Oxidation of hydrocarbons in the liquid phase: n-dodecane in a borosilicate glass chamber at 200 °C

1969 ◽  
Vol 47 (22) ◽  
pp. 4175-4182 ◽  
Author(s):  
B. D. Boss ◽  
R. N. Hazlett

The 5-h oxidation of n-dodecane at 200 °C by air at 1 atm is reported for experiments in a borosilicate glass reaction chamber equipped with a gas bubbler. The rate of reaction was limited by the rate of oxygen diffusion from the gas phase due to the rapid reaction of dissolved oxygen. The reaction products were analyzed in aliquots taken periodically from the reaction chamber. Chemical analyses, gas–liquid phase chromatography (g.l.p.c.), tandem g.l.p.c.-mass spectroscopy, infrared, and ultraviolet were used to identify products accounting for 98% of the oxygen reacted. The isomer distribution of the dodecenes, dodecanols, and dodecanones formed, as well as the distribution of carboxylic acids, were determined. Three classes of intramolecular reaction products, cyclic ethers, cyclic hydrocarbons, and lactones, were detected. Many volatile products were detected. A filterable precipitate obtained after 10 h of oxidation was studied using infrared attenuated total reflectance techniques. A reaction mechanism is discussed based on current knowledge of other systems, the products identified, and the stoichiometry of the reaction.

2021 ◽  
Vol 6 (1) ◽  
Author(s):  
Bin Wang ◽  
Lei Zhang ◽  
Tong Dai ◽  
Ziran Qin ◽  
Huasong Lu ◽  
...  

AbstractEmerging evidence suggests that liquid–liquid phase separation (LLPS) represents a vital and ubiquitous phenomenon underlying the formation of membraneless organelles in eukaryotic cells (also known as biomolecular condensates or droplets). Recent studies have revealed evidences that indicate that LLPS plays a vital role in human health and diseases. In this review, we describe our current understanding of LLPS and summarize its physiological functions. We further describe the role of LLPS in the development of human diseases. Additionally, we review the recently developed methods for studying LLPS. Although LLPS research is in its infancy—but is fast-growing—it is clear that LLPS plays an essential role in the development of pathophysiological conditions. This highlights the need for an overview of the recent advances in the field to translate our current knowledge regarding LLPS into therapeutic discoveries.


2018 ◽  
Vol 197 ◽  
pp. 09005
Author(s):  
Bregas Siswahjono Tatag Sembodo ◽  
Hary Sulistyo ◽  
Wahyudi Budi Sediawan ◽  
Mohammad Fahrurrozi

Corncobs are potentially processed into bio-oil through thermochemical liquefaction processes. It is difficult to construct kinetics models based on the compounds involved in the reaction. It would be made four kinetic models based on four reaction products, i.e., solids, bio-oil, gas and volatile products. The purposes of the study were to seek kinetics model of thermochemical liquefaction of corncobs in ethanol-water solution and to study the effect of ethanol concentration. The experiment of liquefaction processes of corncobs in ethanol-water solution using sodium carbonate catalyst was performed in the 150 ml autoclave equipped with a magnetic stirrer in the temperature up to 280°C. Four kinetic models were applied to predict the yield of four reaction product lumps. The calculation results were compared to the experimental data. Compared to the others, model 4 was the most realistic and closely matching to the experimental data. In model 4 the reaction mechanism was assumed that biomass (corncobs) first decomposed into bio-oil, followed by decomposition of bio-oil into volatile products reversibly and, finally, volatile products decomposed into gaseous products. The yield of bio-oil increased from 42.05% to 54.93% by increasing to ethanol concentration of 0% to 40%.


1993 ◽  
Vol 71 (9) ◽  
pp. 1349-1352 ◽  
Author(s):  
Michel Girard ◽  
François Clairmont ◽  
Aspi Maneckjee ◽  
Nicole Mousseau ◽  
Brian A. Dawson ◽  
...  

Ronidazole and dimetridazole, two important veterinary drugs, were found to react readily in the presence of cysteine, under neutral aqueous conditions, leading to the formation of 5-S-cysteinyl-1-methylimidazole-2-methanol carbamate and 5-S-cysteinyl-1,2-dimethylimidazole respectively through nitro displacement. The reaction products were identified by spectroscopic techniques. The rate of reaction was accelerated by increasing the pH of the medium and was accompanied by a slight change in the product distribution. The reaction was also observed, albeit at a slower rate than that of cysteine, with glutathione, another ubiquitous thiol substrate found in biological systems. While this type of nucleophilic reaction has previously been observed for suitably substituted nitrobenzene derivatives, to the best of our knowledge its occurrence with nitro-heteroaromatics has never been reported. The ready reaction of the parent nitro drugs under such mild aqueous conditions suggests that this may be an alternative path for the formation of nonextractable bound residues in tissues.


