Pd-Oxazolone complexes conjugated to an engineered enzyme: improving fluorescence and catalytic properties

Garcia-Sanz, Carla; Andreu, Alicia; Rivas, Blanca de las; Jiménez, Ana I.; Pop, Alexandra; Silvestru, Cristian; Urriolabeitia, Esteban P.; Palomo, José M.

doi:10.1039/d1ob00305d

Cited by 14 publications

(21 citation statements)

References 43 publications

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“…This assay was performed by measuring in a UV-spectrophotometer the increase in the absorbance at 348 nm produced by the release of p -nitrophenol in the hydrolysis of 0.4 mM ( 1 ) as previously reported, using 3 mg of solid or 20 μL lipase solution and 5 mL of substrate solution, measuring the absorbance (ΔAbs/min) at different times.…”

Section: Methodsmentioning

confidence: 99%

Metal Nanoparticles Incorporated within Graphene-Enzyme Preparations for Synergistic Multiactive Catalysts

Losada-Garcia

Urriolabeitia

Palomo

2022

ACS Appl. Nano Mater.

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The development of catalytic systems with different chemo- and biocatalytic functionalities for sustainable one-pot multistep transformations represents a big challenge in modern chemistry. Here, we have designed and synthesized enzyme-metal hybrids’ materials of palladium and copper as multiactive heterogeneous catalysts. The in situ formation of metallic nanoparticles of different size and species on multilayer graphene-anchored Candida antarctica lipase (G@CALB) at room temperature and aqueous media allowed creation of different kinds of enzyme-metal nanoarchitectures, where the metal nanoparticles were synthesized exclusively when induced by an enzyme, dispersed homogeneously on the enzyme structure as the scaffold. The creation of copper or palladium nanoparticles on the graphene-enzyme preparation allowed obtaining a new type of enzyme-metal bifunctional catalyst conserving the enzymatic activity intact and enhancing the metallic properties. Furthermore, the creation of a CuPd alloy on immobilized enzyme preparation (G@CALB-PdNPs-CuNPs) allowed obtaining a new enzyme-bimetallic trifunctional catalyst, with extremely enhanced metallic activity by the synergistic effect. These hybrids were successfully applied in different cascade processes, where the hybrid G@CALB-PdNPs-CuNPs, based on its property, showed superior efficiency to bifunctional hybrids in the regioselective and asymmetric one-pot tandem processes tested.

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Section: Methodsmentioning

confidence: 99%

Metal Nanoparticles Incorporated within Graphene-Enzyme Preparations for Synergistic Multiactive Catalysts

Losada-Garcia

Urriolabeitia

Palomo

2022

ACS Appl. Nano Mater.

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“…Evaporate the solvent using a rotary evaporator at 40° C under vacuum aspirator (200 mbar) to obtain the product. 1 H NMR (400.13 MHz, D2O, 25 °C): δ= 6.17 13 C could be determined. 13 C chemical shifts were obtained from edited-HSQC and HMBC 2D 1 H-13 C correlation spectra.…”

Section: Cascade Reaction Synthesis Of Disaccharides 7/8 From Peracet...mentioning

confidence: 99%

“…1 H NMR (400.13 MHz, D2O, 25 °C): δ= 6.17 13 C could be determined. 13 C chemical shifts were obtained from edited-HSQC and HMBC 2D 1 H-13 C correlation spectra.…”

Section: Cascade Reaction Synthesis Of Disaccharides 7/8 From Peracet...mentioning

confidence: 99%

“…One has been the direct incorporation of metals or organometallic complexes into a protein structure combining genetic and chemical tools, creating new artificial active sites. [12][13][14][15][16] Another successful approach has been the co-immobilization of both chemo-and biocatalytic systems in a solid material. 17 This methodology introduced the advantage of heterogeneous system although the compatibility of carriers and enzymes, insufficient exposure of active sites, low reactivity of the heterogeneous phase under ambient conditions, and poor molecular transport still remain as major hurdles in their use in cascade reactions.…”

Section: Introductionmentioning

confidence: 99%

“…, 1H, H-5), 2.15 (s, 3H, Ac), 2.06 (s, 3H, Ac), 2.04 (s, 3H, Ac) 13. C NMR (100.61 MHz, D2O, 25 °C): δ= 174.23 (2C collapsed, C=O), 172.18 (C=O), 89.16 (C-2), 71.73 (C-6), 20.30 (Me), 20.18 (2C collapsed, Me).…”

