Statistical Kinetics of Hevea Rubber Cyclization

1952 ◽  
Vol 25 (4) ◽  
pp. 784-800
Author(s):  
M. Gordon
Keyword(s):  
Cyclization Reaction ◽  
Acidity Function ◽  
Statistical Effect ◽  
Copolymer Structure ◽  
Reduced Rate ◽  
Cyclization Rate ◽  
First Time ◽  
Transition Complex ◽  
Kinetics Of ◽  
Better Than

Abstract Rubber cyclization provides a useful illustration of statistical effects intervening in the reactions of long-chain polymers. Analogously to the known cyclizations of simple diisoprenic terpenes, each individual cyclization act links two adjacent isoprene units in the rubber chain into a six-membered ring. However, some of the units remain stranded between neighboring rings and escape cyclization for want of a partner. Thus the final polymer has a copolymer structure of 86.5 per cent of diisoprenic rings and 13.5 per cent of uncyclized monisoprenic units. This result is derived from a statistical theory of Flory, and has previously found accurate experimental verification. The bearing of this statistical effect on the reaction kinetics has now been studied for the first time. Dilatometric experiments on rubber emulsions in sulfuric acid have shown that the cyclization reaction conforms in the main with a statistical cyclization law much better than with a first-order equation uncorrected for the survival of stranded units. High accuracy was required for this experimental distinction, whose importance lies in the implicit proof that the polymer units participate in the rate-determining transition complex, in accordance with the accepted proton transfer mechanism. A kinetic proof has incidentally been furnished for the fact that the rubber polymer contains long chains of identical units. When handled by an emulsion technique, this polymer can provide a useful “model compound” for its simpler terpene analogs. Certain rate abnormalities have been observed, including an induction period of reduced rate, probably connected with diffusion effects. A small volume change subsequent to the cyclization reaction may reflect a prototropic double-bond shift. The activation energy and entropy are found to be lower than in previous work, an effect traced in part to a curvature of the Arrhenius plot. The known dependence of cyclization rate on Hammett's acidity function H0 is quantitatively confirmed.

Statistical Kinetics of Hevea Rubber Cyclization

1951 ◽  
Vol 24 (4) ◽  
pp. 924-939 ◽  
Author(s):  
M. Gordon
Keyword(s):  
Cyclization Reaction ◽  
Acidity Function ◽  
Statistical Effect ◽  
Copolymer Structure ◽  
Reduced Rate ◽  
Cyclization Rate ◽  
First Time ◽  
Transition Complex ◽  
Kinetics Of ◽  
Better Than

Abstract Rubber cyclization provides a useful illustration of statistical effects intervening in the reactions of long-chain polymers. Analogously to known cyclizations of simple diisoprenic terpenes, each individual cyclization act links two adjacent isoprene units in the rubber chain into a six-membered ring. However, some of the units remain stranded between neighboring rings and escape cyclization for want of a partner. Thus the final polymer has a copolymer structure of 86.5 per cent of diisoprenic rings and 13.5 per cent of uncyclized monisoprenic units. This result is derived from a statistical theory of Flory, and has previously found accurate experimental verification. The bearing of this statistical effect on the reaction kinetics has now been studied for the first time. Dilatometric experiments on rubber emulsions in sulfuric acid have shown that the cyclization reaction conforms in the main with a statistical cyclization law much better than with a first-order equation uncorrected for the survival of stranded units. High accuracy was required for this experimental distinction, whose importance lies in the implicit proof that the polymer units participate in the rate-determining transition complex, in accordance with the accepted proton transfer mechanism. A kinetic proof has incidentally been furnished for the fact that the rubber polymer contains long chains of identical units. When handled by an emulsion technique, this polymer can provide a useful “model compound” for its simpler terpene analogs. Certain rate abnormalities have been observed, including an induction period of reduced rate, probably connected with diffusion effects. A small volume change subsequent to the cyclization reaction may reflect a prototropic double-bond shift. The activation energy and entropy are found to be lower than in previous work, an effect traced in part to a curvature of the Arrhenius plot. The known dependence of cyclization rate on Hammett's acidity function H0 is quantitatively confirmed.

