scholarly journals Characterization and Catalytic-Site-Analysis of an Aldo-Keto Reductase with Excellent Solvent Tolerance

Catalysts ◽  
2020 ◽  
Vol 10 (10) ◽  
pp. 1121
Author(s):  
Rui Pei ◽  
Weiliang Wu ◽  
Yuqian Zhang ◽  
Libing Tian ◽  
Wei Jiang ◽  
...  

Aldo-keto reductases (AKRs) mediated stereoselective reduction of prochiral carbonyl compounds is an efficient way of preparing single enantiomers of chiral alcohols due to their high chemo-, enantio-, and regio-selectivity. To date, the application of AKRs in the asymmetric synthesis of chiral alcohols has been limited, due to the challenges of cloning and purifying. In this work, the aldo-keto reductase (AKR3-2-9) from Bacillus sp. was obtained, purified and proved to be NADPH-dependent. It exhibits good bioactivity and stability at 37 °C, pH 6.0. AKR3-2-9 is catalytically active on 11 pairs of substrates such as 3-methylcyclohexanone and methyl pyruvate, among which it showed the highest catalytic activity for acetylacetone. In addition, AKR3-2-9 was able to be resistant to five common organic solvents such as methanol and ethanol, it retained high catalytic activity even in a reaction system containing 10% v/v organic solvent for 6 h, which indicates its broad substrate spectrum and exceptional organic solvent tolerance. Furthermore, its three-dimensional structure was constructed and catalytic-site-analysis of the enzyme was conducted. Notably, it was capable of catalyzing the reaction of the key intermediates of duloxetine. The extensive substrate spectrum and predominant organic solvents resistance makes AK3-2-9 a promising enzyme which can be potentially applied in medicine synthesis.

PLoS ONE ◽  
2021 ◽  
Vol 16 (12) ◽  
pp. e0260787
Author(s):  
Wei Jiang ◽  
Xiaoli Fu ◽  
Weiliang Wu

The biosynthesis of chiral alcohols has important value and high attention. Aldo–keto reductases (AKRs) mediated reduction of prochiral carbonyl compounds is an interesting way of synthesizing single enantiomers of chiral alcohols due to the high enantio-, chemo- and regioselectivity of the enzymes. However, relatively little research has been done on characterization and apply of AKRs to asymmetric synthesis of chiral alcohols. In this study, the AKR from Candida tropicalis MYA-3404 (C. tropicalis MYA-3404), was mined and characterized. The AKR shown wider optimum temperature and pH. The AKR exhibited varying degrees of catalytic activity for different substrates, suggesting that the AKR can catalyze a variety of substrates. It is worth mentioning that the AKR could catalytic reduction of keto compounds with benzene rings, such as cetophenone and phenoxyacetone. The AKR exhibited activity on N,N-dimethyl-3-keto-3-(2-thienyl)-1-propanamine (DKTP), a key intermediate for biosynthesis of the antidepressant drug duloxetine. Besides, the AKR still has high activity whether in a reaction system containing 10%-30% V/V organic solvent. What’s more, the AKR showed the strongest stability in six common organic solvents, DMSO, acetonitrile, ethyl acetate, isopropanol, ethanol, and methanol. And, it retains more that 70% enzyme activity after 6 hours, suggesting that the AKR has strong solvent tolerance. Furthermore, the protein sequences of the AKR and its homology were compared, and a 3D model of the AKR docking with coenzyme NADPH were constructed. And the important catalytic and binding sites were identified to explore the binding mechanism of the enzyme and its coenzyme. These properties, predominant organic solvents resistance and extensive substrate spectrum, of the AKR making it has potential applications in the pharmaceutical field.


2015 ◽  
Vol 44 (46) ◽  
pp. 19800-19804 ◽  
Author(s):  
Mingdong Zhong ◽  
Zhi Yang ◽  
Yafei Yi ◽  
Dongxiang Zhang ◽  
Kening Sun ◽  
...  

Reactions of LSnCl (1) (L = N(2,6-iPr2C6H3)(SiMe3)) with sulfur and selenium, respectively under mild conditions yielded two tin chalcogenide clusters. The two products show high catalytic activity in ROP catalysis.


Materials ◽  
2020 ◽  
Vol 13 (8) ◽  
pp. 1951 ◽  
Author(s):  
Fenglian Huang ◽  
Shiqiang Tian ◽  
Yan Qi ◽  
Erping Li ◽  
Liangliang Zhou ◽  
...  

