Structural elaboration of the surprising ortho-zincation of benzyl methyl ether

Breaking with convention, the reaction of the sodium zincate, [(TMEDA)Na(μ-TMP)(μ-tBu)Zn(tBu)] with benzyl methyl ether (PhCH2OMe) produces exclusively an ortho-zincated intermediate [(TMEDA)Na(μ-TMP)(μ-C6H4CH2OMe)Zn(tBu)] instead of the expected 'thermodynamic' α-metallated product

Homo- and Heteroleptic Copper(I) Complexes with Diazabutadiene Ligands: Synthesis, Solution- and Solid-State Structural Studies

The preparation of novel copper(I) complexes of diazabutadiene (DAB) ligands with aliphatic backbones is reported. [Cu(DABR)2](BF4), [Cu(DABR)(NCMe)2](BF4) and [CuCl(DABR)] are easily synthesised and air-stable. These complexes, which remain scarce in the literature, have been fully characterised, and their behaviour both in the solid state as well as in solution has been studied by means of X-ray crystallography, NMR and UV/Vis spectroscopy

13C n.m.r. investigation on the nitrogen methylation of some azabenzenes

The 1H and 13C n.m.r. spectra of N-methylated pyridine, pyridazine, pyrimidine and pyrazine and N,N-dimethylated pyrimidine and pyrazine have been recorded and analysed. The change in the 13C chemical shifts under the influence of N-methylation (Δδ) in the diazabenzenes could be predicted by the Δδ values of pyridine. A comparison of the Δδ values of N-methylation with those of N-protonation showed that both reactions have a similar effect

Photoelectron spectra of some fluorine substituted diazanaphthalenes

The high resolution He 584 Å photoelectron spectra of fluorine substituted 1,2-diaza-, 1,3-diaza-, 1,4-diaza- and 2,3-diaza-naphthalene are presented. By means of fluorine substitution the analysis of the photoelectron spectra of the parent compounds can be made more definite. Unexpected shifts of the nitrogen “lone-pair” bands can be explained within the through-space and through-bond interaction model. From this explanation one can deduce that fluorine substitution can give experimental evidence about the symmetry character of the “lone-pair” molecular orbitals

Robotic Lepidoptery: Structural Characterization of (mostly) Unexpected Palladium Complexes Obtained from High-Throughput Catalyst Screening

In the course of a high-throughput search for optimal combinations of bidentate ligands with Pd(II) carboxylates to generate oxidation catalysts, we obtained and crystallographically characterized a number of crystalline products. While some combinations afforded the anticipated (L-L)Pd(OC(O)R)_2 structures (L-L = bipyridine, tmeda; R = CH_3, CF_3), many gave unusual oligometallic complexes resulting from reactions such as C−H activation (L-L = sparteine), P−C bond cleavage (L-L = 1,2-bis(diphenylphosphino)ethane, and C−C bond formation between solvent (acetone) and ligand (L-L = 1,4-bis(2,6-diisopropylphenyl)-1,4-diaza-1,3-butadiene). These findings illustrate potential pitfalls of screening procedures based on assuming uniform, in situ catalyst self-assembly

A functional role for small-conductance calcium-activated potassium channels in sensory pathways including nociceptive processes

We investigated the role of small-conductance calcium-activated potassium (SK) and intermediate-conductance calcium-activated potassium channels in modulating sensory transmission from peripheral afferents into the rat spinal cord. Subunit-specific antibodies reveal high levels of SK3 immunoreactivity in laminas I, II, and III of the spinal cord. Among dorsal root ganglion neurons, both peripherin-positive (C-type) and peripherin-negative (A-type) cells show intense SK3 immunoreactivity. Furthermore, dorsal root-stimulated sensory responses recorded in vitro are inhibited when SK channel activity is increased with 1-ethyl-2-benzimidazolinone (1-EBIO). In vivo electrophysiological recordings show that neuronal responses to naturally evoked nociceptive and nonnociceptive stimuli increase after application of the selective SK channel blocker 8,14-diaza-1,7( 1,4)-diquinolinacyclotetradecaphanedium ditrifluoroacetate (UCL 1848), indicating that SK channels are normally active in moderating afferent input. Conversely, neuronal responses evoked by mechanical stimuli are inhibited when SK channel activity is increased with 1-EBIO. These effects are reversed by the subsequent application of UCL 1848. Our data demonstrate that SK channels have an important role in controlling sensory input into the spinal cord

Development of New Methods for the (Q)SAR Applicability Domain Assessment: Using Structural Information in a Statistical Study of the Errors in Prediction

The main aim of (Q)SAR is to build models to evaluate and predict properties of molecules, such as biological and environmental effects, and physicochemical properties. These models are built using available experimental data, whose quality and quantity heavily affect their capability of obtaining reliable predictions for new chemicals. A dataset can be viewed as a "sampling" of the whole chemical space, if a sample is too small and / or too homogeneous, the model will inevitably have limitations in the type of chemicals it can predict. From the point of view of protecting the human health and the environment, it is preferable that a model is able to predict even a small number of chemicals, but with the highest possible reliability. The "coverage" issue can be overcome by integrating results from different models. In this perspective the importance of clearly defining the model's applicability domain is crucial to identify which model is most suitable for each chemical to assess. The definition of the applicability domain (AD) of (Q)SAR models is still an open research field. Several approaches have been proposed and implemented through years, including the use of structural features such as functional groups and atom-centered fragments. These features have also proven to be useful for an a priori definition of AD, making it independent from the specific algorithm chosen to develop the model. Within this study, the definition of (Q)SAR models' applicability domain has been investigated using structural features of different complexity: thresholds for chemical composition and molecular weight, chemical classes related to commonly well and badly predicted molecules, and statistically-extracted structural fragments to model the error in prediction. In the case studies considered, these approaches improved the AD definition provided by the model developers, supporting their integration within the definition of the models' applicability domain

An ambipolar BODIPY derivative for a white exciplex OLED and cholesteric liquid crystal laser toward multifunctional devices

A new interface engineering method is demonstrated for the preparation of an efficient white organic light-emitting diode (WOLED) by embedding an ultrathin layer of the novel ambipolar red emissive compound 4,4-difluoro-2,6-di(4-hexylthiopen-2-yl)-1,3,5,7,8-pentamethyl-4-bora-3a,4a-diaza-s-indacene (bThBODIPY) in the exciplex formation region. The compound shows a hole and electron mobility of 3.3 × 10–4 and 2 × 10–4 cm2 V–1 s–1, respectively, at electric fields higher than 5.3 × 105 V cm–1. The resulting WOLED exhibited a maximum luminance of 6579 cd m–2 with CIE 1931 color coordinates (0.39; 0.35). The bThBODIPY dye is also demonstrated to be an effective laser dye for a cholesteric liquid crystal (ChLC) laser. New construction of the ChLC laser, by which a flat capillary with an optically isotropic dye solution is sandwiched between two dye-free ChLC cells, provides photonic lasing at a wavelength well matched with that of a dye-doped planar ChLC cell

The photoelectron spectra of the diazanaphthalenes

The high-resolution He 584 Å photoelectron spectra of ten diazanaphthalenes are presented. The ordering of the π orbitals and the nitrogen “lone-pair” orbitals is discussed. Several semi-empirical quantum-chemical calculation methods have been screened against the experimental evidence