Statistical kinetics of Hevea rubber cyclization

1951 ◽  
Vol 204 (1079) ◽  
pp. 569-585 ◽  
Keyword(s):  
Cyclization Reaction ◽  
Acidity Function ◽  
Statistical Effect ◽  
Diffusion Effects ◽  
Reduced Rate ◽  
Cyclization Rate ◽  
First Time ◽  
Transition Complex ◽  
Kinetics Of ◽  
Better Than

Rubber cyclization provides a useful illustration of statistical effects intervening in the reactions of long-chain polymers. Analogously to the known cyclizations of simple diisoprenic terpenes, each individual cyclization act links two adjacent isoprene units in the rubber chain into a six-membered ring. However, some of the units remain stranded between neighbouring rings and escape cyclization for want of a partner. Thus the final polymer has a co-polymer structure of 86.5% of di-isoprenic rings and 13.5% of uncyclized monisoprenic units. This result is derived from a statistical theory of Flory, and has previously found accurate experimental verification. The bearing of this statistical effect on the reaction kinetics has now been studied for the first time. Dilatemetric experiments on rubber emulsions in sulphuric acid have shown that the cyclization reaction conforms in the main with a statistical cyclization law much better than with a first-order equation uncorrected for the survival of stranded units. High accuracy was required for this experimental distinction, whose importance lies in the implicit proof that the polymer units participate in the rate-determining transition complex, in accordance with the accepted proton transfer mechanism. A kinetic proof has incidentally been furnished for the fact that the rubber polymer contains long chains of identical units. When handled by an emulsion technique, this polymer can provide a useful ‘model compound’ for its simpler terpene analogues. Certain rate abnormalities have been observed including an induction period of reduced rate, probably connected with diffusion effects. A small volume change subsequent to the cyclization reaction may reflect a prototropic double-bond shift. The activation energy and entropy are found to be lower than in previous work, an effect traced in part to a curvature of the Arrhenius plot. The known dependence of cyclization rate on Hammett’s acidity function H 0 is quantitatively confirmed.

Zeolites Fit For A Crown: Probing Host-Guest Interactions with Thermogravimetric Methods

2018 ◽  
Author(s):  
Asel Sartbaeva ◽  
Paul R. Raithby ◽  
Remi Castaing ◽  
Antony Nearchou
Keyword(s):  
Mass Spectrometry ◽  
Thermal Analysis ◽  
Differential Thermal Analysis ◽  
Petrochemical Industry ◽  
Rational Use ◽  
New Methodologies ◽  
First Time ◽  
Kinetics Of

Through a combination of thermogravimetry, mass spectrometry and differential thermal analysis, we demonstrate for the first time that all four zeolites show experimental differences in their host-guest interactions with 18C6. In addition, we have estimated the kinetics of 18C6 decomposition, which is a technique that has not been applied to zeolites previously. Using these findings as a toolkit, a more rational use of OSDAs can be utilised to prepare designer zeolites. Furthermore, the new methodologies presented herein can be applied to current zeolites, such as MFI-type zeolites used in the petrochemical industry.

scholarly journals Effect of Antibacterial Root Canal Sealer on Persistent Apical Periodontitis

Antibiotics ◽  
2021 ◽  
Vol 10 (6) ◽  
pp. 741
Author(s):  
Zheng Wang ◽  
Ge Yang ◽  
Biao Ren ◽  
Yuan Gao ◽  
Xian Peng ◽  
...  
Keyword(s):  
Enterococcus Faecalis ◽  
Therapeutic Effect ◽  
Root Canal ◽  
Apical Periodontitis ◽  
Control Group ◽  
Root Canal Sealer ◽  
Root Canal Filling ◽  
First Time ◽  
Cone Beam Computer Tomography ◽  
Better Than

The infection of Enterococcus faecalis and its interacting microorganisms in the root canal could cause persistent apical periodontitis (AP). Antibacterial root canal sealer has favorable prospects to inhibit biofilms. The purpose of this study was to investigated the antibacterial effect of root canal sealer containing dimethylaminododecyl methacrylate (DMADDM) on persistent AP in beagle dogs for the first time. Persistent AP was established by a two-step infection with Enterococcus faecalis and multi-bacteria (Enterococcus faecalis, Lactobacillus acidophilus, Actinomycesnaeslundii, Streptococcus gordonii). Root canal sealer containing DMADDM (0%, 1.25%, 2.5%) was used to complete root canal filling. The volume of lesions and inflammatory grade in the apical area were evaluated by cone beam computer tomography (CBCT) and hematoxylin-eosin staining. Both Enterococcus-faecalis- and multi-bacteria-induced persistent AP caused severe apical destruction, and there were no significant differences in pathogenicity between them. DMADDM-modified sealer significantly reduced the volume of periapical lesion and inflammatory grade compared with the control group, among them, the therapeutic effect of the 2.5% group was better than the 1.25% group. In addition, E.faecalis-induced reinfection was more sensitive to the 2.5% group than multi-bacteria reinfection. This study shows that root canal sealer containing DMADDM had a remarkable therapeutic effect on persistent AP, especially on E. faecalis-induced reinfection.

