Detection of the reduced forms of radical adducts on the ESR trace using HPLC‐electrochemical detector‐ultraviolet absorption detector‐electron spin resonance‐MS

To detect and identify the electron spin resonance (ESR) silent forms of the α‐(4‐pyridyl‐1‐oxide)‐N‐tert‐butylnitrone (4‐POBN) radical adducts, an electrochemical detector (ECD) was employed as a reactor in the HPLC‐ECD‐UV absorption detector‐ESR‐MS (HPLC‐ECD‐UV‐ESR‐MS). The ECD was employed to regenerate the radical forms from the reduced forms. The reduced forms of the 4‐POBN/pentyl radical adducts were analyzed using the HPLC‐ECD‐UV‐ESR‐MS. On addition of the ECD applied potential of +0.3 V, a peak appeared on the ESR trace of the HPLC‐ECD‐UV‐ESR‐MS analyses, indicating that the radical forms are regenerated from the reduced forms. The HPLC‐ECD‐UV‐ESR‐MS analyses were also performed for the reaction mixtures of phenylhydrazine with CuCl₂. Two peaks (peaks I and II) were detected on the UV trace (300 nm) of the HPLC‐ECD‐UV‐ESR‐MS. The mass spectra showed that the peak I and peak II compounds are radical and reduced forms of the 4‐POBN/phenyl radical adducts under the ECD applied potential of 0.0 V. Peak I was only detected on the ESR trace under the ECD applied potential of 0.0 V. In addition to peak I, peak II appeared on the ESR trace under the ECD applied potential of +0.3 V, indicating that the reduced forms are oxidized to the corresponding radical forms.     

Population rate codes carried by mean, fluctuation and synchrony of neuronal firings

A population of firing neurons is expected to carry information not only by the mean firing rate but also by fluctuation and synchrony among neurons. In order to examine this possibility, we have studied responses of neuronal ensembles to three kinds of inputs: mean-, fluctuation- and synchrony-driven inputs. The generalized rate-code model including additive and multiplicative noise [H. Hasegawa, Phys. Rev. E 75 (2007) 051904] has been studied by direct simulations (DSs) and the augmented moment method (AMM) in which equations of motion for mean firing rate, fluctuation and synchrony are derived. Results calculated by the AMM are in good agreement with those by DSs. The independent component analysis (ICA) of our results has shown that mean firing rate, fluctuation (or variability) and synchrony may carry independent information in the population rate-code model. The input-output relation of mean firing rates is shown to have higher sensitivity for larger multiplicative noise, as recently observed in prefrontal cortex. A comparison is made between results obtained by the integrate-and-fire (IF) model and our rate-code model.     

Photoinduced chirality in a photochromic stilbene-molecule-doped polymeric liquid crystal film

Photoinduced chirality has been demonstrated in thin films of a main-chain polymeric liquid crystal (PLC) system doped with photochromic stilbene molecules by irradiation with circularly polarized light (CPL). CPL-induced chirality was observed in the intrinsically achiral films which were doped with low-molecular-weight stilbene molecules. It was found that the level of photoinduced chirality of the stilbene-molecule-doped system is comparable to that of the azobenzene-molecule-doped system. Moreover, reversible photo-rewriting property for the stilbene-doped system was also demonstrated by alternating irradiation with right- and left-CPL.     

Pressure broadening coefficients of induced by for Venus atmosphere

Carbon dioxide (CO₂) induced pressure broadening coefficients of water vapor (H₂O) lines have been determined using a terahertz time-domain spectrometer (TDS). Thirty-two rotational transitions of H₂O were observed in the spectral range of 18– (550–3050 GHz) for the first time. Using TDS allows one to measure absorption spectra with one order of magnitude better precision than Fourier transform spectrometer in this frequency region. The precision of our broadening coefficient measurements was 2.4% in average. The measured CO₂ induced pressure broadening coefficients are compared to those calculated by the complex Robert–Bonamy formalism. The difference between the measurement and the theoretical estimation was in the range of -10.7% to +19.0% confirming the credibility of the theoretical approach. The impact on retrieval of water vapor abundance was examined by performing inversion analysis on H₂O spectra of Venus atmosphere obtained with the Submillimeter Wave Astronomy Satellite. In this example case, the retrieved water vapor mixing ratio reduces by half at the altitude region of 70–85 km when applying the newly measured broadening coefficient compared to the air-broadening coefficient, and changes by 5% compared to that estimated by the complex Robert–Bonamy formalism.     

