. In most of the reactions with rubber, as in its action with nitrosobenzene, oxidizing agents, hydrogen halides, and halogens, an extensive decomposition takes place as a result of the instability of the molecule, which is referred to in another work. Therefore derivatives of rubber are not formed, but derivatives of hemi-colloidal decomposition products. The catalytic reduction of rubber in the cold appears to be the most suitable process of making it react without changing its molecular size in order to prove that in a chemical transposition its molecular weight remains the same.

Isoprene and Rubber. Part 44. Viscosity Measurements of Squalene and Hydrosqualene Solutions

1936 ◽  
Vol 9 (4) ◽  
pp. 573-578
Author(s):  
H. Staudinger ◽  
H. P. Mojen
Keyword(s):  
Physical Properties ◽  
General Relation ◽  
Basic Structure ◽  
Degree Of Polymerization ◽  
Specific Viscosity ◽  
Viscosity Measurements ◽  
Molecular Weights ◽  
Gutta Percha ◽  
Rubber Part

Abstract The physical properties of highly polymerized substances, which are composed of fiber molecules, depend on the lengths of the chains of these fiber molecules. Thus tensile strength, elasticity, tendency to swell in solvents, and above all viscosity, are dependent on the length of chain of the particular substance. Among the substances, the properties of which vary thus, are rubber, gutta-percha, and balata. Since the length of fiber molecules can vary within wide limits, such physical properties as those mentioned above show wide variations in the case of rubber, gutta-percha, and balata. This is evident for example by a comparison of the properties of unmasticated rubber, which consists of long fiber molecules of a degree of polymerization of 2000, with the properties of masticated rubber, the greatly dissociated molecules of which have a degree of polymerization of only 500. The determination of the length of the fiber molecules is therefore of great importance in the case of highly polymerized substances. It has already been proved in past experiments with members of a series of homologous polymers, i. e., of substances the macromolecules of which have the same basic structure and differ only in length, that the molecular weights can be determined from viscosity measurements. This determination is based on the fact that there is a general relation between the specific viscosity and the length of the dissolved molecules, which can be expressed by the formula:

Isoprene and Rubber. XIX. The Molecular Size of Rubber and Balata

1930 ◽  
Vol 3 (3) ◽  
pp. 519-521 ◽  
Author(s):  
H. Staudinger ◽  
H. F. Bondy
Keyword(s):  
Molecular Weight ◽  
Organic Solvent ◽  
Average Molecular Weight ◽  
Molecular Size ◽  
Dilute Solution ◽  
Decomposition Products ◽  
Viscosity Measurements ◽  
Gutta Percha ◽  
Preceding Work

Abstract It was shown in the preceding work that a very dilute solution of balata in an organic solvent contains macromolecules in solution and not micelles. The same is true of rubber. On the basis of these findings it is possible to calculate the molecular weight of rubber and balata from viscosity measurements by means of the formula developed in a previous work: M=η8p/c. Km. The supposition is made that the molecules of rubber and balata have the form of threads and double threads, respectively. Also it is necessary to determine the constant KKm, and this may be calculated in the case of low molecular products, where the average molecular weight can be determined as well as the viscosity of the solutions. Such semi-colloidal decomposition products were obtained by heating rubber or gutta-percha in either tetralin or xylene. As shown by the following table the four samples thus obtained gave the constant: 0.3×10−3,5

Molecular Weight and Chain-Length of Natural and Synthetic Rubber

1934 ◽  
Vol 7 (1) ◽  
pp. 34-39 ◽  
Author(s):  
A. J. Wildschut
Keyword(s):  
Chain Length ◽  
Freezing Point ◽  
Specific Viscosity ◽  
Molecular Weights ◽  
Gutta Percha ◽  
Synthetic Rubber ◽  
The Subject ◽  
Molecular Substances ◽  
Very High

Abstract The determination of the chain-length of high molecular substances, as, e.g., rubber and gutta-percha, has lately been the subject of many investigations, though as yet the problem has not been definitely solved. The ordinary methods—measurements of the raising of the boiling point and of the depression of the freezing point—can be used only for molecular weights of some thousands, and there always remains a large gap between these compounds and the far greater natural ones. To bridge over this gap Staudinger has developed a supposition according to which it is possible to determine very high molecular weights by means of a viscosimetric method. This method depends on the known fact that for dilute solutions, in which the molecules do not hinder each other (so-called sol-solutions), the specific viscosity is proportional to the length of the molecule. For homologs we have:

Isoprene and Rubber. Part 41. The Hydrogenation of Rubber and Balata

1934 ◽  
Vol 7 (3) ◽  
pp. 496-502
Author(s):  
H. Staudinger ◽  
E. O. Leupold
Keyword(s):  
Molecular Weight ◽  
Particle Sizes ◽  
Colloidal Solutions ◽  
Uniform Size ◽  
Micellar Structure ◽  
Molecular Weights ◽  
Rubber Particles ◽  
Rubber Part ◽  
Points Of View ◽  
Molecular Substances

