In Vivo Biocatalytic Cascades Featuring an Artificial-Enzyme-Catalysed New-to-Nature Reaction**

Artificial enzymes utilizing the genetically encoded non-proteinogenic amino acid p-aminophenylalanine (pAF) as a catalytic residue are able to react with carbonyl compounds through an iminium ion mechanism to promote reactions that have no equivalent in nature. Herein, we report an in vivo biocatalytic cascade that is augmented with such an artificial enzyme-catalysed new-to-nature reaction. The artificial enzyme in this study is a pAF-containing evolved variant of the lactococcal multidrug-resistance regulator, designated LmrR_V15pAF_RMH, which efficiently converts benzaldehyde derivatives produced in vivo into the corresponding hydrazone products inside E. coli cells. These in vivo biocatalytic cascades comprising an artificial-enzyme-catalysed reaction are an important step towards achieving a hybrid metabolism.     

Computational Study of Bridge Splitting,Aryl Halide Oxidative Addition to PtII,and Reductive Elimination from PtIV: Route to Pincer-PtII Reagents with Chemical and Biological Applications

Density functional theory computation indicates that bridge splitting of [Pt^IIR₂(μ-SEt₂)]₂ proceeds by partial dissociation to form R₂Pt^a(μ-SEt₂)Pt^bR₂(SEt₂), followed by coordination of N-donor bromoarenes (L-Br) at Pt^a leading to release of Pt^bR₂(SEt₂), which reacts with a second molecule of L-Br, providing two molecules of PtR₂(SEt₂)(L-Br-N). For R=4-tolyl (Tol), L-Br=2,6-(pzCH₂)₂C₆H₃Br (pz=pyrazol-1-yl) and 2,6-(Me₂NCH₂)₂C₆H₃Br, subsequent oxidative addition assisted by intramolecular N-donor coordination via Pt^IITol₂(L-N,Br) and reductive elimination from Pt^IV intermediates gives mer-Pt^II(L-N,C,N)Br and Tol₂. The strong σ-donor influence of Tol groups results in subtle differences in oxidative addition mechanisms when compared with related aryl halide oxidative addition to palladium(II) centres. For R=Me and L-Br=2,6-(pzCH₂)₂C₆H₃Br, a stable Pt^IV product, fac-Pt^IVMe₂{2,6-(pzCH₂)₂C₆H₃-N,C,N)Br is predicted, as reported experimentally, acting as a model for undetected and unstable Pt^IVTol₂{L-N,C,N}Br undergoing facile Tol₂ reductive elimination. The mechanisms reported herein enable the synthesis of Pt^II pincer reagents with applications in materials and bio-organometallic chemistry.     

Kinetics of cementite mechanosynthesis

The influence of ball to powder ratio and discontinous milling during ball milling of Fe_0.75C_0.25 elemental powder mixture is presented. The formation of Fe₃C cementite, Hägg and ε carbides has been follwed by X-ray diffraction and Mössbauer Spectroscopy. Higher ball to powder ratios induce faster kinetics. Synthesized cementite has crystallite sizes 9 to 11 nm.     

Ion mixed Co-Nb amorphous films

Multilayers of cobalt and niobium have been deposited in ultra high vacuum, using two E-beams onto both corning glass and silicon wafers substrates kept at 20°C. These films were then ion mixed using Xe ions at 200, 300 and 400 keV. The dose was 3 × 10¹⁵ ions cm^-2 in all cases. FMR and usual magnetization measurements were made to characterize the samples. Films mixed at 300 and 400 keV are homogeneous. FMR line width of 60 Oe and the simple spectra obtained lead us to conclude that these films are much more homogeneous than co-evaporated amorphous films of the same composition.     

On Eckhoff's conjecture for Radon numbers; or how far the proof is still away

Eckhoff's conjecture for the Τ-Radon numbers r(Τ) of a convexity space. (X,C) says r(Τ) ≦ (r?1)(Τ?1)+1, with r = r(2). The main result of this note is that Eckhoff's conjecture is true in case ¦X¦ ≦ 2r and Τ = 3, i.e. each (2r?1)-set in a space with 2r?1 or 2r elements has a 3-Radon partition.