scholarly journals Rapid systemic surge of IL-33 after severe human trauma: a prospective observational study

2021 ◽  
Vol 27 (1) ◽  
Author(s):  
Olav Sundnes ◽  
William Ottestad ◽  
Camilla Schjalm ◽  
Peter Lundbäck ◽  
Lars la Cour Poulsen ◽  
...  
Keyword(s):  
High Resolution ◽  
Prospective Observational Study ◽  
Tissue Injury ◽  
Trauma Patients ◽  
Decoy Receptor ◽  
Interleukin 33 ◽  
Injured Patients ◽  
First Time ◽  
Kinetics Of ◽  
Insight Into

Abstract Background Alarmins are considered proximal mediators of the immune response after tissue injury. Understanding their biology could pave the way for development of new therapeutic targets and biomarkers in human disease, including multiple trauma. In this study we explored high-resolution concentration kinetics of the alarmin interleukin-33 (IL-33) early after human trauma. Methods Plasma samples were serially collected from 136 trauma patients immediately after hospital admission, 2, 4, 6, and 8 h thereafter, and every morning in the ICU. Levels of IL-33 and its decoy receptor sST2 were measured by immunoassays. Results We observed a rapid and transient surge of IL-33 in a subset of critically injured patients. These patients had more widespread tissue injuries and a greater degree of early coagulopathy. IL-33 half-life (t1/2) was 1.4 h (95% CI 1.2–1.6). sST2 displayed a distinctly different pattern with low initial levels but massive increase at later time points. Conclusions We describe for the first time early high-resolution IL-33 concentration kinetics in individual patients after trauma and correlate systemic IL-33 release to clinical data. These findings provide insight into a potentially important axis of danger signaling in humans.

scholarly journals CPC2 Reduction with Hipparcos and Proper Motions in The Southern Hemisphere

1998 ◽  
Vol 11 (1) ◽  
pp. 551-551
Author(s):  
N. Zacharias ◽  
M.I. Zacharias ◽  
C. de Vegt ◽  
C.A. Murray
Keyword(s):  
Southern Hemisphere ◽  
Systematic Errors ◽  
Reference Star ◽  
Proper Motions ◽  
Positional Accuracy ◽  
Star Catalog ◽  
Naval Observatory ◽  
Celestial Reference System ◽  
First Time ◽  
Better Than

The Second Cape Photographic Catalog (CPC2) contains 276,131 stars covering the entire Southern Hemisphere in a 4-fold overlap pattern. Its mean epoch is 1968, which makes it a key catalog for proper motions. A new reduction of the 5687 plates using on average 40 Hipparcos stars per plate has resulted in a vastly improved catalog with a positional accuracy of about 40 mas (median value) per coordinate, which comes very close to the measuring precision. In particular, for the first time systematic errors depending on magnitude and color can be solved unambiguously and have been removed from the catalog. In combination with the Tycho Catalogue (mean epoch 1991.25) and the upcoming U.S. Naval Observatory CCD Astrograph Catalog (UCAC) project proper motions better than 2 mas/yr can be obtained. This will lead to a vastly improved reference star catalog in the Southern Hemisphere for the final Astrographic Catalogue (AC) reductions, which will then provide propermotions for millions of stars when combined with new epoch data. These data then will allow an uncompromised reduction of the southern Schmidt surveys on the International Celestial Reference System (ICRS).

scholarly journals Investigation of Solubility Behavior of Canagliflozin Hydrate Crystals Combining Crystallographic and Hirshfeld Surface Calculations

Molecules ◽  
2021 ◽  
Vol 26 (2) ◽  
pp. 298
Author(s):  
Yefen Zhu ◽  
Yanlei Kang ◽  
Ling Zhu ◽  
Kaxi Yu ◽  
Shuai Chen ◽  
...  
Keyword(s):  
Crystal Structure ◽  
Intermolecular Forces ◽  
Hirshfeld Surface ◽  
Reversible Inhibitor ◽  
Solubility Behavior ◽  
Hydrogen Bond Networks ◽  
Solvent Molecules ◽  
First Time ◽  
Better Than