Abstract Viscosity measurements of dilute solutions of rubber and of balata led to the following values for the size and form of the molecules of these hydrocarbons. It is therefore not a question of definition whether the particle sizes shown above are to be regarded as the molecular or the micellar weights of these substances, for here the concept of molecular weight has the same significance as in the case of lower molecular substances, i. e., the molecule comprises the sum of all atoms combined by normal, i. e., homopolar atoms. The only difference between low and high molecular substances is that low molecular substances are composed of molecules of uniform size, whereas high molecular substances are a mixture of homologous polymers, so that the values above refer to average molecular weights. These results, which explain the nature of colloidal solutions of rubber, are at variance with the views of most investigators of colloids, who ascribe a micellar structure to the rubber particles, and in this way explain the property which rubber has of forming colloidal solutions. This makes clear why until very recently explanations of the constitution of rubber have been open to question among these particular investigators themselves. In order to lend further support to our opinion, the reduction of rubber and balata and low molecular homologous polymeric hydrocarbons was undertaken from certain points of view, as shown in the work which follows.

Isoprene and Rubber. Part 45. Viscosity Measurements of Solutions of Rubber and Hydrorubber in Various Solvents

1936 ◽  
Vol 9 (4) ◽  
pp. 579-584
Author(s):  
H. Staudinger ◽  
H. P. Mojen
Keyword(s):  
Carbon Tetrachloride ◽  
Chain Length ◽  
Homologous Series ◽  
Chlorinated Solvents ◽  
Cellulose Derivatives ◽  
Specific Viscosity ◽  
Molecular Weights ◽  
Rubber Part ◽  
Viscous Solutions ◽  
Chain Lengths

Abstract It has been observed many times that solutions of the same concentration of rubber in various solvents show marked differences in viscosity. For example, solutions of rubber in chlorinated solvents such as carbon tetrachloride have higher viscosities than do solutions of the same concentration in benzene or benzine. These differences in viscosity are attributable to the fact that the rubber molecules are solvated in different ways in the various solvents. It may be further assumed that in a particular homologous series of polymers, all members, i. e., substances of both high and low molecular weights, are solvated in the same solvent in the same way, for only in this way is it possible to believe that the specific viscosity of solutions of like concentration increases with increase in the chain length, as has been found to be true of cellulose derivatives. In the previous experiments with squalene and hydrosqualene (cf. preceding article), the constants necessary for calculating molecular weights and chain member indices n were determined. The constants for carbon tetrachloride are higher than those for benzene. In the case of squalene, therefore, as in the case of rubber, carbon tetrachloride gives more viscous solutions than does benzene. If, now, rubbers and hydrorubbers are solvated in the same way as squalene and hydrosqualene, then the same chain lengths of an homologous series of rubber polymers would be obtained by calculations using constants derived from the simple compounds of the chain member index, and from this the degrees of polymerization, are calculated by means of these constants in the formula:

Isoprene and Rubber. Part 32.The Constitution of Rubber

1931 ◽  
Vol 4 (3) ◽  
pp. 368-380
Author(s):  
H. Staudinger
Keyword(s):  
Molecular Weight ◽  
Colloidal Particles ◽  
Molecular Size ◽  
Group Method ◽  
Decomposition Products ◽  
True Solution ◽  
Rubber Part ◽  
Molecular Substances ◽  
Molecular Compounds ◽  
End Group

Abstract 1. The establishment of the molecular size of high molecular compounds which are composed of fiber molecules by the end-group method of determination is only possible if homologous polymeric series of similar type are concerned. 2. The end-group method assures reliable values with molecules up to a molecular weight of 1000 at the highest. With higher molecular products, like cellulose and rubber, the method is inexact. 3. The molecular weight of rubber and balata may be determined by viscosity determinations in the following two ways: (a) M=ηsp/cKm (b) M=Kc.Kcm. The constants Km and Kcm are determined with low molecular decomposition products. 4. Rubber and balata are composed of fiber molecules, which in one dimension have the magnitude of colloidal particles and in both the others, the dimensions of low molecular substances. 5. In highly viscous rubber solutions, there is the characteristic state of solution. As a result, the sphere of action of the dissolved molecule is greater than the volume at the disposal of the solution. This solution is midway between a true solution and a gel, and is therefore designated as a gel solution. It occurs only with high molecular substances, and is characteristic of them. 6. The readiness with which rubber solutions vary is explained by the fact that the rubber molecules are very sensitive to chemical influences and to changes in temperature as a result of the position of the double bonds. This sensitivity varies with the length of the molecules.

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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