scholarly journals Synthesis of Linoleic Acid 13-Hydroperoxides from Safflower Oil Utilizing Lipoxygenase in a Coupled Enzyme System with In-Situ Oxygen Generation

Catalysts ◽  
2021 ◽  
Vol 11 (9) ◽  
pp. 1119
Author(s):  
Valentin Gala Marti ◽  
Anna Coenen ◽  
Ulrich Schörken

Linoleic acid hydroperoxides are versatile intermediates for the production of green note aroma compounds and bifunctional ω-oxo-acids. An enzyme cascade consisting of lipoxygenase, lipase and catalase was developed for one-pot synthesis of 13-hydroperoxyoctadecadienoic acid starting from safflower oil. Reaction conditions were optimized for hydroperoxidation using lipoxygenase 1 from Glycine max (LOX-1) in a solvent-free system. The addition of green surfactant Triton CG-110 improved the reaction more than two-fold and yields of >50% were obtained at linoleic acid concentrations up to 100 mM. To combine hydroperoxidation and oil hydrolysis, 12 lipases were screened for safflower oil hydrolysis under the reaction conditions optimized for LOX-1. Lipases from Candida rugosa and Pseudomonas fluorescens were able to hydrolyze safflower oil to >75% within 5 h at a pH of 8.0. In contrast to C. rugosa lipase, the enzyme from P. fluorescens did not exhibit a lag phase. Combination of P. fluorescens lipase and LOX-1 worked well upon LOX-1 dosage and a synergistic effect was observed leading to >80% of hydroperoxides. Catalase from Micrococcus lysodeikticus was used for in-situ oxygen production with continuous H2O2 dosage in the LOX-1/lipase reaction system. Foam generation was significantly reduced in the 3-enzyme cascade in comparison to the aerated reaction system. Safflower oil concentration was increased up to 300 mM linoleic acid equivalent and 13-hydroperoxides could be produced in a yield of 70 g/L and a regioselectivity of 90% within 7 h.

2016 ◽  
Vol 843 ◽  
pp. 173-177
Author(s):  
S.M. Lipkin ◽  
V.S. Elsukov ◽  
V.I. Lachin

This article is about adaptive adjustment of reaction conditions in local electrochemical rapid analysis. These conditions include in-situ current correction during pulse chronopotentiogram mesuarements. Optimal values of correction parameters were obtained by steep ascent optimization method. Treatment of gold alloys chronopotentiograms was made by the decomposition modeling method. As a result, application of a probe current adjustment system to chronopotentiometry process allows more than 3-time increase in reproducibility of experimental results. The most significant factors in optimizing the parameters of the proposed system are the slope of the linear regression coefficient of the reaction system.


2008 ◽  
Vol 63 (2) ◽  
pp. 108-110 ◽  
Author(s):  
A. B. Maidina ◽  
A. B. Belova ◽  
A. V. Levashov ◽  
N. L. Klyachko

2015 ◽  
Vol 2015 ◽  
pp. 1-10 ◽  
Author(s):  
Marya Aziz ◽  
Florence Husson ◽  
Selim Kermasha

Commercial lipases, from porcine pancreas (PPL),Candida rugosa(CRL), andThermomyces lanuginosus(Lipozyme TL IM), were investigated in terms of their efficiency for the hydrolysis of safflower oil (SO) for the liberation of free linoleic acid (LA), used as a flavor precursor. Although PPL, under the optimized conditions, showed a high degree of hydrolysis (91.6%), its low tolerance towards higher substrate concentrations could limit its use for SO hydrolysis. In comparison to the other investigated lipases, Lipozyme TL IM required higher amount of enzyme and an additional 3 h of reaction time to achieve its maximum degree of SO hydrolysis (90.2%). On the basis of the experimental findings, CRL was selected as the most appropriate biocatalyst, with 84.1% degree of hydrolysis. The chromatographic analyses showed that the CRL-hydrolyzed SO is composed mainly of free LA.


2012 ◽  
Vol 3 ◽  
pp. 667-673 ◽  
Author(s):  
Thomas Simons ◽  
Ulrich Simon

In a proof-of-concept study we demonstrate in situ reaction monitoring of DeNOx-SCR on proton-conducting zeolites serving as catalyst and gas sensor at the same time. By means of temperature-dependent impedance spectroscopy we found that the thermally induced NH3 desorption in H-form and in Fe-loaded zeolite H-ZSM-5 follow the same process, while a remarkable difference under DeNOx-SCR reaction conditions was found. The Fe-loaded catalyst shows a significantly lower onset temperature, and time-dependent measurements suggest different SCR reaction mechanisms for the two catalysts tested. These results may help in the development of catalysts for the reduction of NOx emissions and ammonia consumption, and provide insight into the elementary catalytic process promoting a full description of the NH3-SCR reaction system.


Molecules ◽  
2021 ◽  
Vol 26 (13) ◽  
pp. 3844
Author(s):  
Lijuan Li ◽  
Bingdong Li ◽  
Liwei Feng ◽  
Xiaoqiu Zhang ◽  
Yuqian Zhang ◽  
...  

In this work, Au-modified F-TiO2 is developed as a simple and efficient photocatalyst for H2O2 production under ultraviolet light. The Au/F-TiO2 photocatalyst avoids the necessity of adding fluoride into the reaction medium for enhancing H2O2 synthesis, as in a pure TiO2 reaction system. The F− modification inhibits the H2O2 decomposition through the formation of the ≡Ti–F complex. Au is an active cocatalyst for photocatalytic H2O2 production. We compared the activity of TiO2 with F− modification and without F− modification in the presence of Au, and found that the H2O2 production rate over Au/F-TiO2 reaches four times that of Au/TiO2. In situ electron spin resonance studies have shown that H2O2 is produced by stepwise single-electron oxygen reduction on the Au/F-TiO2 photocatalyst.


