This minireview deals with the recent advances on synthetic strategies for immobilization of enzymes in metal–organic frameworks.

N-Substituted aziridines are formed by Fe- or Mn-Porphyrin catalysed reactions of PhlNR compounds (R = tosyl COCF7) with alkenes; the stereochemical characteristics these very different from those analogous epoxidation alkenes PhlO.

Abstract Microperoxidase‐8, a small, peroxidase‐type enzyme was immobilized into nanoparticles of the mesoporous and ultra‐stable metal–organic framework (MOF) MIL‐101(Cr). The fully retained its catalytic activity exhibited enhanced resistance to acidic conditions. biocatalyst reusable showed long‐term stability. By exploiting properties MOF′s framework, we demonstrated, for first time, that MOF matrix could act in synergy with (Microperoxidase‐8) enhance selectivity oxidation reaction...

meso-Tetra-arylporphyriniron(III) derivatives catalyse the N-tosylaziridination of aryl-substituted styrenes by tosylimidoiodobenzene, PhlNTs, a nitrogen analogue iodosylbenzene. Three secondary reactions were found to limit yield N-tosylaziridination: (i) formation toluene-p-sulphonamide, TsNH2, which is presumably derived from hydrolysis possible iron-nitrene, FeNTs, intermediate, (ii) conversion Fe(TPP)(Cl)(TPP = tetraphenylporphyrin) catalyst into an iron(III) complex where NTs moiety...

Artificial metalloenzymes are known to be promising tools for biocatalysis, but their recent compartmentalization has led compatibly with cell components thus shedding light on possible therapeutic applications. We prepared and characterized artificial based the A2A adenosine receptor embedded in cytoplasmic membranes of living human cells. The wild type was chemically engineered into by its association strong antagonists that were covalently bound copper(II) catalysts. resulting cells...

Abstract We demonstrate that the devised incorporation of an alkylamine group into second coordination sphere Fe II complex allows to switch its reactivity with H 2 O from usual formation III species towards selective generation IV ‐oxo intermediate. The was characterized by UV/Vis absorption and Mössbauer spectroscopy. Variable‐temperature kinetic analyses point a mechanism in which heterolytic cleavage O−O bond is triggered proton transfer proximal distal oxygen atom ‐H assistance pendant...

The crystal structure of an inorganic linear polymer consisting Mn(II) and N-centered tripodal ligand N,N-bis(2-(6-methyl)pyridylmethyl)glycinate is presented (1, C(16)H(20)N(3)O(3)F(6)P(1)Mn(1), a = 9.993(2) A, b 13.285(3) c 16.040(3) orthorhombic, Pnam, Z 4). polymeric ensured by carboxylato ligands connecting two in rather rare syn-anti geometry. magnetic properties this infinite chain have been investigated, together with the dimeric compound (3) from closely related...

Abstract Two crystal structures are described in this article: (a) the structure of a monomeric Mn II complex with tridentate N ‐centered 3 ligand tris[(1‐methyl‐2‐imidazolyl)methyl]amine (TMIMA) ([Mn 2 ] 2+ ); and (b) III O 2‐{[(1‐methyl‐2‐imidazolyl)methyl]amino}phenolate (PI – ) (PI) + ( 5 ). The latter was isolated both state, although only crystals were successfully grown. They part series complexes prepared as SOD mimics, namely [Mn(BMPG)(H O)] {BMPG = ,...

Abstract Here we report the best artificial metalloenzyme to date for selective oxidation of aromatic alkenes; it was obtained by noncovalent insertion Mn III ‐ meso ‐tetrakis( p ‐carboxyphenyl)porphyrin [Mn(T CPP), 1 ‐Mn] into a host protein, xylanase 10A from Streptomyces lividans (Xln10A). Two metallic complexes— N , N′ ‐ethylene bis(2‐hydroxybenzylimine)‐5,5′‐dicarboxylic acid [(Mn‐salen), 2 and ‐Mn—were associated with Xln10A, two hybrid biocatalysts were characterised UV–visible...

The design of artificial hemoproteins that could catalyze selective oxidations using clean oxidants such as O2 or H2O2 under ecocompatible conditions constitutes a real challenge for wide range industrial applications. In vivo, reactions are performed by heme-thiolate proteins, cytochromes P450, which the oxidation substrates dioxygen in presence electrons delivered from NADPH cytochrome P450 reductase. Several strategies were used to new mimic these enzymes. first one involved non-covalent...

Two new artificial hemoproteins or "hemozymes", obtained by non covalent insertion of Fe(III)-meso-tetra-p-carboxy- and -p-sulfonato-phenylporphyrin into xylanase A from Streptomyces lividans, were characterized UV-visible spectroscopy molecular modeling studies, found to catalyze the chemo- stereoselective oxidation thioanisole S sulfoxide, best yield (85 ± 4%) enantiomeric excess (40% 3%) being with Fe(III)-meso-tetra-p-carboxyphenylporphyrin-Xln10A as catalyst in presence imidazole co-catalyst.