(1) Background: Iron tetrasulfophthalocyanine with a large nonlinear optical coefficient, good stability, and high catalytic activity has aroused the attention of researchers in the field of photo-Fenton reaction. Further improvement of the visible light photo-Fenton catalytic activity under circumneutral pH conditions for their practical application is still of great importance. (2) Methods: In this paper, iron tetrasulfophthalocyanine (FePcS) and phosphomolybdic acid (PMA) cointercalated layered double hydroxides (LDH) were synthesized by the ion-exchange method. All samples were fully characterized by various techniques and the results showed that FePcS and PMA were successfully intercalated in layered double hydroxides and the resulted compound exhibited strong absorption in the visible light region. The cointercalation compound was tested as a heterogeneous catalyst for the visible light photo-Fenton degradation of bisphenol A (BPA) at circumneutral pH. (3) Results: The results showed that the degradation and total organic carbon removal efficiencies of bisphenol A were 100% and 69.2%, respectively. (4) Conclusions: The cyclic voltammetry and electrochemical impedance spectroscopy measurements demonstrated that the main contribution of PMA to the enhanced photo-Fenton activity of FePcS–PMA–LDH comes from the acceleration of electron transfer in the reaction system. Additionally, the possible reaction mechanism in the photo-Fenton system catalyzed by FePcS–PMA–LDH was also proposed.


1998 ◽  
Vol 180 (11) ◽  
pp. 2987-2991 ◽  
Author(s):  
Xian-Zhi Li ◽  
Li Zhang ◽  
Keith Poole

ABSTRACT Multidrug efflux pumps with a broad substrate specificity make a major contribution to intrinsic and acquired multiple antibiotic resistance in Pseudomonas aeruginosa. Using genetically defined efflux pump mutants, we investigated the involvement of the three known efflux systems, MexA-MexB-OprM, MexC-MexD-OprJ, and MexE-MexF-OprN, in organic solvent tolerance in this organism. Our results showed that all three systems are capable of providing some level of tolerance to organic solvents such as n-hexane andp-xylene. Expression of MexAB-OprM was correlated with the highest levels of tolerance, and indeed, this efflux system was a major contributor to the intrinsic solvent tolerance of P. aeruginosa. Intrinsic organic solvent tolerance was compromised by a protonophore, indicating that it is substantially energy dependent. These data suggest that the efflux of organic solvents is a factor in the tolerance of P. aeruginosa to these compounds and that the multidrug efflux systems of this organism can accommodate organic solvents, as well as antibiotics.


AMB Express ◽  
2021 ◽  
Vol 11 (1) ◽  
Author(s):  
Noriyuki Doukyu ◽  
Katsuya Taguchi

AbstractEscherichia coli strains are generally sensitive to hydrophobic organic solvents such as n-hexane and cyclohexane. Oxidative stress in E. coli by exposure to these hydrophobic organic solvents has been poorly understood. In the present study, we examined organic solvent tolerance and oxygen radical generation in E. coli mutants deficient in reactive oxygen species (ROS)-scavenging enzymes. The organic solvent tolerances in single gene mutants lacking genes encoding superoxide dismutase (sodA, sodB, and sodC), catalase (katE and katG), and alkyl hydroperoxide reductase (ahpCF) were similar to that of parent strain BW25113. We constructed a BW25113-based katE katG double mutant (BW25113∆katE∆katG) and sodA sodB double mutant (BW25113sodA∆sodB). These double-gene mutants were more sensitive to hydrophobic organic solvents than BW25113. In addition, the intracellular ROS levels in E. coli strains increased by the addition of n-hexane or cyclohexane. The ROS levels in BW25113∆katE∆katG and BW25113∆sodA∆sodB induced by exposure to the solvents were higher than that in BW25113. These results suggested that ROS-scavenging enzymes contribute to the maintenance of organic solvent tolerance in E. coli. In addition, the promoter activities of sodA and sodB were significantly increased by exposure to n-hexane.


RSC Advances ◽  
2014 ◽  
Vol 4 (93) ◽  
pp. 51745-51753 ◽  
Author(s):  
Tanmoy Maji ◽  
Sanjib Banerjee ◽  
Mrinmoy Biswas ◽  
Tarun K. Mandal

Ultra-small platinum nanoparticles are generated by in situ polymer reduction technique which shows high catalytic activity in water and in organic solvent.


