Heavy‐Atom Tunneling in the Ring Opening of a Strained Cyclopropene at Very Low Temperatures

The highly strained 1H‐bicyclo[3.1.0]‐hexa‐3,5‐dien‐2‐one 1 is metastable, and rearranges to 4‐oxacyclohexa‐2,5‐dienylidene 2 in inert gas matrices (neon, argon, krypton, xenon, and nitrogen) at temperatures as low as 3 K. The kinetics for this rearrangement show pronounced matrix effects, but in a given matrix, the reaction rate is independent of temperature between 3 and 20 K. This temperature independence means that the activation energy is zero in this temperature range, indicating that the reaction proceeds through quantum mechanical tunneling from the lowest vibrational level of the reactant. At temperatures above 20 K, the rate increases, resulting in curved Arrhenius plots that are also indicative of thermally activated tunneling. These experimental findings are supported by calculations performed at the CASSCF and CASPT2 levels by using the small‐curvature tunneling (SCT) approximation.     

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.