Photoionization and Pyrolysis of a 1,4‐Azaborinine: Retro‐Hydroboration in the Cation and Identification of Novel Organoboron Ring Systems

The photoionization and dissociative photoionization of 1,4‐di‐tert‐butyl‐1,4‐azaborinine by means of synchrotron radiation and threshold photoelectron photoion coincidence spectroscopy is reported. The ionization energy of the compound was determined to be 7.89 eV. Several low‐lying electronically excited states in the cation were identified. The various pathways for dissociative photoionization were modeled by statistical theory, and appearance energies AE_0K were obtained. The loss of isobutene in a retro‐hydroboration reaction is the dominant pathway, which proceeds with a reverse barrier. Pyrolysis of the parent compound in a chemical reactor leads to the generation of several yet unobserved boron compounds. The ionization energies of the C₄H₆BN isomers 1,2‐ and 1,4‐dihydro‐1,4‐azaborinine and the C₃H₆BN isomer 1,2‐dihydro‐1,3‐azaborole were determined from threshold photoelectron spectra.     

Chemical Probing of the Human Sirtuin 5 Active Site Reveals Its Substrate Acyl Specificity and Peptide‐Based Inhibitors

Sirtuins are NAD⁺‐dependent deacetylases acting as sensors in metabolic pathways and stress response. In mammals there are seven isoforms. The mitochondrial sirtuin 5 is a weak deacetylase but a very efficient demalonylase and desuccinylase; however, its substrate acyl specificity has not been systematically analyzed. Herein, we investigated a carbamoyl phosphate synthetase 1 derived peptide substrate and modified the lysine side chain systematically to determine the acyl specificity of Sirt5. From that point we designed six potent peptide‐based inhibitors that interact with the NAD⁺ binding pocket. To characterize the interaction details causing the different substrate and inhibition properties we report several X‐ray crystal structures of Sirt5 complexed with these peptides. Our results reveal the Sirt5 acyl selectivity and its molecular basis and enable the design of inhibitors for Sirt5.     

Magnetic Resonance Imaging of Electrochemical Cells Containing Bulk Metal

The development of improved energy‐storage devices, as well as corrosion prevention and metal‐electrofinishing technologies, requires knowledge of local composition and transport behaviour in electrolytes near bulk metals, in situ and in real time. It remains a challenge to acquire such data and new analytical methods are required. Recent work shows that magnetic resonance imaging (MRI) is able to map concentration gradients and visualise electrochemical processes in electrochemical cells containing bulk metals. This recent work, along with the challenges, and solutions, associated with MRI of these electrochemical cells are reviewed.     

Azoalkanes—novel flame retardants and their structure–property relationship

A number of symmetrical and unsymmetrical azoalkanes of the general formula R′?N = N?R and related azoxy, hydrazone as well as azine derivatives have been synthesized in order to assess their potential as novel flame retardants for polypropylene alone or in combination with commercially available flame retardants such as alumina trihydrate (ATH), decabromodiphenyl ether (DecaBDE) and tris(3‐bromo‐2,2‐bis(bromomethyl)‐propyl)phosphate (TBBPP). The experimental results show that in the series of different sized azocycloalkanes the flame retardant efficacy decreased in the following order: R = cyclohexyl > cyclopentyl > cyclobutyl > cyclooctanyl >> cyclododecanyl. Whereas in the series of aliphatic azoalkanes compounds the efficacy decreased in the following order: R = n‐alkyl > tert‐butyl > tert‐octyl. In addition, also some of the prepared azoxy, azine, and hydrazone derivatives provide flame retardancy to polypropylene films at already very low concentrations (0.25–1 wt%). Noteworthy is that in contrast to other halogen‐free radical generators, the azoalkanes are also very effective as flame retardants in polypropylene thick moldings. Interestingly, it was found that 4,4′‐bis(cyclohexylazocyclohexyl)‐methane) shows a strong synergistic effect with ATH. Thus, in the presence of 0.5 wt% of azoalkane the ATH loading could be reduced from 60 to 25 wt% and still UL94 V‐2 rating could be reached. Furthermore, the fire testing data reveal that azoalkanes show a synergistic effect with DecaBDE and when used in conjunction with very low loadings of TBBPP. Copyright © 2010 John Wiley & Sons, Ltd.     

Hydrazine (N2H4) adsorption on Ni(1 0 0) – Density functional theory investigation

A theoretical study on the structure and adsorption mechanism of hydrazine (N₂H₄) on Ni(1 0 0) are presented. The hydrazine molecule was found to adsorb on the surface through one of its nitrogen atom in its anti-conformation. The charge transfer from hydrazine lone pair orbitals played a key role in the formation of the bonding. The mechanism involved in the bonding was found to reduce the necessity of hyper-conjugation interaction, that reduces the gauche effect found in hydrazine at the gas-phase. Upon adsorption to the surface, the reduced interaction resulted in the promotion of a more favored conformation through its anti-conformation.     

Economy of effort in different speaking conditions. I. A preliminary study of intersubject differences and modeling issues

This study explores the hypothesis that clear speech is produced with greater "articulatory effort" than normal speech. Kinematic and acoustic data were gathered from seven subjects as they pronounced multiple repetitions of utterances in different speaking conditions, including normal, fast, clear, and slow. Data were analyzed within a framework based on a dynamical model of single-axis frictionless movements, in which peak movement speed is used as a relative measure of articulatory effort (Nelson, 1983). There were differences in peak movement speed, distance and duration among the conditions and among the speakers. Three speakers produced the "clear" condition utterances with movements that had larger distances and durations than those for "normal" utterances. Analyses of the data within a peak speed, distance, duration "performance space" indicated increased effort (reflected in greater peak speed) in the clear condition for the three speakers, in support of the hypothesis. The remaining four speakers used other combinations of parameters to produce the clear condition. The validity of the simple dynamical model for analyzing these complex movements was considered by examining several additional parameters. Some movement characteristics differed from those required for the model-based analysis, presumably because the articulators are complicated structurally and interact with one another mechanically. More refined tests of control strategies for different speaking styles will depend on future analyses of more complicated movements with more realistic models.