Molecules ◽  
2021 ◽  
Vol 26 (5) ◽  
pp. 1466
Author(s):  
Ye Eun Kim ◽  
Hyunsung Cho ◽  
Yoo Jin Lim ◽  
Chorong Kim ◽  
Sang Hyup Lee

Studies on a one-pot synthesis of novel multisubstituted 1-alkoxyindoles 1 and their mechanistic investigations are presented. The synthesis of 1 was successfully achieved through consecutive four step reactions from substrates 2. The substrates 2, prepared through a two-step synthetic sequence, underwent three consecutive reactions of nitro reduction, intramolecular condensation, and nucleophilic 1,5-addition to provide the intermediates, 1-hydroxyindoles 8, which then were alkylated in situ with alkyl halide to afford the novel target products 1. We optimized the reaction conditions for 1 focusing on the alkylation step, along with the consideration of formation of intermediates 8. The optimized condition was SnCl2·2H2O (3.3 eq) and alcohols (R1OH, 2.0 eq) for 1–2 h at 40 °C and then, base (10 eq) and alkyl halides (R2Y, 2.0 eq) for 1–4 h at 25–50 °C. Notably, all four step reactions were performed in one-pot to give 1 in good to modest yields. Furthermore, the mechanistic aspects were also discussed regarding the reaction pathways and the formation of side products. The significance lies in development of efficient one-pot reactions and in generation of new 1-alkoxyindoles.


Nanoscale ◽  
2015 ◽  
Vol 7 (40) ◽  
pp. 16952-16959 ◽  
Author(s):  
Kaige Zhang ◽  
Gongke Li ◽  
Yuling Hu

The surface-enhanced Raman spectroscopy (SERS) technique is of great importance for insight into the transient reaction intermediates and mechanistic pathways involved in heterogeneously catalyzed chemical reactions under actual reaction conditions, especially in water.


1994 ◽  
Vol 48 (10) ◽  
pp. 1208-1212 ◽  
Author(s):  
J. J. Benítez ◽  
I. Carrizosa ◽  
J. A. Odriozola

The reactivity of a Lu2O3-promoted Rh/Al2O3 catalyst in the CO/H2 reaction is reported. Methane, heavier hydrocarbons, methanol, and ethanol are obtained. In situ DRIFTS has been employed to record the infrared spectra under the actual reaction conditions. The structure of the observed COads DRIFTS bands has been resolved into its components. The production of oxygenates (methanol and ethanol) has been correlated with the results of the deconvolution calculation. Specific sites for the production of methanol and ethanol in the CO/H2 reaction over a Rh,Lu2O3/Al2O3 catalyst are proposed.


2016 ◽  
Vol 12 ◽  
pp. 2588-2601 ◽  
Author(s):  
Vladimir A Stepchenko ◽  
Anatoly I Miroshnikov ◽  
Frank Seela ◽  
Igor A Mikhailopulo

The trans-2-deoxyribosylation of 4-thiouracil (4SUra) and 2-thiouracil (2SUra), as well as 6-azauracil, 6-azathymine and 6-aza-2-thiothymine was studied using dG and E. coli purine nucleoside phosphorylase (PNP) for the in situ generation of 2-deoxy-α-D-ribofuranose-1-phosphate (dRib-1P) followed by its coupling with the bases catalyzed by either E. coli thymidine (TP) or uridine (UP) phosphorylases. 4SUra revealed satisfactory substrate activity for UP and, unexpectedly, complete inertness for TP; no formation of 2’-deoxy-2-thiouridine (2SUd) was observed under analogous reaction conditions in the presence of UP and TP. On the contrary, 2SU, 2SUd, 4STd and 2STd are good substrates for both UP and TP; moreover, 2SU, 4STd and 2’-deoxy-5-azacytidine (Decitabine) are substrates for PNP and the phosphorolysis of the latter is reversible. Condensation of 2SUra and 5-azacytosine with dRib-1P (Ba salt) catalyzed by the accordant UP and PNP in Tris∙HCl buffer gave 2SUd and 2’-deoxy-5-azacytidine in 27% and 15% yields, respectively. 6-Azauracil and 6-azathymine showed good substrate properties for both TP and UP, whereas only TP recognizes 2-thio-6-azathymine as a substrate. 5-Phenyl and 5-tert-butyl derivatives of 6-azauracil and its 2-thioxo derivative were tested as substrates for UP and TP, and only 5-phenyl- and 5-tert-butyl-6-azauracils displayed very low substrate activity. The role of structural peculiarities and electronic properties in the substrate recognition by E. coli nucleoside phosphorylases is discussed.


2014 ◽  
Vol 997 ◽  
pp. 368-370
Author(s):  
Ping Zhong ◽  
Lin Xiu Cheng ◽  
Xing Lu

In this paper,ZnO/PANI transparent conductive film has been prepared by in situ chemical oxidative polymerization, APS as an oxidant. The conductivity and transmittance of ZnO/PANI was measured. It has been investigated of the effects of reaction conditions and the doping component on conductivity, transmissivity and adhesion. With the increase of doping ZnO, the conductivity of ZnO/PANI transparent conductive film, transmittance and adhesion reduced. The optimal conditions is that the concentration of An, APS and PVA are 0.75 mol / L, 0.8 mol / L and 0.5wt%, respectively.


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