Dimethylcuprate Undergoes a Dyotropic Rearrangement

Abstract

The use of graphene electrodes with hydrogenated edges for solid‐state nanopore‐based DNA sequencing is proposed, and molecular dynamics simulations in conjunction with electronic transport calculations are performed to explore the potential merits of this idea. The results of the investigation show that, compared to the unhydrogenated system, edge‐hydrogenated graphene electrodes facilitate the temporary formation of H‐bonds with suitable atomic sites in the translocating DNA molecule. As a consequence, the average conductivity is drastically raised by about 3 orders of magnitude while exhibiting significantly reduced statistical variance. Furthermore, the effect of the distance between opposing electrodes is investigated and two regimes identified: for narrow electrode separation, the mere hindrance due to the presence of protruding hydrogen atoms in the nanopore is deemed more important, while for wider electrode separation, the formation of H‐bonds becomes the dominant effect. Based on these findings, it is concluded that hydrogenation of graphene electrode edges represents a promising approach to reduce the translocation speed of DNA through the nanopore and substantially improve the accuracy of the measurement process for whole‐genome sequencing.

The Role of Ate Complexes in the Copper‐Mediated Trifluoromethylation of Alkynes

“…In gas‐phase fragmentation experiments, ions of interest were mass‐selected with isolation widths between 1.0 and 8.0 u, accelerated to kinetic energies E LAB , and allowed to collide with nitrogen gas. Additional experiments were performed with an HCT quadrupole‐ion trap mass spectrometer (Bruker Daltonik),, and afforded ESI mass spectra, which were similar to those obtained with the micrOTOF‐Q II instrument, but suffered from lower mass resolution. The quadrupole‐ion trap mass spectrometer was operated at a trap drive of 40, and an ESI voltage of 3.0 kV was applied.…”

Origin of the different reactivity of the high-valent coinage-metal complexes [RCuIIIMe3]− and [RAgIIIMe3]− (R = allyl)

“…2b). In this regard, it is also worth mentioning that studies on the unimolecular reactivity of [RMMe] − and [MMe 2 ] − from Rijs et al 46,75 strongly argue against secondary fragmentations of these product complexes in the context of our CID experiments (for corresponding DLPNO-CCSD(T)//PBE-D3BJ bond dissociation energies, see Table S5). The therein calculated energy profiles are not only in agreement with the absence of [RM] •− , [MMe] •− or [HMMe] − signals, but also emphasize that the obtained fragmentation spectra are not biased by R − and Me − loss reactions of the organometallate(i) complexes, which would not be detectable because of the m/z cutoff of the mass spectrometer used in this study.…”

Unimolecular reactivity of organotrifluoroborate anions, RBF3−, and their alkali metal cluster ions, M(RBF3)2− (M = Na, K; R = CH3, CH3CH2, CH3(CH2)3, CH3(CH2)5, c‐C3H5, C6H5, C6H5CH2, CH2CHCH2, CH2CH, C6H5CO)

“…In contrast to the fragmentation reactions of organomagnesate anions, organozincate, organoferrate, organoindates and coinage metal organometallate anions, reductive elimination, beta hydride transfer reactions and bond homolysis reactions that release radicals are not observed for organotrifluoroborate anions, RBF 3 − .…”