Arene oxidation with malonoyl peroxides

Malonoyl peroxide 7, prepared in a single step from the commercially available diacid, is an effective reagent for the oxidation of aromatics. Reaction of an arene with peroxide 7 at room temperature leads to the corresponding protected phenol which can be unmasked by aminolysis. An ionic mechanism consistent with the experimental findings and supported by isotopic labeling, Hammett analysis, EPR investigations and reactivity profile studies is proposed

Online conferences – Towards a new (virtual) reality

The recent article: Nature 579, 327–328 (2020), ending with the phrase: “You can’t just suddenly make a conference be online.”, has motivated us to write about the practicalities and philosophy of running online events, drawing on our extensive experience running an annual online computational chemistry conference. Our goals for this online conference series have always been: (1) Availability; (2) Community building and (3) Supporting young scientists. In this article, we highlight the motivations behind our initiative, how this has influenced the organisation of our online meeting, and discuss the benefits as well as the drawbacks of virtual meetings. Virtual conferences may not fully replace in-person meetings, but they are rapidly becoming an accepted alternative format. We discuss the hybrid online/in-person conference format as a future possibility that may offer an opportunity to reduce the environmental impact and accessibility barriers associate with in-person meetings without comprising networking and community-building opportunities

Methanol-to-Olefins Catalysis with Hydrothermally Treated Zeolite SSZ-39

Zeolite SSZ-39 is evaluated for catalyzing the methanol-to-olefins (MTO) reaction. By steaming NH_4–SSZ-39, Al can be removed from framework positions, resulting in an increase in framework-Si/AlT and thus a lowered active acid site density. The Si/Al_T ratios can be controlled by the steaming temperatures. SSZ-39 steamed at 750 °C, with preserved pore volume and morphology, is an excellent MTO catalyst, as high, stable olefin selectivities, long time-on-stream activity, and low alkane production are observed. Moreover, interesting propylene/ethylene/butylene ratios of 2.8/1/1.1 are obtained, likely related to the shape of the AEI cage. By Cu^(2+)-exchanging SSZ-39, evidence is provided to show that Al_T sites in close proximity (high AlT density) produce the unwanted effects (higher alkane-make and carbonaceous deposits) in nonsteamed materials during MTO

Investigating Ca II emission in the RS CVn binary ER Vulpeculae using the Broadening Function Formalism

The synchronously rotating G stars in the detached, short-period (0.7 d), partially eclipsing binary, ER Vul, are the most chromospherically active solar-type stars known. We have monitored activity in the Ca II H & K reversals for almost an entire orbit. Rucinski's Broadening Function Formalism allows the photospheric contribution to be objectively subtracted from the highly blended spectra. The power of the BF technique is also demonstrated by the good agreement of radial velocities with those measured by others from less crowded spectral regions. In addition to strong Ca II emission from the primary and secondary, there appears to be a high-velocity stream flowing onto the secondary where it stimulates a large active region on the surface 30 - 40 degrees in advance of the sub-binary longitude. A model light curve with a spot centered on the same longitude also gives the best fit to the observed light curve. A flare with approximately 13% more power than at other phases was detected in one spectrum. We suggest ER Vul may offer a magnified view of the more subtle chromospheric effects synchronized to planetary revolution seen in certain `51 Peg'-type systems.Comment: Accepted to AJ; 17 pages and 16 figure

Photo-fragmentation spectroscopy of benzylium and 1-phenylethyl cations

The electronic spectra of cold benzylium (C6H5-CH2+) and 1-phenylethyl (C6H5-CH-CH3+)cations have been recorded via photofragment spectroscopy. Benzylium and 1-phenylethyl cations produced from electrosprayed benzylamine and phenylethylamine solutions, respectively, were stored in a cryogenically cooled quadrupole ion trap and photodissociated by an OPO laser, scanned in parts of the UV and visible regions (600-225 nm). The electronic states and active vibrational modes of the benzylium and 1-phenylethyl cations as well as those of their tropylium or methyl tropylium isomers have been calculated with ab initio methods for comparison with the spectra observed. Sharp vibrational progressions are observed in the visible region while the absorption features are much broader in the UV. The visible spectrum of the benzylium cation is similar to that obtained in an argon tagging experiment [V. Dryza, N. Chalyavi, J.A. Sanelli, and E.J. Bieske, J. Chem. Phys. 137, 204304 (2012)], with an additional splitting assigned to Fermi resonances. The visible spectrum of the 1-phenylethyl cation also shows vibrational progressions. For both cations, the second electronic transition is observed in the UV, around 33 000 cm-1 (4.1 eV), and shows a broadened vibrational progression. In both cases the S2 optimized geometry is non planar. The third electronic transition observed around 40 000 cm-1 (5.0 eV) is even broader with no apparent vibrational structures, which is indicative of either a fast non-radiative process or a very large change in geometry between the excited and the ground states. The oscillator strengths calculated for tropylium and methyl tropylium are weak. Therefore, these isomeric structures are most likely not responsible for these absorption features. Finally, the fragmentation pattern changes in the second and third electronic states: C2H2 loss becomes predominant at higher excitation energies, for both cations