Facile transformation of benzocyclobutenones into 2,3-benzodiazepines via 4pi-8pi tandem electrocyclic reactions involving net insertion of diazomethylene compounds

Efficient transformations of benzocyclobutenones into 2,3-benzodiazepines by a formal insertion of diazomethylene compounds are described. This sequential process includes nucleophilic addition of diazomethylene anion, oxy-anion accelerated o-quinodimethane formation by an electrocyclic ring-opening reaction, and 8pi-electrocyclization in one-pot under remarkably mild conditions. Intermediary oxy-anion plays an important role for the efficient transformations.     

Stereoretentive elimination and trans-olefination of the dicationic dipalladium moiety [Pd2Ln]2+ bound on 1,3,5-trienes

The reaction of [Pd(2)(CH(3)CN)(6)][BF(4)](2) (1) with 1,3,5-hexatriene, 1,6-diphenyl-1,3,5-hexatriene (DPHT), or 2,2,9,9-tetramethyl-3,5,7-decatriene (DBHT) afforded bi-eta(3)-allyldipalladium complexes 3, 4, or 5. The reaction of 1 and DBHT proceeded in a stereospecific (syn) manner when the reaction was carried out in CD(2)Cl(2) under aerobic conditions, while a mixture of two diastereomers was formed under N(2) atmosphere. The two diastereomers (5-E,Z,E-antifacial and 5-E,E,E-antifacial) formed from DBHT were isolated, and the structure of 5-E,Z,E-antifacial, which was kinetically formed from the reaction of 1 and (E,E,E)-DBHT, was determined by X-ray diffraction analysis. Addition of phosphine ligands (PPh(3) or dppm) to the dinuclear adduct 5-E,Z,E-antifacial or 5-E,E,E-antifacial in acetonitrile resulted in the stereospecific (syn) elimination of [Pd(2)(PPh(3))(2)(CH(3)CN)(4)][BF(4)](2) (2) or [Pd(2)(dppm)(2)(CH(3)CN)(2)][BF(4)](2) (6). During the PPh(3)-induced dinuclear elimination, the phosphine adducts 7 that retain bi-eta(3)-allyldipalladium structure were observed initially. The phosphine adduct generated from 5-E,E,E-antifacial was isolated and structurally characterized by X-ray diffraction analysis. The reaction of 1 and DPHT in CH(2)Cl(2) afforded unique dipalladium sandwich compounds [Pd(2)(mu-eta(3):eta(3)-DPHT)(2)][BF(4)](2) (8). Interconversion between the sandwich complexes and half-sandwich complexes occurred in a stereoretentive manner. The structure of the sandwich complex 8-E,Z,E formed from 4-E,E,E-antifacial and (E,Z,E)-DPHT was determined by X-ray diffraction analysis. Transfer of the dipalladium moiety [Pd(2)(CH(3)CN)(4)](2+) from DPHT ligand of 4-E,E,E-antifacial onto DBHT ligand proceeded in a stereoretentive manner. The observed stereoretentive dinuclear process is featured by the pairwise behavior of two palladium atoms sitting on the triene pi-plane. In the dinuclear elimination, the two Pd atoms that are initially in the divalent state and bound on the opposite faces (antifacial) come to the synfacial positions to form a Pd-Pd bond prior to dissociation. These results represent the unique property of conjugated olefin as the multidentate ligands for metal-metal moieties.