Site-selective guest inclusion in molecular networks of butadiyne-bridged pyridino and benzeno square macrocycles on a surface

We present here the formation of a modular 2D molecular network composed of two different types of square-shaped butadiyne-bridged macrocycles, having intrinsic molecular voids, aligned alternately at the solid-liquid interface. Site-selective inclusion of a guest cation took place at every other molecular void in the molecular network with two different recognition sites.     

Crystal structure of thioflavin T bound to the peripheral site of Torpedo californica acetylcholinesterase reveals how thioflavin T acts as a sensitive fluorescent reporter of ligand binding to the acylation site

Acetylcholinesterase plays a key role in cholinergic synaptic transmission by hydrolyzing the neurotransmitter acetylcholine with one of the highest known catalytic rate constants. Hydrolysis occurs in a narrow and deep gorge that contains two sites of ligand binding: A peripheral site, or P-site, near the gorge entrance that contributes to catalytic efficiency both by transiently trapping substrate molecules as they enter the gorge and by allosterically accelerating the transfer of the substrate acyl group to a serine hydroxyl in an acylation site or A-site at the base of the gorge. Thioflavin T is a useful reporter of ligand interactions with the A-site. It binds specifically to the P-site with fluorescence that is enhanced approximately 1000-fold over that of unbound thioflavin T, and the enhanced fluorescence is quenched 1.5- to 4-fold when another ligand binds to the A-site in a ternary complex. To clarify the structural basis of this advantageous signal change, we here report the X-ray structure of the complex of thioflavin T with Torpedo californica acetylcholinesterase. The two aromatic rings in thioflavin T are coplanar and are packed snugly parallel to the aromatic side chains of Trp279, Tyr334, and Phe330. Overlays of this structure with the crystal structures of Torpedo californica acetylcholinesterase complexes with either edrophonium or m-( N, N, N-trimethylammonio)-2,2,2-trifluoroacetophenone, two small aromatic ligands that bind specifically to the A-site, indicate that the phenyl side chain of Phe330 must rotate to sterically accommodate both thioflavin T and the A-site ligand in the ternary complex. This rotation may allow some relaxation of the strict coplanarity of the aromatic rings in the bound thioflavin T and result in partial quenching of its fluorescence.     

N-carbonylation of lithium azaenolates of amides, formamides, ureas, and carbamates with carbon monoxide mediated by selenium

N-Carbonylation of less nucleophilic nitrogen compounds was achieved by the reaction of the lithium azaenolates with carbon monoxide and selenium. This reaction proceeds in the cases of amides, formamides, ureas, and carbamates, leading to the formation of the corresponding carbamoselenoates in good to high yields after trapping with BuI.     

Copper-catalyzed tandem reaction directed toward synthesis of 2,2-disubstituted quinazolinones from vinyl halides and 2-aminobenzamides

A copper-catalyzed tandem reaction with vinyl halides and 2-aminobenzamides has been developed. In this synthetic route, cross-coupling reaction of the amide moiety with vinyl halides initially progresses, followed by hydroamination, to provide 2,2-disubstituted quinazolinone derivatives. Moreover, the tandem reaction is used in a one-pot synthesis beginning with alkyne hydroiodination by PPh₃, I₂, and H₂O.     

Decay study of neutron-rich zirconium isotopes employing a Penning trap as a spectroscopy tool

A new technique to produce isobarically pure ion beams for decay spectroscopy by using a gas-filled Penning trap was commissioned at the ion guide isotope separator on-line facility, IGISOL. β-decays of neutron-rich ¹⁰⁰Zr, ¹⁰²Zr and ¹⁰⁴Zr isotopes were studied with this technique. In addition, the values of ^100,102,104Zr β-decays were determined from the direct mass measurements of zirconium and niobium isotopes performed with a high-precision Penning trap. The mass of ¹⁰⁴Nb was directly measured for the first time and the obtained mass excess value for the longer-living (1⁺) state is -71823±10 keV. For the ground states of ¹⁰⁰Nb and ¹⁰²Nb the obtained mass excess values were -79802±20 keV and -76309±10 keV, respectively. The observed distribution of the β strength supports a prolate deformation assignment for ^100,102,104Zr isotopes.     

IrCl3 or FeCl3-catalyzed convenient synthesis of 3-hydroxyphthalates

IrCl₃·3H₂O or FeCl₃-catalyzed convenient synthesis of 3-hydroxyphthalates has been achieved by a Diels-Alder reaction of furans with dimethyl acetylenedicarboxylate, followed by ring-opening aromatization reaction of the Diels-Alder adducts, 7-oxabicyclo[2.2.1]hepta-2,5-diene derivatives. In addition, 7-azabicyclo[2.2.1]hepta-2,5-diene derivative, derived from N-Boc-pyrrole and dimethyl acetylenedicarboxylate, also converted into 3-aminophthalate derivative.     

Reactor decay heat in 239Pu: solving the γ discrepancy in the 4-3000-s cooling period

The β feeding probability of (102,104,105,106,107)Tc, 105Mo, and 101Nb nuclei, which are important contributors to the decay heat in nuclear reactors, has been measured using the total absorption technique. We have coupled for the first time a total absorption spectrometer to a Penning trap in order to obtain sources of very high isobaric purity. Our results solve a significant part of a long-standing discrepancy in the γ component of the decay heat for 239Pu in the 4-3000 s range.     

Determining isotopic distributions of fission products with a Penning trap

A novel method to determine independent yields in particle-induced fission employing the ion guide technique and ion counting after a Penning trap has been developed. The method takes advantage of the fact that a Penning trap can be used as a precision mass filter, which allows an unambiguous identification of the fission fragments. The method was tested with 25MeV and 50MeV proton-induced fission of ²³⁸U . The data is internally reproducible with an accuracy of a few per cent. A satisfactory agreement was obtained with older ion guide yield measurements in 25MeV proton-induced fission. The results for Rb and Cs yields in 50MeV proton-induced fission agree with previous measurements performed at an isotope separator equipped with a chemically selective ion source.