Catalytic amidolysis of amino acid p -nitroanilides using transition state analogue imprinted artificial enzymes: Cooperative effect of pyridine moiety

Mathew, Dona; Thomas, Benny; Christy, Philip; Aparna, E.; Devaky, K. S.

doi:10.1016/j.bioorg.2017.07.015

Cited by 6 publications

(6 citation statements)

References 34 publications

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“…Based on polymer supports, several promising strategies were devised to construct cooperative multifunctional catalysts. − For instance, the molecular imprinting strategy was widely used to synthesize highly cross-linked polymer catalysts using the lock-and-key principle, − exhibiting excellent activity, efficiency, and proficiency. Such a strategy requires carefully designed transition state analogues as templates, causes high structural rigidity, lacks versatility, and limits the catalytic scope.…”

Section: Introductionmentioning

confidence: 99%

Polystyrene-Supported Cu/2,2,6,6-Tetramethyl-1-piperidine-N-oxyl Catalytic Systems Constructed by Nanoprecipitation and Their Cooperative Catalysis for Benzyl Alcohol Oxidation

Chen

Wang

Xiao

et al. 2021

ACS Appl. Polym. Mater.

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Transformation of multifunctional homogeneous catalysts to the corresponding heterogeneous catalytic systems makes catalytic reactions interesting from both economic and environmental points of view. Here, we have devised a controllable and efficient strategy for the preparation of supported multifunctional catalysts by taking the Cu/2,2,6,6-tetramethyl-1-piperidine-N-oxyl (TEMPO) catalytic system as an example. Polystyrene-supported Cu/TEMPO catalysts were, for the first time, prepared via nanoprecipitation of polymers in water and efficient for aerobic oxidation of benzyl alcohol (BnOH). Cooperative behaviors could be regulated by precise control of local concentrations of functional groups. We have demonstrated that the incorporation of functional groups into polystyrene supports can make better use of catalytic components, resulting from confinement-enhanced cooperation. This strategy provides access to build more efficient multifunctional heterogeneous catalysts through establishing structure–activity relationships.

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Section: Introductionmentioning

confidence: 99%

Polystyrene-Supported Cu/2,2,6,6-Tetramethyl-1-piperidine-N-oxyl Catalytic Systems Constructed by Nanoprecipitation and Their Cooperative Catalysis for Benzyl Alcohol Oxidation

Chen

Wang

Xiao

et al. 2021

ACS Appl. Polym. Mater.

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“…An attempt to directly correlate the research results with literature data is quite difficult. This is due to the incompatibility of catalytic structures with other synzymes with peptidic active fragment [44,45,46,47,48,49,50]. The comparison of the effectiveness of N -lipidated peptides immobilized on cellulose to catalyse the hydrolysis of esters [40,41] and amides indicates that degradation of amide/peptide bond is more demanding and possible only with highly active catalytic systems.…”

Section: Resultsmentioning

confidence: 99%

N-Lipidated Amino Acids and Peptides Immobilized on Cellulose Able to Split Amide Bonds

Frączyk

Kamiński

2019

Materials

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N-lipidated short peptides and amino acids immobilized on the cellulose were used ascatalysts cleaved amide bonds under biomimetic conditions. In order to select catalytically mostactive derivatives a library of 156 N-lipidated amino acids, dipeptides and tripeptides immobilizedon cellulose was obtained. The library was synthesized from serine, histidine and glutamic acidpeptides N-acylated with heptanoic, octanoic, hexadecanoic and (E)-octadec-9-enoic acids.Catalytic efficiency was monitored by spectrophotometric determination of p-nitroaniline formedby the hydrolysis of a 0.1 M solution of Z-Leu-NP. The most active 8 structures contained tripeptidefragment with 1-3 serine residues. It has been found that incorporation of metal ions into catalyticpockets increase the activity of the synzymes. The structures of the 17 most active catalysts selectedfrom the library of complexes obtained with Cu2+ ion varied from 16 derivatives complexed withZn2+ ion. For all of them, a very high reaction rate during the preliminary phase of measurementswas followed by a substantial slowdown after 1 h. The catalytic activity gradually diminished aftersubsequent re-use. HPLC analysis of amide bond splitting confirmed that substrate consumptionproceeded in two stages. In the preliminary stage 24–40% of the substrate was rapidly hydrolysedfollowed by the substantially lower reaction rate. Nevertheless, using the most competentsynzymes product of hydrolysis was formed with a yield of 60–83% after 48h under mild andstrictly biomimetic conditions.

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“…Hydrolysis of esters or amides using natural chymotrypsin is usually carried out at room temperatures because of the denaturation of the enzyme at higher temperatures. The optimum temperature for catalytic amidolysis using MIPs was found to be 45-50 C [63][64][65][66][67].…”

Section: Effect Of Temperaturementioning

confidence: 99%

“…Replacement of allyl alcohol from the monomer triad by vinylpyridine afforded a catalyst with better enzymatic activity. The pyridine moiety was found to be capable of exerting H-bonding interaction with carboxyl group of methacrylic acid and p-stacking interaction with aromatic side chain of amino acid residue of the substrate p-nitroanilide ( Figure 33) [66].…”

Section: Transition State Analogue Imprinted Amidasesmentioning

confidence: 99%

“…The enzyme mimic polymer catalyst exhibited bell-shaped pH profile in catalytic amidolysis like natural chymotrypsin. The optimum rate was observed at pH 7.75. in acidic medium protonation of the imidazole moiety is thought to be the retarding force of catalytic rate [63][64][65][66][67]. However, MIPs possess many disadvantageous: it is hard to completely remove the print molecule from MIPs; the imprinted polymer is insoluble; and the polymer contains heterogeneous binding sites.…”

Section: Effect Of Phmentioning

confidence: 99%

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Design, synthesis and characterization of enzyme-analogue-built polymer catalysts as artificial hydrolases

Mathew

Thomas

Devaky

2019

Artificial Cells, Nanomedicine, and Biotechnology

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In this review, the concept and various strategies in molecular imprinting is discussed briefly. How the concept of transition state analogue can be used to design a template to prepare catalytic imprinted polymers is described in detail. The use of the "bait and switch" approach and alternative covalent template strategies show how functional groups which assist in the catalytic properties can be assembled within the imprint. Thus, there are so many reports on P catalyzed reactions. Owing to their advantageous properties over natural biological recognition agents, molecularly imprinted polymers (MIPs) therefore offer great potential for various applications.

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Catalytic amidolysis of amino acid p -nitroanilides using transition state analogue imprinted artificial enzymes: Cooperative effect of pyridine moiety

Cited by 6 publications

References 34 publications

Polystyrene-Supported Cu/2,2,6,6-Tetramethyl-1-piperidine-N-oxyl Catalytic Systems Constructed by Nanoprecipitation and Their Cooperative Catalysis for Benzyl Alcohol Oxidation

Polystyrene-Supported Cu/2,2,6,6-Tetramethyl-1-piperidine-N-oxyl Catalytic Systems Constructed by Nanoprecipitation and Their Cooperative Catalysis for Benzyl Alcohol Oxidation

N-Lipidated Amino Acids and Peptides Immobilized on Cellulose Able to Split Amide Bonds

Design, synthesis and characterization of enzyme-analogue-built polymer catalysts as artificial hydrolases

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