RESUMEN
In order to asses performance of the LDA in describing physisorption on graphene, adsorptions of TCNE, TCNQ, TNF, TTF, and DMPD as well as four benzene derivatives on C(54)H(18) and C(110)H(30) were explored with a variety of DFTs such as MPWB1K, M06-2X, PBE-D and LSDA. Although it is well known that the LDA considerably overestimate non-covalent interaction, the LSDA predicted adsorption energies except for TCNE on C(110)H(30) are systematically lower than those from the M06-2X by 0.4-3.2 kcal/mol, and they are more significantly lower than those from the PBE-D for all the molecules by 3-6 kcal/mol. However, the LSDA adsorption energy sequence is consistent with that from the PBE-D, TNF~TCNQ>TCNE~DMPD>TTF. Moreover, the domain interaction between the electron donor and acceptor molecules with graphene through cooperative π···π, C-H···π and N-H···π were visualized with sign(λ(2))×ρ, and the relationships between the binding energy with London force, molecular electronegativity, and frontier orbital level were extensively discussed.
RESUMEN
A photocaged N(epsilon)-methyl-L-lysine has been genetically incorporated into proteins at amber codon positions in Escherichia coli using an evolved pyrrolysyl-tRNA synthetase-pylT pair. Its genetic incorporation and following photolysis to recover N(epsilon)-methyl-L-lysine at physiological pH provide a convenient method for the biosynthesis of proteins with monomethylated lysines at specific sites.