Abstract Microperoxidase‐8, a small, peroxidase‐type enzyme was immobilized into nanoparticles of the mesoporous and ultra‐stable metal–organic framework (MOF) MIL‐101(Cr). The fully retained its catalytic activity exhibited enhanced resistance to acidic conditions. biocatalyst reusable showed long‐term stability. By exploiting properties MOF′s framework, we demonstrated, for first time, that MOF matrix could act in synergy with (Microperoxidase‐8) enhance selectivity oxidation reaction...

Microperoxidase 8 (MP8) was immobilized within MIL-101(Cr) bearing terephthalate linkers with functionalized groups (-NH2 and -SO3H). A synthesis protocol for MIL-101(Cr)-SO3H that avoids the use of toxic Cr(VI) HF developed. The electrostatic interactions between MP8 molecules MOF matrices were found to be crucial a successful immobilization. Raman spectroscopy revealed dispersion in MIL-101(Cr)-X as monomers without aggregation. presence functional resulted higher amounts comparison bare...

ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTIsolation of an iron-nitrene complex from the dioxygen- and iron porphyrin-dependent oxidation a hydrazineD. Mansuy, P. Battioni, J. MahyCite this: Am. Chem. Soc. 1982, 104, 16, 4487–4489Publication Date (Print):August 1, 1982Publication History Published online1 May 2002Published inissue 1 August 1982https://pubs.acs.org/doi/10.1021/ja00380a031https://doi.org/10.1021/ja00380a031research-articleACS PublicationsRequest reuse permissionsArticle...

Abstract New N ‐alkylaminoacridine derivatives attached to nitrogen heterocycles were synthesized, and their antimalarial potency was examined. They tested in vitro against the growth of Plasmodium falciparum , including chloroquine (CQ)‐susceptible CQ‐resistant strains. This biological evaluation has shown that presence a heterocyclic ring significantly increases activity P. . The best compound shows nanomolar IC 50 value toward parasite proliferation on both CQ‐susceptible these new...

A copper(II) cofactor coupled to a testosterone anchor, copper(II)-(5-(Piperazin-1-yl)-1,10-phenanthroline)testosterone-17-hemisuccinamide (10) was synthesized and associated with neocarzinostatin variant, NCS-3.24 (KD =3 μm), thus generating new artificial metalloenzyme by following "Trojan horse" strategy. Interestingly, the enzyme able efficiently catalyze Diels-Alder cyclization reaction of cyclopentadiene (1) 2-azachalcone (2). In comparison what observed 10 alone, enzymes favored...

Following the Trojan Horse strategy, a new artificial metalloenzyme, obtained by non-covalent insertion of an anionic Fe-porphyrin–testosterone conjugate into neocarzinostatin NCS-3.24 variant, catalysed enantioselective sulfoxidation thioanisole H₂O₂.

Abstract Development of artificial systems, capable delivering electrons to metal-based catalysts for the reductive activation dioxygen, has been proven very difficult decades, constituting a major scientific lock elaboration environmentally friendly oxidation processes. Here we demonstrate that incorporation flavin mononucleotide (FMN) in water-soluble polymer, bearing locally hydrophobic microenvironment, allows efficient reduction FMN by NADH. This supramolecular entity is then catalysing...

A complete analysis of the modulated structure NbTe4 is presented, using newly developed formalism de Wolff [Acta Cryst. (1974). A30, 777-785] and Yamamoto (1982). A38, 87-92]. The diffraction pattern was measured at room temperature, including first-order second-order satellites. superspace group |'l/Pa/mcc,, 1 T I final R~ value 0.095 (0.044 for main reflections only), a total 3894 unique (923 reflections). average found previously [Selte & Kjekshus (1964). Acta Chem. Scand. 18, 690-696]...

To develop artificial hemoproteins that could lead to new selective oxidation biocatalysts, a strategy based on the insertion of various iron-porphyrin cofactors into Xylanase A (Xln10A) was chosen. This protein has globally positive charge and wide enough active site accommodate metalloporphyrins possess negatively charged substituents such as microperoxidase 8 (MP8), iron(III)-tetra-α4-ortho-carboxyphenylporphyrin (Fe(ToCPP)), iron(III)-tetra-para-carboxyphenylporphyrin (Fe(TpCPP))....

Closing the loop: Light absorption by a sensitizer–diiron(III) complex in presence of sacrificial electron donor and subsequent exposure to O2 led formation corresponding active diiron(III)–peroxo species, which can transfer an oxygen atom substrate (see scheme). As service our authors readers, this journal provides supporting information supplied authors. Such materials are peer reviewed may be re-organized for online delivery, but not copy-edited or typeset. Technical support issues...