Studies on the Nature of the Action of Organic Accelerators of Vulcanization. The Action of Organic Accelerators on Rubber Sols I–III

1933 ◽  
Vol 6 (2) ◽  
pp. 273-277
Author(s):  
Keiichi Shimada
Keyword(s):  
Direct Evidence ◽  
Active Form ◽  
Intermediate Formation ◽  
Difference Of Opinion ◽  
Vulcanization Process

Abstract While there is a difference of opinion as to the exact mechanism involved, it is generally agreed that the action of organic accelerators in hastening the vulcanization process is usually attributed to the conversion of the sulfur into an active form, probably through the intermediate formation of a compound capable of yielding “nascent” sulfur. But some workers, (Ames, J. Soc. Chem. Ind., 43, 117T (1924); Kirchhof, Kolloid-Z.,, 14, 35 (1914); Twiss, J. Soc. Chem. Ind., 35, 782 (1917); Ditmar, Z. angew. Chem., 34, 465 (1921)) have suggested that the action of organic accelerators might be on the rubber hydrocarbon itself. This theory has not been generally developed, though it has received some small amount of evidence through the works of Le Blanc and Kröger (Z. Elektrochem., 27, 335 (1921)) and Naunton (J. Soc. Chem. Ind., 44, 243T (1925)). These investigators found that the viscosity of rubber solutions decreased with the introduction of an organic accelerator, and referred this phenomenon as a “depolymerization” of rubber. These observations possibly suggest that the influence of accelerators is exerted upon the rubber and constitute the only direct evidence in favor of this view.

Reaction of Elemental Sulfur and Mercaptobenzothiazole

1956 ◽  
Vol 29 (4) ◽  
pp. 1369-1372
Author(s):  
G. A. Blokh ◽  
E. A. Golubkova ◽  
G. P. Miklukhin
Keyword(s):  
Elemental Sulfur ◽  
Active Form ◽  
Chemical Properties ◽  
Intermediate Compound ◽  
Point Of View ◽  
Experimental Fact ◽  
Acceleration Process ◽  
Physico Chemical ◽  
Lower Temperature ◽  
Vulcanization Process

Abstract One of the most important problems in the field of the physics and chemistry of rubber is that of vulcanization. Until now no single theory has been established, which elucidates the complex physico-chemical changes which occur during this process. Still more obscure has been the mechanism of the action of vulcanization accelerators, which, as is well known, not only reduce the time and the temperature of vulcanization, but also influence the physico-mechanical and chemical properties of the rubber. Most investigators have assumed that in the acceleration process a reaction with sulfur converts it to an active form which is capable of bringing about vulcanization at a lower temperature and at a greater rate, than with ordinary elemental sulfur in the absence of an accelerator. This point of view is based on the experimental fact that the vulcanization of rubber by sulfur dioxide and hydrogen sulfide, for example, which form sulfur in the nascent condition, proceeds rapidly even at room temperature. Investigators have also assumed that in the vulcanization process activation of sulfur in the presence of accelerators may occur by different mechanisms. It is possible that the accelerator, reacting with elemental sulfur, forms unstable intermediate compounds, which decompose with liberation of sulfur in an active form. The latter reacts with rubber, and the regenerated accelerator reacts again with elemental sulfur, etc. However, a different process is possible for the activation of elemental sulfur. By this second mechanism the unstable combination of accelerator and sulfur reacts directly with rubber without the formation of active sulfur. Both these mechanisms necessarily assume the formation of intermediate unstable combinations of the accelerator with sulfur. However, direct, experimentally-based demonstrations of such an interaction are lacking in the literature. There exist only theoretical hypotheses concerning the nature of the possible intermediate combination of the accelerator with sulfur. According to Ostromislensky's concepts, further developed by Bedford, such an intermediate compound has the character of a polysulfide. According to Bruni and Romani, this intermediate compound is a disulfide. As is well known, the disulfide theory was placed in doubt by Zaide and Petrov on the basis of data from the vulcanization of rubber in the presence of benzothiazolyl disulfide.

scholarly journals The slow combustion of ethylene

1933 ◽  
Vol 143 (848) ◽  
pp. 16-37 ◽  
Keyword(s):  
Formic Acid ◽  
Intermediate Formation ◽  
Circulation Apparatus ◽  
Initial Product ◽  
Atmosphere Pressure ◽  
Slow Combustion ◽  
Difference Of Opinion

Although much work has been done in the slow oxidation of ethylene since one of us with R. V. Wheeler discovered that it involves the intermediate formation of acet- and form-aldehydes and formic acid, without any liberation of either carbon or hydrogen, some difference of opinion has recently arisen as to the nature of the initial product. Bone and Wheeler -who worked with ethylene-oxygen mixtures both in sealed bulbs at 300° to 350° and about 2 atmosphere pressure, and in their circulation apparatus in contact with porous porcelain at 400° and pressures below 500 mm. -concluded that the main course of the combustion could be represented by the following hydroxylation scheme.