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confidence: 99%

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Enzyme-Graphene Nanometal biohybrid Architectures as Highly Efficient Multifunctional Catalysts for Cascade Reactions

Losada-Garcia

Urriolabeitia

Palomo

2022

Preprint

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The development of new catalytic systems with different chemo- and biocatalytic functionalities for sustainable one-pot multistep transformations represents a big challenge in modern chemistry. Here, we have designed and synthesized novel enzyme-graphene nanometal hybrids of palladium and copper as multiactive heterogeneous catalysts. The in-situ formation of metallic nanoparticles of different size and species on enzymes (C. antartica lipase, CALB and and T. lanuginosus lipase), TLL) immobilized on multilayer graphene-anchored enzymes (G@CALB and G@TLL preparations) at room temperature and aqueous media allowed to create different kind of enzyme-metal nanoarchitectures, containing up to two enzymes and metallic nanoparticles of two different metals in the same compartment. The metallic nanoparticles were synthesized exclusively induced by the enzyme, homogeneously distributed on the enzymatic structure used as scaffold. The cooperative and synergistic participation of different chemo and biocatalytic components in the reduction process and especially in different cascade reactions was demonstrated. Domino cascade in aqueous media (enzymatic hydrolysis, metal reduction, and metal oxidation) was successfully performed from the different hybrid systems. The synthesis of glycoderivatives, transforming selectively peracetylated glucal to novel disaccharides, using G@CALB-Cu3(PO4)2NPs and G@CALB-Cu(0)NPs or α-peracetylated glucose to diacetyl-gluconic acid by G@TLL@CRL-Cu3(PO4)2NPs was successfully performed. Finally, the successful application in the dynamic kinetic resolution of racemic arylamine (>99% conversion and ee) in organic solvent catalyzed by G@CALB-Pd(0)NPs-Cu3(PO4)2NPs demonstrated the potential effect in synthetic chemistry, and the synergistic effect of catalysis between enzyme and metals. Furthermore, recycling studies demonstrated the high robustness of them.

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Solid‐Phase Lipase‐CuNPs Biohybrids as Catalysts for One‐Pot Parallel Synthesis of 2,3,4‐Triacetyl‐D‐Gluconic Acid

2023

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Solid-phase lipase/metal nanobiohybrids, generated by growth of copper nanoparticles on enzyme matrixes immobilized on graphene, were used as heterogeneous catalysts with dualactivity for the regioselective production of 2,3,4-triacetyl-Dgluconic acid from α-peracetylated-glucose in a one-pot parallel process combining a lipase-mediated regioselective hydrolytic monodeprotection with a metal-catalyzed oxidation in aqueous media. A novel synthetic strategy, based on the in situ fabrication of Cu nanoparticles induced by lipase molecules specifically immobilized on a multi-layer graphene material by interfacial adsorption fixing them in the active open conformation, has been described. Thermomyces lanuginosus lipase was firstly used to prepare the functionalized multi-layer graphene from graphite as a biographene preparation (Biographene, BIOG), support used to successfully immobilize Candida rugosa lipase (CRL). This immobilized form BIOG-CRL was further used to create successful active bifunctional enzyme-metal nanoarchitectures. Two different Cu-lipase hybrids were synthesised, where Cu species and nanoparticles size were different depending on the methodology. Regioselectivity and stability of the hybrids were evaluated successfully in the production of monosaccharide building blocks, besides the robustness of the hybrids in recyclability experiments. These findings highlight the potential of these solid-phase nanoarchitectures as useful tools in the synthesis of complex glycoderivatives for use in food, medicine, and cosmetics.

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Pd-Oxazolone complexes conjugated to an engineered enzyme: improving fluorescence and catalytic properties

Abstract: Different Pd-complexes containing orthometallated push-pull oxazolones were inserted by supramolecular Pd-amino acid coordination on two genetically engineered modified variants of the thermoalkalophilic Geobacillus thermocatenolatus lipase (GTL). The Pd-lipase conjugation was...

Cited by 14 publications

References 43 publications

Metal Nanoparticles Incorporated within Graphene-Enzyme Preparations for Synergistic Multiactive Catalysts

Metal Nanoparticles Incorporated within Graphene-Enzyme Preparations for Synergistic Multiactive Catalysts

Enzyme-Graphene Nanometal biohybrid Architectures as Highly Efficient Multifunctional Catalysts for Cascade Reactions

Solid‐Phase Lipase‐CuNPs Biohybrids as Catalysts for One‐Pot Parallel Synthesis of 2,3,4‐Triacetyl‐D‐Gluconic Acid

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