Kinetic Studies in the Chemistry of Rubber and Related Materials. III. Thermochemistry and Mechanisms of Olefin Oxidation

1947 ◽  
Vol 20 (3) ◽  
pp. 617-626
Author(s):  
J. L. Bolland ◽  
Geoffrey Gee
Keyword(s):  
Kinetic Studies ◽  
Ethyl Linoleate ◽  
Oxidation Products ◽  
Oxidation Reactions ◽  
Olefin Oxidation ◽  
Primary Products ◽  
Resonance Energies ◽  
Oxidation Chain ◽  
Bond Strengths

Abstract A new estimate of the O—O bond strength in hydroperoxides is reported, based on a determination of the heats of oxidation of ethyl linoleate and linolenate. This value is employed, together with other known bond strengths and resonance energies, to estimate the heats of a number of alternative oxidation reactions of olefins. By considering the effects of the olefin structure on these heats of reaction, it is possible to see how structural differences can lead to the formation of different oxidation products. The discussion is confined to primary products of the oxidation chain, but, even so, a considerable diversity of behavior is shown to be possible. The final material may include simple monomeric hydroperoxides, polymers with varying amounts of oxygen incorporated in the chain, cyclic peroxides, and scission products. The very limited experimental evidence available falls generally into line with expectation.

Stability Indicating Liquid Chromatographic Method for the Determination of Fenofibrate and its Application to Kinetic Studies

2013 ◽  
Vol 5 (4) ◽  
pp. 1866-1874
Author(s):  
K. Srinivasa Rao ◽  
Keshar N K ◽  
N Jena ◽  
M.E.B Rao ◽  
A K Patnaik
Keyword(s):  
Degradation Products ◽  
Kinetic Studies ◽  
Pharmaceutical Formulations ◽  
Assay Method ◽  
Pharmaceutical Dosage Form ◽  
Stability Indicating ◽  
Zero Order Kinetics ◽  
Relative Standard ◽  
Liquid Chromatographic

A stability-indicating LC assay method was developed for the quantitative determination of fenofibrate (FFB) in pharmaceutical dosage form in the presence of its degradation products and kinetic determinations were evaluated in acidic, alkaline and peroxide degradation conditions. Chromatographic separation was achieved by use of Zorbax C18 column (250 × 4.0 mm, 5 μm). The mobile phase was established by mixing phosphate buffer (pH adjusted 3 with phosphoric acid) and acetonitrile (30:70 v/v). FFB degraded in acidic, alkaline and hydrogen peroxide conditions, while it was more stable in thermal and photolytic conditions. The described method was linear over a range of 1.0-500 μg/ml for determination of FFB (r= 0.9999). The precision was demonstrated by relative standard deviation (RSD) of intra-day (RSD= 0.56– 0.91) and inter-day studies (RSD= 1.47). The mean recovery was found to be 100.01%. The acid and alkaline degradations of FFB in 1M HCl and 1M NaOH solutions showed an apparent zero-order kinetics with rate constants 0.0736 and 0.0698  min−1 respectively and the peroxide degradation with 5% H2O2 demonstrated an apparent first-order kinetics with rate constant k = 0.0202 per min. The t1/2, t90   values are also determined for all the kinetic studies. The developed method was found to be simple, specific, robust, linear, precise, and accurate for the determination of FFB in pharmaceutical formulations.  

scholarly journals Lifetime predictions of non-ionic and ionic biopolymers: kinetic studies by non-isothermal thermogravimetric analysis

2021 ◽  
Author(s):  
Martina Maria Calvino ◽  
Lorenzo Lisuzzo ◽  
Giuseppe Cavallaro ◽  
Giuseppe Lazzara ◽  
Stefana Milioto
Keyword(s):  
Degradation Kinetics ◽  
Kinetic Studies ◽  
Ionic Polymers ◽  
Heating Rates ◽  
Exponential Factor ◽  
Master Plot ◽  
Plot Analysis ◽  
Sustainable Polymers ◽  
Master Plot Analysis

