Deep penetration by substrates through the size‐restricted channels of an apo‐ferritin cage results in size‐selective olefin hydrogenation at the Pd nanocluster core (see picture). The encapsulated zero‐valent cluster is synthesized in situ by chemical reduction of PdII ions in the apo‐ferritin cage.
In many subfields of chemistry and physics, numerous attempts have been made to accelerate scientific discovery using data-driven experimental design algorithms. Among them, Bayesian optimization has been proven to be an effective tool. A standard implementation (e.g., scikit-learn), however, can accommodate only small training data. We designed an efficient protocol for Bayesian optimization that employs Thompson sampling, random feature maps, one-rank Cholesky update and automatic hyperparameter tuning, and implemented it as an open-source python library called COMBO (COMmon Bayesian Optimization library). Promising results using COMBO to determine the atomic structure of a crystalline interface are presented. COMBO is available at https: //github.com/tsudalab/combo.
Construction of artificial metalloenzymes is one of the most important subjects in bioinorganic chemistry, because metalloenzymes catalyze chemical transformations with high selectivity and reactivity under mild conditions. [1][2][3][4] There are several reports on protein design: introduction of metal binding sites, [1,3,[5][6][7][8] design of substrate binding cavities, [9][10][11][12] chemical modification of prosthetic groups, [13][14][15][16] and covalent attachment of metal cofactors. [2,[17][18][19][20] In particular, the covalent modification of proteins is a powerful tool for the generation of new metalloenzymes, while the efficiency of the modification is very much dependent on the position and reactivity of the cysteinyl thiol functional group.[2] Herein, we describe a novel strategy for the preparation of artificial metalloenzymes by noncovalent insertion of metal-complex catalysts into protein cavities. The resulting semisynthetic metalloenzymes, apo-myoglobin (apo-Mb) reconstituted with Cr III Schiff base complexes, are able to catalyze enantioselective sulfoxidation.Manganese(iii) and chromium(iii) Schiff base complexes are known to be catalysts for various oxidations in organic solvents. [21,22] Jacobsen, [23] and Katsuki [24]
Polymerization reactions of phenylacetylene derivatives are promoted by rhodium complexes within the discrete space of apo-ferritin in aqueous media. The catalytic reaction provides polymers with restricted molecular weight and a narrow molecular weight distribution. These results suggest that protein nanocages have potential for use as various reaction spaces through immobilization of metal catalysts on the interior surfaces of the protein cages.
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