Canagliflozin (CG) was a highly effective, selective and reversible inhibitor of sodium-dependent glucose co-transporter 2 developed for the treatment of type 2 diabetes mellitus. The crystal structure of CG monohydrate (CG-H2O) was reported for the first time while CG hemihydrate (CG-Hemi) had been reported in our previous research. Solubility and dissolution rate results showed that the solubility of CG-Hemi was 1.4 times higher than that of CG-H2O in water and hydrochloric acid solution, and the dissolution rates of CG-Hemi were more than 3 folds than CG-H2O in both solutions. Hirshfeld surface analysis showed that CG-H2O had stronger intermolecular forces than CG-Hemi, and water molecules in CG-H2O participated three hydrogen bonds, forming hydrogen bond networks. These crystal structure features might make it more difficult for solvent molecules to dissolve CG-H2O than CG-Hemi. All these analyses might explain why the dissolution performance of CG-Hemi was better than CG-H2O. This work provided an approach to predict the dissolution performance of the drug based on its crystal structure.

The kinetics of the decarboxylation of β-resorcylic acid in catechol

1976 ◽  
Vol 29 (2) ◽  
pp. 443 ◽  
Author(s):  
MA Haleem ◽  
MA Hakeem
Keyword(s):  
Rate Equation ◽  
Kinetic Data ◽  
Reaction Rate ◽  
Complex Mechanism ◽  
First Order ◽  
Absolute Reaction Rate ◽  
First Time ◽  
Kinetics Of ◽  
Absolute Reaction ◽  
Reaction Rate Equation

Kinetic data are reported for the decarboxylation of β-resorcylic acid in resorcinol and catechol for the first time. The reaction is first order. The observation supports the view that the decomposition proceeds through an intermediate complex mechanism. The parameters of the absolute reaction rate equation are calculated.

Etude par spectrométrie infrarouge de l'action de solvants aprotiques sur l'association ester–eau et ester–Ba2+. Discussion du rôle catalytique du solvant et de l'ion Ba2+ dans l'hydrolyse alcaline du propionate de methyle

1979 ◽  
Vol 57 (4) ◽  
pp. 400-403 ◽  
Author(s):  
Anne Le Narvor ◽  
Pierre Saumagne
Keyword(s):  
Ir Spectra ◽  
Charge Density ◽  
Carbonyl Group ◽  
Alkaline Hydrolysis ◽  
Experimental Results ◽  
Methyl Propionate ◽  
Orbital Control ◽  
Different Types ◽  
Kinetics Of ◽  
Better Than

The ir spectra of mixtures of methyl propionate/water and methyl propionate/Ba2+ in dimethylsulfoxide and in acetonitrile have been recorded in the region of the νCO mode of the ester. Evidence is presented to indicate the presence of different types of complexes; their concentration was determined as a function of the composition of the medium. The spectroscopic results are compared to those from the kinetics of the alkaline hydrolysis in the same conditions. It is demonstrated that the orbital control explains the experimental results better than does the charge density on the carbon of the carbonyl group. [Journal translation]

Research of the Workpiece-Stage Control System Based on the ACR9000 in the Composite Coating Equipment of MEVVAII and FAD

2013 ◽  
Vol 668 ◽  
pp. 410-414
Author(s):  
Rui Xia Zhang ◽  
Bin Liao ◽  
Zhi Guo Liu ◽  
Xian Ying Wu
Keyword(s):  
Control System ◽  
Servo Control ◽  
Uniform Rotation ◽  
Coating Films ◽  
Servo Control System ◽  
Motion Modes ◽  
Speed Rotation ◽  
Micro Tools ◽  
First Time ◽  
Better Than

In order to realize the extensive application of technologies of MEVVAII and FAD, the composite equipment has been developed for surface modification and coating films. In this paper, for the first time, the servo control system based on ACR9000 has been used to control workpiece-stage of the composite equipment. Eight target disks are installed on workpiece-stage. Each of target disks can be mounted about 1300 PCB micro tools. So, the equipment can satisfy the requirement for mass production. Experimental results show that the coating unevenness is less than ±14%, better than those of traditional equipments which is less than ±29%. The main purpose of the paper is to introduce the design of workpiece-stage and its three motion modes of rotary positioning, uniform rotation and variable speed rotation, and coating effects corresponding to three motion modes have been verified by experiments.

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