1965 ◽  
Vol 8 (6) ◽  
pp. 442-446
Author(s):  
Yoshinobu Takegami ◽  
Yoshikazu Fujimura ◽  
Kosaku Kamio

2013 ◽  
Vol 19 (No. 2) ◽  
pp. 41-45 ◽  
Author(s):  
J. Rössner ◽  
J. Velíšek ◽  
F. Pudil ◽  
J. Davídek

Aspartic and glutamic acids, asparagine and glutamine were oxidised with either potassium peroxodisulphate or glyoxal. Nonvolatile products were derivatised and analysed by GC/FID and GC/MS. Volatile reaction products were isolated and analysed by the same methods. It was found that the degradation reactions of amino acids are complex. Amino acids are principally degraded via the corresponding a-keto acids to Strecker aldehydes (aspartic acid to oxalacetic and 3-oxopropionic acids and glutamic acid to a-ketoglutaric and 4-oxobutyric acids), which are unstable and decomposed by decarboxylation to the corresponding aldehydes. Aspartic acid also eliminates ammonia and yields fumaric acid whereas glutamic acid gives rise to an imine, pyroglutamic acid. A recombination of free radicals leads to dicarboxylic acids (succinic acid from aspartic acid, succinic, glutaric and adipic acids from glutamic acid). The major volatile products (besides the aldehydes) are lower carboxylic acids (acetic acid from aspartic acid and propionic acid acid from glutamic acid) that can at least partly arise by radical reactions. In both quality and quantity terms, a higher amount of degradation products arises by oxidation of amino acids by peroxodisulphate.


1987 ◽  
Vol 33 (7) ◽  
pp. 1129-1132 ◽  
Author(s):  
M H Kroll ◽  
N A Roach ◽  
B Poe ◽  
R J Elin

Abstract We investigated the mechanism of the Jaffé reaction for determination of creatinine by studying the spectrophotometric, kinetic, and equilibrium properties of the reaction of picrate with creatinine and with cyclic and aliphatic ketones. Absorbance spectra for the reaction products of picrate with all the ketones were superimposable with that of creatinine (Amax, 490 nm). Cyclic ketones not containing nitrogen had a molar absorptivity less than half that of creatinine and equilibrium constants approximately 0.01 that of creatinine. Aliphatic ketones, except for benzylacetone, had molar absorptivities similar to that of creatinine, but all of these compounds had equilibrium constants approximately a tenth or less that of creatinine. The common structure for all of the compounds reacting with picrate is the carbonyl group. The variable magnitude of interference for aliphatic and cyclic ketones is ascribable to the different rate constants, molar absorptivities, and equilibrium constants as compared with creatinine. Structures adjacent to the carbonyl group significantly affect the absorptivity and equilibrium constant, but steric hindrance is the major factor affecting the rate of reaction. We postulate that the carbonyl group is required for the Jaffé reaction, and we suggest a mechanism for the reaction.


2008 ◽  
Vol 78 (8) ◽  
pp. 1533-1544 ◽  
Author(s):  
O. T. Kasaikina ◽  
Z. S. Kartasheva ◽  
L. M. Pisarenko

1965 ◽  
Vol 13 (6) ◽  
pp. 423-430 ◽  
Author(s):  
ARNE DAHLQVIST ◽  
INGE OLSSON ◽  
ÅKE NORDÉN

A quantitative test-tube method has been used to study the periodate-Schiff reaction of a number of pure substances. The rate of reaction, the amount of color produced, and in some cases the amount of periodate consumed, have been measured. The dye produced by different carbohydrates has been analyzed by spectrophotometry and paper chromatography. Glycogen, starch and dextran reacted slowly and produced much less color than the corresponding amount of free monosaccharides. Oligosaccharides and heteropolysaccharides were either periodate-Schiff-negative or very weakly positive. Proteins and nucleic acids were negative. There was no simple relation between the intensity of the periodate-Schiff reaction and the amount of periodate consumed or the amount of aldehyde groups formed on the oxidation by periodate. The dyes formed with different carbohydrates had essentially the same absorption curve, but differed in their chromatographic mobility.


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