Dehydration‐fragmentation mechanism of cathinones and their metabolites in ESI‐CID

Various cathinone‐derived designer drugs (CATs) have recently appeared on the drug market. This study examined the mechanism for the generation of dehydrated ions for CATs during electrospray ionization collision‐induced dissociation (ESI‐CID). The generation mechanism of dehydrated ions is dependent on the amine classification in the cathinone skeleton, which is used in the identification of CATs. The two hydrogen atoms eliminated during the dehydration of cathinone (primary amine) and methcathinone (secondary amine) were determined, and the reaction mechanism was elucidated through the deuterium labeling experiments. The hydrogen atom bonded to the amine nitrogen was eliminated with the proton added during ESI, in both of the tested compounds. This provided evidence that CATs with tertiary amine structures (such as dimethylcathinone and α‐pyrrolidinophenones [α‐PPs]) do not undergo dehydration. However, it was shown that the two major tertiary amine metabolites (1‐OH and 2″‐oxo) of CATs generate dehydrated ions in ESI‐CID. The dehydration mechanisms of the metabolites of α‐pyrrolidinobutiophenone (α‐PBP) belongs to α‐PPs were also investigated. Stable‐isotope labeling showed the dehydration of the 1‐OH metabolite following a simple mechanism where the hydroxy group was eliminated together with the proton added during ESI. In contrast, the dehydration mechanism of the 2″‐oxo metabolite involved hydrogen atoms in three or more locations along with the carbonyl group oxygen, indicating that dehydration occurred via multiple mechanisms likely including the rearrangement reaction of hydrogen atoms. These findings presented herein indicate that the dehydrated ions in ESI‐CID can be used for the structural identification of CATs.     

Amide-Directed C−H Sodiation by a Sodium Hydride/Iodide Composite

A new protocol for amide-directed ortho and lateral C−H sodiation is enabled by sodium hydride (NaH) in the presence of either sodium iodide (NaI) or lithium iodide (LiI). The transient organosodium intermediates could be transformed into functionalized aromatic compounds.     

Direct probe of the bent and linear geometries of the core-excited Renner-Teller pair states by means of the triple-ion-coincidence momentum imaging technique

The doubly degenerate core-excited Pi state of CO2 splits into two due to static Renner-Teller effect. Using the triple-ion-coincidence momentum imaging technique and focusing on the dependence of the measured quantities on the polarization of the incident light, we have probed, directly and separately, the linear and bent geometries for the B1 and A1 Renner-Teller pair states, as a direct proof of the static Renner-Teller effect.     

Variational principle for gravitational equations of the Bianchi identity type

It is shown that a square invariant of the Weyl conformal curvature tensor can lead to a Lagrangian in a variational principle for a gravitational equation in vacuum of the Bianchi identity type which is compatible with the Einstein equation. Moreover we show that such a Lagrangian implicitly includes a conformally invariant theory characterized by two gauge fields and the metric tensor.     

Self-energy correction to momentum-density distribution of positron-electron pairs

Positron two-dimensional angular correlation of annihilation radiation (2D ACAR), i.e., the 2D projection of the electron momentum densities sampled by positron, in Si is employed to verify the prediction of the density functional theory within the local-density approximation (LDA). Carefully conducted test shows that the LDA introduces small but definite discrepancies to the 2D-ACAR anisotropies. Self-energy calculation using the GW method indicates that density-fluctuation contributes anisotropic momentum-density correction and thus improves the agreement between theory and experiment. These results provide valuable annotations to the arguments concerning the accuracy and validity of the LDA and GW schemes.     

Efficient synthesis of poly(phenylazomethine) dendrons allowing access to higher generation dendrimers

We have developed a novel synthetic method of phenylazomethine dendrons that uses 4,4'-methylenedianiline instead of 4,4'-diaminobenzophenone to synthesize the precursor of the phenylazomethine dendron and then oxidized the precursor to the next-generation dendron. For this method, the productivity of the dendrons has been significantly increased. Furthermore, as the synthesis of high-generation dendrons becomes easier, synthesis of DPA G5 was achieved. [structure--see text]     

Measurement of nonrandom event-by-event fluctuations of average transverse momentum in square root of (sNN)=200 GeV Au+Au and p+p collisions

Event-by-event fluctuations of the average transverse momentum of produced particles near midrapidity have been measured by the PHENIX Collaboration in square root of (sNN)=200 GeV Au+Au, and p+p collisions at the Relativistic Heavy Ion Collider. The fluctuations are observed to be in excess of the expectation for statistically independent particle emission for all centralities. The excess fluctuations exhibit a dependence on both the centrality of the collision and on the pT range over which the average is calculated. Both the centrality and pT dependence can be well reproduced by a simulation of random particle production with the addition of contributions from hard-scattering processes.     

Strongly red-fluorescent novel donor-pi-bridge-acceptor-pi-bridge-donor (D-pi-A-pi-D) type 2,1,3-benzothiadiazoles with enhanced two-photon absorption cross-sections

Novel donor-pi-bridge-acceptor-pi-bridge-donor (D-pi-A-pi-D) type 2,1,3-benzothiadiazole fluorescent dyes connected to the N,N-diarylamino terminus via various type pi-conjugate spacers exhibits large two-photon absorption cross-sections and high fluorescent quantum yields in orange-red color.