AbstractIn this paper, films based on sustainable polymers with variable charge have been investigated by non-isothermal thermogravimetry in order to predict their lifetime, which is a key parameter for their potential use in numerous technological and biomedical applications. Specifically, chitosan has been selected as positively charged biopolymer, while alginate has been chosen as negatively charged biopolymer. Among non-ionic polymers, methylcellulose has been investigated. Thermogravimetric measurements at variable heating rates (5, 10, 15 and 20 °C min−1) have been performed for all the polymers to study their degradation kinetics by using isoconversional procedures combined with ‘Master plot’ analyses. Both integral (KAS and Starink methods) and differential (Friedman method) isoconversional procedures have shown that chitosan possesses the highest energetic barrier to decomposition. Based on the Master plot analysis, the decomposition of ionic polymers can be described by the R2 kinetic model (contracted cylindrical geometry), while the degradation of methylcellulose reflects the D2 mechanism (two-dimensional diffusion). The determination of both the decomposition mechanism and the kinetic parameters (activation energy and pre-exponential factor) has been used to determine the decay time functions of the several biopolymers. The obtained insights can be helpful for the development of durable films based on sustainable polymers with variable electrostatic characteristics. Graphical abstract

scholarly journals Micellar Electrokinetic Chromatographic Study of the Separation of an Aromatase Inhibitor and a Tryciclic Antidepressant in the Breast Cancer Treatment

2008 ◽  
Vol 3 ◽  
pp. ACI.S939 ◽  
Author(s):  
J. Rodríguez Flores ◽  
A.M. Contento Salcedo ◽  
L. Muñoz Fernández
Keyword(s):  
Micellar Electrokinetic Chromatography ◽  
Solid Phase ◽  
Background Electrolyte ◽  
Kinetic Studies ◽  
Breast Cancer Treatment ◽  
Chromatographic Study ◽  
Optimal Conditions ◽  
Sodium Dodecylsulphate ◽  
Experimental Parameters

Micellar electrokinetic chromatography (MEKC) was investigated for the simultaneous determination of letrozole, imipramine and their metabolites in human urine samples over a concentration range of therapeutic interest. Experimental parameters such as pH of the running electrolyte, sodium dodecylsulphate (SDS) concentration, borate concentration, voltage, etc were investigated. Under optimal conditions of 25 mM SDS, 15 mM borate buffer (pH 9.2), 15% 2-propanol, as background electrolyte; 28 kV and 40 °C, as voltage and cartridge temperature, respectively; resolution between the peaks was greater than 1.7. Before the determination, a solid phase extraction (SPE) procedure with a C18 cartridge was optimized. Good linearity, accuracy, precision, robustness and ruggedness were achieved and detection limits of 12.5 ng/mL for letrozole and its metabolite and 37.5 ng/mL, were obtained for imipramine and their metabolites. Real determinations of these analytes in two patient urines were carried out. Sensitivity achieved in this method is sufficient to perform kinetic studies in humans.

Determination of true Ki values in enzyme dead-end inhibition kinetic studies

1976 ◽  
Vol 71 (2) ◽  
pp. 507-518 ◽  
Author(s):  
Michael F. Thompson ◽  
Herman S. Bachelard
Keyword(s):  
Kinetic Studies ◽  
Dead End ◽  
Inhibition Kinetic

Isolation of radioactive iodothyronines for kinetic studies: a comparison of two methods

1982 ◽  
Vol 99 (1) ◽  
pp. 64-71 ◽  
Author(s):  
Jens Faber ◽  
lb Bo Lumholtz ◽  
Carsten Kirkegaard ◽  
Kaj Siersbæk-Nielsen ◽  
Thorkild Friis
Keyword(s):  
Radioactive Iodine ◽  
Single Injection ◽  
Kinetic Studies ◽  
Acid Precipitation ◽  
Relative Difference ◽  
Metabolic Clearance ◽  
Metabolic Clearance Rate ◽  
Minor Degree ◽  
A Minor