Catalysts ◽  
2020 ◽  
Vol 10 (9) ◽  
pp. 1015 ◽  
Author(s):  
Gentaro Sakamoto ◽  
Hiroyasu Tabe ◽  
Yusuke Yamada

Iridium hydroxide (Ir(OH)3) nanoparticles exhibiting high catalytic activity for water oxidation were immobilized inside mesospaces of a silica-nanoparticles assembly (SiO2NPA) to suppress catalytic deactivation due to agglomeration. The Ir(OH)3 nanoparticles immobilized in SiO2NPA (Ir(OH)3/SiO2NPA) catalyzed water oxidation by visible light irradiation of a solution containing persulfate ion (S2O82−) and tris(2,2′-bipyridine)ruthenium(II) ion ([RuII(bpy)3]2+) as a sacrificial electron acceptor and a photosensitizer, respectively. The yield of oxygen (O2) based on the used amount of S2O82− was maintained over 80% for four repetitive runs using Ir(OH)3/SiO2NPA prepared by the co-accumulation method, although the yield decreased for the reaction system using Ir(OH)3/SiO2NPA prepared by the equilibrium adsorption method or Ir(OH)3 nanoparticles without SiO2NPA support under the same reaction conditions. Immobilization of Ir(OH)3 nanoparticles in Al3+-doped SiO2NPA (Al-SiO2NPA) results in further enhancement of the catalytic stability with the yield of more than 95% at the fourth run of the repetitive experiments.


MRS Advances ◽  
2020 ◽  
Vol 5 (57-58) ◽  
pp. 2961-2972
Author(s):  
P.C. Meléndez-González ◽  
E. Garza-Duran ◽  
J.C. Martínez-Loyola ◽  
P. Quintana-Owen ◽  
I.L. Alonso-Lemus ◽  
...  

In this work, low-Pt content nanocatalysts (≈ 5 wt. %) supported on Hollow Carbon Spheres (HCS) were synthesized by two routes: i) colloidal conventional polyol, and ii) surfactant-free Bromide Anion Exchange (BAE). The nanocatalysts were labelled as Pt/HCS-P and Pt/HCS-B for polyol and BAE, respectively. The physicochemical characterization of the nanocatalysts showed that by following both methods, a good control of chemical composition was achieved, obtaining in addition well dispersed nanoparticles of less than 3 nm TEM average particle size (d) on the HCS. Pt/HCS-B contained more Pt0 species than Pt/HCS-P, an effect of the synthesis method. In addition, the structure of the HCS remains more ordered after BAE synthesis, compared to polyol. Regarding the catalytic activity for the Oxygen Reduction Reaction (ORR) in 0.5 M KOH, Pt/HCS-P and Pt/HCS-B showed a similar performance in terms of current density (j) at 0.9 V vs. RHE than the benchmark commercial 20 wt. % Pt/C. However, Pt/HCS-P and Pt/HCS-B demonstrated a 6 and 5-fold increase in mass catalytic activity compared to Pt/C, respectively. A positive effect of the high specific surface area of the HCS and its interactions with metal nanoparticles and electrolyte, which promoted the mass transfer, increased the performance of Pt/HCS-P and Pt/HCS-B. The high catalytic activity showed by Pt/HCS-B and Pt/HCS-P for the ORR, even with a low-Pt content, make them promising cathode nanocatalysts for Anion Exchange Membrane Fuel Cells (AEMFC).


2019 ◽  
Author(s):  
Du Sun ◽  
yunfei wang ◽  
Kenneth Livi ◽  
chuhong wang ◽  
ruichun luo ◽  
...  

<div> <p>The synthesis of alloys with long range atomic scale ordering (ordered intermetallics) is an emerging field of nanochemistry. Ordered intermetallic nanoparticles are useful for a wide variety of applications such as catalysis, superconductors, and magnetic devices. However, the preparation of nanostructured ordered intermetallics is challenging in comparison to disordered alloys, hindering progress in materials development. We report a process for converting colloidally synthesized ordered intermetallic PdBi<sub>2</sub> to ordered intermetallic Pd<sub>3</sub>Bi nanoparticles under ambient conditions by an electrochemically induced phase transition. The low melting point of PdBi<sub>2</sub> corresponds to low vacancy formation energies which enables the facile removal of the Bi from the surface, while simultaneously enabling interdiffusion of the constituent atoms via a vacancy diffusion mechanism under ambient conditions. The resulting phase-converted ordered intermetallic Pd<sub>3</sub>Bi exhibits 11x and 3.5x higher mass activty and high methanol tolerance for the oxygen reduction reaction compared to Pt/C and Pd/C, respectively,which is the highest reported for a Pd-based catalyst, to the best of our knowledge. These results establish a key development in the synthesis of noble metal rich ordered intermetallic phases with high catalytic activity, and sets forth guidelines for the design of ordered intermetallic compounds under ambient conditions.</p> </div>


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