scholarly journals Specific accumulation of 17α-hydroxyprogesterone in microsomal membranes during the process of cytochrome P-450(C-17)-catalysed androgen biosynthesis. A dynamic study of intermediate formation and turnover

1988 ◽  
Vol 256 (1) ◽  
pp. 53-59 ◽  
Author(s):  
N Kühn-Velten ◽  
M Lessmann ◽  
M E Förster ◽  
W Staib
Keyword(s):  
Direct Evidence ◽  
Intermediate Formation ◽  
Specific Accumulation ◽  
Membrane Compartment ◽  
Microsomal Membranes ◽  
Double Label ◽  
Double Substrate ◽  
Label Distribution ◽  
Cytochrome P 450 ◽  
Substrate State

A complete dynamic analysis of cytochrome P-450(C-17)-catalysed androgen biosynthesis from a single dose of progesterone and 17 alpha-hydroxyprogesterone in a double-label double-substrate experiment was performed in order to elucidate the controversial intermediacy of 17 alpha-hydroxyprogesterone. Label distribution within the steroid fractions as well as in the membrane and buffer compartments yields direct evidence that the endogenously formed 17 alpha-hydroxyprogesterone (which is in an ‘intermediate state’) accumulates to a higher degree in microsomal membranes than does the exogenously added 17 alpha-hydroxyprogesterone (which is in a ‘substrate state’) under certain conditions. It is also demonstrated that endogenously formed 17 alpha-hydroxyprogesterone may partly leave the membrane compartment (in terms of a ‘leakage’ or ‘overflow’ phenomenon) and is then able to equilibrate with the pool of exogenously added 17 alpha-hydroxyprogesterone. Since only the label distribution in the membrane-associated (but not always in the aqueous) 17 alpha-hydroxyprogesterone pool corresponds to the label distribution in the androgen fraction, it is concluded that only the membrane-associated 17 alpha-hydroxyprogesterone pool is directly accessible to cytochrome P-450(C-17)-catalysed conversion into androgens.

scholarly journals DIRECT EVIDENCE FOR HAGEMAN FACTOR (FACTOR XII) ACTIVATION BY BACTERIAL LIPOPOLYSACCHARIDES (ENDOTOXINS)

1974 ◽  
Vol 140 (3) ◽  
pp. 797-811 ◽  
Author(s):  
David C. Morrison ◽  
Charles G. Cochrane
Keyword(s):  
Escherichia Coli ◽  
Lipid A ◽  
Direct Evidence ◽  
Active Form ◽  
Fluid Phase ◽  
Factor Xii ◽  
Hageman Factor ◽  
High Concentrations ◽  
Bacterial Lipopolysaccharides ◽  
Factor Interaction

Purified precursor Hageman factor has been demonstrated to bind to soluble bacterial lipopolysaccharide (LPS, endotoxin) isolated from Escherichia coli 0111:B4, and this complex has been shown to have the capacity to convert prekallikrein to its active form. In addition, LPS-activated Hageman factor substantially reduces clotting times in XII-deficient plasma. The capacity to activate Hageman factor has been demonstrated to reside in the lipid A region of the LPS molecule. Activation of Hageman factor by LPS contrasts with fluid-phase activation (e.g., by kallikrein or trypsin) in that no cleavage to lower molecular weight fragments occurs. High concentrations of LPS inhibit the activity of Hageman factor, probably by a direct LPS-Hageman factor interaction.

The Immuno-Electron Microscopic Localization of the Mo-Fe Protein Component of Nitrogenase in Cells of Azotobacter Vinelandii

1973 ◽  
Vol 31 ◽  
pp. 574-575
Author(s):  
J. T. Stasny ◽  
R. C. Burns ◽  
R. W. F. Hardy
Keyword(s):  
Cellular Localization ◽  
Direct Evidence ◽  
Azotobacter Vinelandii ◽  
Intracellular Localization ◽  
Protein Component ◽  
Electron Microscopic ◽  
Thin Sections ◽  
Fe Protein ◽  
Intracytoplasmic Membranes

Structure-functlon studies of biological N2-fixation have correlated the presence of the enzyme nitrogenase with increased numbers of intracytoplasmic membranes in Azotobacter. However no direct evidence has been provided for the internal cellular localization of any nitrogenase. Recent advances concerned with the crystallizatiorTand the electron microscopic characterization of the Mo-Fe protein component of Azotobacter nitrogenase, prompted the use of this purified protein to obtain antibodies (Ab) to be conjugated to electron dense markers for the intracellular localization of the protein by electron microscopy. The present study describes the use of ferritin conjugated to goat antitMo-Fe protein immunoglobulin (IgG) and the observations following its topical application to thin sections of N2-grown Azotobacter.

