scholarly journals Imine Reductase Based All-Enzyme Hydrogel with Intrinsic Cofactor Regeneration for Flow Biocatalysis

Micromachines ◽  
2019 ◽  
Vol 10 (11) ◽  
pp. 783 ◽  
Author(s):  
Patrick Bitterwolf ◽  
Felix Ott ◽  
Kersten S. Rabe ◽  
Christof M. Niemeyer

All-enzyme hydrogels are biocatalytic materials, with which various enzymes can be immobilized in microreactors in a simple, mild, and efficient manner to be used for continuous flow processes. Here we present the construction and application of a cofactor regenerating hydrogel based on the imine reductase GF3546 from Streptomyces sp. combined with the cofactor regenerating glucose-1-dehydrogenase from Bacillus subtilis. The resulting hydrogel materials were characterized in terms of binding kinetics and viscoelastic properties. The materials were formed by rapid covalent crosslinking in less than 5 min, and they showed a typical mesh size of 67 ± 2 nm. The gels were applied for continuous flow biocatalysis. In a microfluidic reactor setup, the hydrogels showed excellent conversions of imines to amines for up to 40 h in continuous flow mode. Variation of flow rates led to a process where the gels showed a maximum space-time-yield of 150 g·(L·day)−1 at 100 μL/min.

2021 ◽  
Author(s):  
Manuel Köckinger ◽  
Paul Hanselmann ◽  
Dominique M. Roberge ◽  
Pierro Geotti-Bianchini ◽  
C. Oliver Kappe ◽  
...  

Introduction of acetoxy groups to organic molecules is important for the preparation of many active ingredients and synthetic intermediates. A commonly used and attractive strategy is the oxidative decarboxylation of aliphatic carboxylic acids, which entails the generation of a new C(sp3)-O bond. This reaction has been traditionally carried out using excess amounts of harmful lead(IV) acetate. A sustainable alternative to stoichiometric oxidants is the Hofer-Moest reaction, which relies in the 2-electron anodic oxidation of the carboxylic acid. However, examples showing electrochemical acetoxylation of amino acids are scarce. Herein we present a general and scalable procedure for the anodic decarboxylative acetoxylation of amino acids in batch and continuous flow mode. The procedure has been applied to the derivatization of several natural and synthetic amino acids, including key intermediates for the synthesis of active pharmaceutical ingredients. Good to excellent yields were obtained in all cases. Transfer of the process from batch to a continuous flow cell signficantly increased reaction throughput and space-time yield, with excellent product yields obtained even in a single-pass. The sustainability of the electrochemical protocol has been examined by evaluating its green metrics. Comparison with the conventional method demonstrates that an electrochemical approach has a significant positive effect on the greenness of the process


2021 ◽  
Author(s):  
Manuel Köckinger ◽  
Paul Hanselmann ◽  
Dominique M. Roberge ◽  
Pierro Geotti-Bianchini ◽  
C. Oliver Kappe ◽  
...  

Introduction of acetoxy groups to organic molecules is important for the preparation of many active ingredients and synthetic intermediates. A commonly used and attractive strategy is the oxidative decarboxylation of aliphatic carboxylic acids, which entails the generation of a new C(sp3)-O bond. This reaction has been traditionally carried out using excess amounts of harmful lead(IV) acetate. A sustainable alternative to stoichiometric oxidants is the Hofer-Moest reaction, which relies in the 2-electron anodic oxidation of the carboxylic acid. However, examples showing electrochemical acetoxylation of amino acids are scarce. Herein we present a general and scalable procedure for the anodic decarboxylative acetoxylation of amino acids in batch and continuous flow mode. The procedure has been applied to the derivatization of several natural and synthetic amino acids, including key intermediates for the synthesis of active pharmaceutical ingredients. Good to excellent yields were obtained in all cases. Transfer of the process from batch to a continuous flow cell signficantly increased reaction throughput and space-time yield, with excellent product yields obtained even in a single-pass. The sustainability of the electrochemical protocol has been examined by evaluating its green metrics. Comparison with the conventional method demonstrates that an electrochemical approach has a significant positive effect on the greenness of the process