Solid-State and Gas-Phase Structures and Energetic Properties of the Dangerous Methyl and Fluoromethyl Nitrates

Reichel M, Krumm B, Vishnevskiy Y, et al. Solid-State and Gas-Phase Structures and Energetic Properties of the Dangerous Methyl and Fluoromethyl Nitrates. Angewandte Chemie (International ed. in English). 2019;58(51):18557-18561.An improved synthesis of the simplest nitric acid ester, methyl nitrate, and a new synthesis of fluoromethyl nitrate use the metathesis of the corresponding iodomethanes with silver nitrate. Both compounds were identified by spectroscopy and the structures determined for in situ grown crystals by X-ray diffraction as well as in the gas phase by electron diffraction. Fluorination leads to structures with shorter C-O and N-O bonds, has an energetically destabilizing effect and increases friction sensitivity, but decreases detonation performance. © 2019 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA

The design of organic catalysis for epoxidation by hydrogen peroxide

The potential of various organic species to catalyze epoxidation of ethene by hydrogen peroxide is explored with B3LYP/6-31G* DFT calculations

A star under multiple influences. Magnetic activity in V815 Her, a compact 2+2 hierarchical system

We are conducting a comprehensive investigation of V815 Her using photometric and spectroscopic data to understand the origin of the activity and what influences it in the short and long term. Using TESS photometry we performed light curve modeling in order to derive astrophysical and orbital parameters for the eclipsing binary subsystem V815 Her B. Using archival photometric data covering a century we carried out a time frequency analysis. Spectral synthesis was applied to determine the basic astrophysical parameters of the rapidly rotating primary using high-resolution STELLA spectra recorded in 2018. Photometric analysis revealed multiple cycles on timescales between ~6.5 and ~26 years. From TESS photometry we obtained orbital solution for the V815 Her B subsystem. The STELLA spectra covering the 200 day-long observing season enabled to create 19 time-series Doppler images, which revealed a constantly changing spotted surface. From the consecutive image pairs we measured a weak solar-type surface differential rotation of the spotted star. We found evidence that the V815 Her B component previously apostrophized as a third body is actually an eclipsing close binary subsystem of two M dwarfs with a period of 0.5 d, i.e., V815 Her is a 2+2 hierarchical quadruple system. The system is apparently young, only a few times ten million years old, consistent with the spotted primary V815 Her Aa being a zero-age main sequence star. Spot activity on the primary was found to be vivid. Fast starspot decay suggests that convective-turbulent erosion plays a more significant role in such a rapidly rotating star. The weak differential rotation of V815 Her Aa is presumably confined by tidal forces of the close companion V815 Her Ab. The slowly increasing photometric cycle of 6.5 years on average is interpreted as a spot cycle of V815 Her Aa, which is probably modulated by the eccentric wide orbit.Comment: 26 pages, to be published in Astronomy and Astrophysics (after final revision

Molecular Spiders in One Dimension

Molecular spiders are synthetic bio-molecular systems which have "legs" made of short single-stranded segments of DNA. Spiders move on a surface covered with single-stranded DNA segments complementary to legs. Different mappings are established between various models of spiders and simple exclusion processes. For spiders with simple gait and varying number of legs we compute the diffusion coefficient; when the hopping is biased we also compute their velocity.Comment: 14 pages, 2 figure

Mesenchymal Stem Cells Loaded with p5, Derived from CDK5 Activator p35, Inhibit Calcium-Induced CDK5 Activation in Endothelial Cells.

The potential use of stem cells as therapeutics in disease has gained momentum over the last few years and recently phase-I clinical trials have shown favourable results in treatment of a small cohort of acute stroke patients. Similarly, they have been used in preclinical models drug-loaded for the effective treatment of solid tumours. Here we have characterized uptake and release of a novel p5-cyclin-dependent kinase 5 (CDK5) inhibitory peptide by mesenchymal stem cells and showed release levels capable of blocking aberrant cyclin-dependent kinase 5 (CDK5) signaling pathways, through phosphorylation of cyclin-dependent kinase 5 (CDK5) and p53. These pathways represent the major acute mechanism stimulating apoptosis after stroke and hence its modulation could benefit patient recovery. This work indicates a potential use for drug-loaded stem cells as delivery vehicles for stroke therapeutics and in addition as anticancer receptacles particularly, if a targeting and/or holding mechanism can be defined