Structural similarity of ribosomes from E. coli and A. salina

1978 ◽  
Vol 36 (2) ◽  
pp. 242-243
Author(s):  
M. Boublik ◽  
R.M. Wydro ◽  
W. Hellmann ◽  
F. Jenkins
Keyword(s):  
Ribosomal Proteins ◽  
Direct Evidence ◽  
Structural Similarity ◽  
Carbon Support ◽  
Artemia Salina ◽  
Uranyl Acetate ◽  
Biological Assays ◽  
E Coli ◽  
And Function ◽  
Fine Carbon

Ribosomes are ribonucleoprotein particles necessary for processing the genetic information of mRNA into proteins. Analogy in composition and function of ribosomes from diverse species, established by biochemical and biological assays, implies their structural similarity. Direct evidence obtained by electron microscopy seems to be of increasing relevance in understanding the structure of ribosomes and the mechanism of their role in protein synthesis.The extent of the structural homology between prokaryotic and eukaryotic ribosomes has been studied on ribosomes of Escherichia coli (E.c.) and Artemia salina (A.s.). Despite the established differences in size and in the amount and proportion of ribosomal proteins and RNAs both types of ribosomes show an overall similarity. The monosomes (stained with 0.5% aqueous uranyl acetate and deposited on a fine carbon support) appear in the electron micrographs as round particles with a diameter of approximately 225Å for the 70S E.c. (Fig. 1) and 260Å for the 80S A.s. monosome (Fig. 2).

Dupuytren's Contracture and Microvessels

1981 ◽  
Vol 39 ◽  
pp. 470-471
Author(s):  
C. W. Klscher ◽  
D. Speer
Keyword(s):  
Hypertrophic Scar ◽  
Active Form ◽  
Scar Tissue ◽  
Vascular Supply ◽  
Fiber Bundles ◽  
Dupuytren’S Contracture ◽  
Palmar Fascia ◽  
Immune Disease ◽  
Dupuytren's Contracture ◽  
Longitudinal Fiber

Dupuytren's Contracture is a nodular proliferation of the longitudinal fiber bundles of palmar fascia with its attendant contraction. The factors attributed to its etiology have included trauma, diabetes, alcoholism, arthritis, and auto-immune disease. The tissue has been observed by electron microscopy and found to contain myofibroblasts.Dupuytren's Contracture constitutes a scar, and as such, excessive collagen can be observed, along with an active form of fibroblast.Previous studies of the hypertrophic scar have led us to propose that integral in the initiation and sustenance of scar tissue is a profusion of microvascular regeneration, much of which becomes and remains occluded producing a hypoxia which stimulates fibroblast synthesis. Thus, when considering a study of Dupuytren's Contracture, we predicted finding occluded microvessels at or near the fascial scarring focus.Three cases of Dupuytren's Contracture yielded similar specimens, which were fixed in Karnovskys fluid for 2 to 20 days. Upon removal of the contracture bands care was taken to include the contiguous fatty and areolar tissue which contain the vascular supply and to identify the junctional area between old and new fascia.

Stress Relaxation and the Formation of Silicides in the Process of the Crystallization of NI-NB Films on SI

1991 ◽  
Vol 49 ◽  
pp. 898-899
Author(s):  
N. Rozhanski ◽  
V. Lifshitz
Keyword(s):  
Thin Films ◽  
Stress Relaxation ◽  
Integrated Circuits ◽  
Direct Evidence ◽  
Alloy Film ◽  
Diffusion Barriers ◽  
Effective Barrier

Thin films of amorphous Ni-Nb alloys are of interest since they can be used as diffusion barriers for integrated circuits on Si. A native SiO2 layer is an effective barrier for Ni diffusion but it deformation during the crystallization of the alloy film lead to the appearence of diffusion fluxes through it and the following formation of silicides. This study concerns the direct evidence of the action of stresses in the process of the crystallization of Ni-Nb films on Si and the structure of forming NiSi2 islands.

Point and planar defects in the iron sulfide compounds Fe1-xS

1984 ◽  
Vol 42 ◽  
pp. 434-435
Author(s):  
Thao A. Nguyen
Keyword(s):  
Low Temperatures ◽  
Direct Evidence ◽  
Iron Sulfide ◽  
Planar Defects ◽  
Selective Area ◽  
Vacancy Ordering ◽  
Different Types ◽  
Lattice Images ◽  
The Subject ◽  
Beam Lattice

It is well known that the large deviations from stoichiometry in iron sulfide compounds, Fe1-xS (0≤x≤0.125), are accommodated by iron vacancies which order and form superstructures at low temperatures. Although the ordering of the iron vacancies has been well established, the modes of vacancy ordering, hence superstructures, as a function of composition and temperature are still the subject of much controversy. This investigation gives direct evidence from many-beam lattice images of Fe1-xS that the 4C superstructure transforms into the 3C superstructure (Fig. 1) rather than the MC phase as previously suggested. Also observed are an intrinsic stacking fault in the sulfur sublattice and two different types of vacancy-ordering antiphase boundaries. Evidence from selective area optical diffractograms suggests that these planar defects complicate the diffraction pattern greatly.

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