2020 ◽  
Vol 02 (03) ◽  
pp. e128-e132
Author(s):  
Shao-Zheng Guo ◽  
Zhi-Qun Yu ◽  
Wei-Ke Su

AbstractThe development of highly efficient C–C bond formation methods for the synthesis of ethyl 2-(2,4-dichloro-5-fluorobenzoyl)-3-(dimethylamino)acrylate 1 in continuous flow processes has been described, which is based on the concept of rapid and efficient activation of carboxylic acid. 2,4-Dichloro-5-fluorobenzoic acid is rapidly converted into highly reactive 2,4-dichloro-5-fluorobenzoyl chloride by treating with inexpensive and less-toxic solid bis(trichloromethyl)carbonate. And then it rapidly reacts with ethyl 3-(dimethylamino)acrylate to afford the desired 1. This process can be performed under mild conditions. Compared with the traditional tank reactor process, less raw material consumption, higher product yield, less reaction time, higher operation safety ensured by more the environmentally friendly procedure, and process continuity are achieved in the continuous-flow system.


1990 ◽  
Vol 19 (1-4) ◽  
pp. 258-262 ◽  
Author(s):  
John R. English ◽  
Tep Sastri

2009 ◽  
Vol 52 (1-3) ◽  
pp. 15-18 ◽  
Author(s):  
L. B. He ◽  
B. Xie ◽  
F. Q. Song ◽  
C. H. Xu ◽  
J. F. Zhou ◽  
...  

2021 ◽  
Author(s):  
Long-Zhou Qin ◽  
Xin Yuan ◽  
Jie Liu ◽  
Meng-yu Wu ◽  
Qi Sun ◽  
...  

Herein, we develop a novel method for the selective alkynylation of cysteine-containing peptides and 1-thioglycoside residues by the use of continuous flow. This method was characterised by the mild conditions...


Chemosphere ◽  
2019 ◽  
Vol 219 ◽  
pp. 328-334 ◽  
Author(s):  
Victor Augusto Araújo de Freitas ◽  
Samuel Moura Breder ◽  
Flávia Paulucci Cianga Silvas ◽  
Patrícia Radino Rouse ◽  
Luiz Carlos Alves de Oliveira

ChemSusChem ◽  
2013 ◽  
Vol 7 (2) ◽  
pp. 536-542 ◽  
Author(s):  
Krzysztof Skowerski ◽  
Stefan J. Czarnocki ◽  
Paweł Knapkiewicz

2015 ◽  
Vol 74 (3) ◽  
Author(s):  
S. M. Zain ◽  
N. L. Ching ◽  
S. Jusoh ◽  
S. Y. Yunus

The aim of this study is to identify the relationship between the rate of electricity generation and the rate of carbon and nitrogen removal from wastewater using different MFC processes.  Determining whether the generation of electricity using MFC process could be related to the rate of pollutant removal from wastewater is noteworthy. Three types of MFC process configurations include the batch mode (SS), a continuous flow of influent with ferricyanide (PF) as the oxidizing agent and a continuous flow of influent with oxygen (PU) as the oxidizing agent. The highest quantity of electricity generation was achieved using the continuous flow mode with ferricyanide (0.833 V), followed by the continuous flow mode with oxygen (0.589 V) and the batch mode (0.352 V). The highest efficiency of carbon removal is also achieved by the continuous flow mode with ferricyanide (87%), followed by the continuous flow mode with oxygen (51%) and the batch mode (46%). Moreover, the continuous flow mode with ferricyanide produced the highest efficiency for nitrogen removal (63%), followed by the continuous flow mode with oxygen (54%) and the batch mode (27%).


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