Molecular Modeling Clarifies the Mechanism of Chromophore Maturation in the Green Fluorescent Protein

10.1021/jacs.7b00676

2017-07-19

We report the first complete theoretical description of the chain of elementary reactions resulting in chromophore maturation in the green fluorescent protein (GFP). All reaction steps including cyclization, dehydration, and oxidation are characterized at the...

Pyro-Borates, Spiro-Borates, and Boroxinates of BINOL—Assembly, Structures, and Reactivity

10.1021/jacs.7b02317

2017-07-19

VANOL and VAPOL ligands are known to react with three equivalents of B(OPh)3 to form a catalytic species that contains a boroxinate core with three boron atoms, and these have proven to be effective catalysts for a number of reactions. However, it was not kno...

Programming Cell Adhesion for On-Chip Sequential Boolean Logic Functions

10.1021/jacs.7b04040

2017-07-19

Programmable remodelling of cell surfaces enables high-precision regulation of cell behavior. In this work, we developed in vitro constructed DNA-based chemical reaction networks (CRNs) to program on-chip cell adhesion. We found that the RGD-functionalized DN...

Chemical Synthesis and Luminescence Applications of Colloidal Semiconductor Quantum Dots

10.1021/jacs.7b05267

2017-07-19

We describe the close connection between novel chemical synthesis and optimized light emission by colloidal semiconductor quantum dots (qdots). We describe how new insights and systematic improvement in synthesis and characterization have led to highly lumine...

Unprecedented (μ-1,1-Peroxo)diferric Structure for the Ambiphilic Orange Peroxo Intermediate of the Nonheme N-Oxygenase CmlI

10.1021/jacs.7b05389

2017-07-19

The final step in the biosynthesis of the antibiotic chloramphenicol is the oxidation of an aryl-amine substrate to an aryl-nitro product catalyzed by the N-oxygenase CmlI in three two-electron steps. The CmlI active site contains a diiron cluster ligated by ...

Enzyme Architecture: Modeling the Operation of a Hydrophobic Clamp in Catalysis by Triosephosphate Isomerase

10.1021/jacs.7b05576

2017-07-19

Triosephosphate isomerase (TIM) is a proficient catalyst of the reversible isomerization of dihydroxyacetone phosphate (DHAP) to d-glyceraldehyde phosphate (GAP), via general base catalysis by E165. Historically, this enzyme has been an extremely important mo...

Formally Copper(III)–Alkylperoxo Complexes as Models of Possible Intermediates in Monooxygenase Enzymes

10.1021/jacs.7b05754

2017-07-19

Reaction of [NBu4][LCuIIOH] with excess ROOH (R = cumyl or tBu) yielded [NBu4][LCuIIOOR], the reversible one-electron oxidation of which generated novel species with [CuOOR]2+ cores (formally CuIIIOOR), identified by spectroscopy and theory for the case R = c...

Controlling Cooperative CO2 Adsorption in Diamine-Appended Mg2(dobpdc) Metal–Organic Frameworks

10.1021/jacs.7b05858

2017-07-19

In the transition to a clean-energy future, CO2 separations will play a critical role in mitigating current greenhouse gas emissions and facilitating conversion to cleaner-burning and renewable fuels. New materials with high selectivities for CO2 adsorption, ...

Mechanism and Selectivity of Cooperatively Catalyzed Meyer–Schuster Rearrangement/Tsuji–Trost Allylic Substitution. Evaluation of Synergistic Catalysis by Means of Combined DFT and Kinetics Simulations

10.1021/jacs.7b01931

2017-07-18

The reaction between propargylic alcohols and allylic carbonates, engaging vanadium and palladium catalysts, is an exemplary case of a cooperatively catalyzed process. This combined Meyer–Schuster rearrangement/Tsuji–Trost allylic substitution clearly illustr...

Photoelectron Transfer Dissociation Reveals Surprising Favorability of Zwitterionic States in Large Gaseous Peptides and Proteins

10.1021/jacs.7b02428

2017-07-18

Structural characterization of proteins in the gas phase is becoming increasingly popular, highlighting the need for a greater understanding of how proteins behave in the absence of solvent. It is clear that charged residues exert significant influence over s...