Abstract. A method based on the principle of gel separation followed by antibody extraction (GSAE) has been developed for isolation of radioactive thyroxine (T4), 3,5,3'-triiodothyronine (T3), 3,3',5'-triiodothyronine (rT3), 3,3'-diiodothyronine (3,3'-T2), 3',5'-diiodothyronine (3',5'-T2) and 3'-monoiodothyronine (3'-T1) in serum. This method was used for the estimation of the metabolic clearance rate (MCR) of the iodothyronines using the single injection, non-compartmental approach, and was compared to the conventional trichloroacetic acid precipitation/ethanol extraction (TCA-E) technique. The GSAE method excluded the co-determination of radioactive iodine and iodoproteins, whereas the co-determination of radiolabelled daughter iodothyronines was found negligible. The relative difference of duplicate estimations of MCR was approximately 10%. Using the TCA-E method for isolation of tracer, the MCR of T4, T3 and rT3 was underestimated to a minor degree (20%), whereas the MCRs of 3,3'-T2, 3',5'-T2 and 3'-T1 were 20–40% of those estimated by the GSAE method. In conclusion the GSAE method was found suitable for kinetic studies of iodothyronines, whereas the TCA-E method cannot be used for turnover studies of 3,3'-T2, 3',5'-T2 or 3'-T1.

Photooxidation and ozonolysis of Δ3-carene and its oxidation product caronaldehyde in the atmospheric simulation chamber SAPHIR

2021 ◽  
Author(s):  
Luisa Hantschke ◽  
Anna Novelli ◽  
Birger Bohn ◽  
Changmin Cho ◽  
David Reimer ◽  
...  
Keyword(s):  
Oxidation Product ◽  
Boreal Forests ◽  
Oxidation Products ◽  
Organic Nitrate ◽  
Organic Nitrates ◽  
Peroxy Radicals ◽  
Atmospheric Conditions ◽  
Oxidation Reactions ◽  
Reaction Rate Constants ◽  
Simulation Chamber

<p>Of the total global annual monoterpene emissions, Δ<sup>3</sup>-carene contributes 4.5 %, making it the 7<sup>th</sup> most abundant monoterpene worldwide. As it is primarily emitted by pine trees, Δ<sup>3</sup>-carene can regionally gain in importance, for example in boreal forests and Mediterranean regions.  Oxidation products of monoterpenes such as organic nitrates and aldehydes are known to impact the formation of secondary pollutants such as ozone and particles, so understanding their atmospheric formation and fate is crucial.</p><p>The photooxidation and ozonolysis of Δ<sup>3</sup>-carene and the photooxidation and photolysis of its main daytime photooxidation product caronaldehyde were investigated in the atmospheric simulation chamber SAPHIR. Oxidation reactions were studied under atmospheric conditions with high (> 8 ppbv) and low (< 2 ppbv) NOx concentrations. Reaction rate constants of the reaction of Δ<sup>3</sup>-carene with OH and O<sub>3</sub>, and of the reaction of caronaldehyde with OH as well as photolysis frequencies of caronaldehyde were determined. Production and destruction rates of the sum of hydroxyl and peroxy radicals (ROx = OH+HO2+RO2) were analysed to determine if there were unaccounted production and loss processes of radicals in the oxidation of Δ<sup>3</sup>-carene. The yield of Δ<sup>3</sup>-carene’s oxidation product caronaldehyde was determined from measured timeseries from OH photooxidation and ozonolysis experiments. Additionally, the OH yield from ozonolysis of Δ<sup>3</sup>-carene was determined.</p><p>Organic nitrate (RONO<sub>2</sub>) yields of the reaction of RO<sub>2</sub> + NO, from RO<sub>2</sub> produced from the reactions of Δ<sup>3</sup>-carene and caronaldehyde with OH were determined by analyzing the reactive nitrogen species (NOy) in the chamber.</p>

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