Unexpected Acetylation of Endogenous Aliphatic Amines by Arylamine N-Acetyltransferase NAT2

N-Acetyltransferases play critical roles in the deactivation and clearance of xenobiotics, including clinical drugs. NAT2 has been classified as an arylamine N-acetyltransferase that mainly converts aromatic amines, hydroxylamines, and hydrazines. Herein, we demonstrate that the human arylamine N-acetyltransferase NAT2 also acetylates aliphatic endogenous amines. Metabolomic analysis and chemical synthesis revealed increased intracellular concentrations of mono- and diacetylated spermidine in human cell lines expressing the rapid compared to the slow acetylator NAT2 phenotype. The regioselective N⁸-acetylation of monoacetylated spermidine by NAT2 answers the long-standing question of the source of diacetylspermidine. We also identified selective acetylation of structurally diverse alkylamine-containing drugs by NAT2, which may contribute to variations in patient responses. The results demonstrate a previously unknown functionality and potential regulatory role for NAT2, and we suggest that this enzyme should be considered for re-classification.     

Symmetry‐Breaking Charge‐Transfer Chromophore Interactions Supported by Carbon Nanodots

Carbon dots (CDs) and their derivatives are useful platforms for studying electron‐donor/acceptor interactions and dynamics therein. Herein, we couple amorphous CDs with phthalocyanines (Pcs) that act as electron donors with a large extended π‐surface and intense absorption across the visible range of the solar spectrum. Investigations of the intercomponent interactions by means of steady‐state and pump‐probe transient absorption spectroscopy reveal symmetry‐breaking charge transfer/separation and recombination dynamics within pairs of phthalocyanines. The CDs facilitate the electronic interactions between the phthalocyanines. Thus, our findings suggest that CDs could be used to support electronic couplings in multichromophoric systems and further increase their applicability in organic electronics, photonics, and artificial photosynthesis.     

On Dean–Kawasaki Dynamics with Smooth Drift Potential

Journal of Statistical Physics - We consider the Dean–Kawasaki equation with smooth drift interaction potential and show that measure-valued solutions exist only in certain parameter regimes...     

Site-Selective Late-Stage Aromatic [18F]Fluorination via Aryl Sulfonium Salts

Site-selective functionalization of C−H bonds in small complex molecules is a long-standing challenge in organic chemistry. Herein, we report a broadly applicable and site-selective aromatic C−H dibenzothiophenylation reaction. The conceptual advantage of this transformation is further demonstrated through the two-step C−H [¹⁸F]fluorination of a series of marketed small-molecule drugs.     

Enantiomerically Pure Tetravalent Neptunium Amidinates: Synthesis and Characterization

The synthesis of a tetravalent neptunium amidinate [NpCl((S)-PEBA)₃] ( 1 ) ((S)-PEBA=(S,S)-N,N′-bis-(1-phenylethyl)-benzamidinate) is reported. This complex represents the first structurally characterized enantiopure transuranic compound. Reactivity studies with halide/pseudohalides yielding [NpX((S)-PEBA)₃] (X=F ( 2 ), Br ( 3 ), N₃ ( 4 )) have shown that the chirality-at-metal is preserved for all compounds in the solid state. Furthermore, they represent an unprecedented example of a structurally characterized metal–organic Np complex featuring a Np−Br ( 3 ) bond. In addition, 4 is the only reported tetravalent transuranic azide. All compounds were additionally characterized in solution using para-magnetic NMR spectroscopy showing an expected C₃-symmetry at low temperatures.