Copper and iron interactions with angiotensin-converting enzyme inhibitors. A study by fast-atom bombardment tandem mass spectrometry

Fast atom bombardment, combined with high-energy collision-induced tandem mass spectrometry, has been used to investigate gas-phase metal-ion interactions with captopril, enalaprilat and lisinopril, all angiotensin-converting enzyme inhibitors.Suggestions for the location of metal-binding sites are presented. For captopril, metal binding occurs most likely at both the sulphur and the nitrogen atom. For enalaprilat and lisinopril, binding preferably occurs at the amine nitrogen. Copyright 1999 John Wiley & Sons, Ltd.     

Comparing Poynting flux dominated magnetic tower jets with kinetic-energy dominated jets

Magnetic towers represent one of two fundamental forms of MHD outflows. Driven by magnetic pressure gradients, these flows have been less well studied than magneto-centrifugally launched jets even though magnetic towers may well be as common. Here we present new results exploring the behavior and evolution of magnetic tower outflows and demonstrate their connection with pulsed power experimental studies and purely hydrodynamic jets which might represent the asymptotic propagation regimes of magneto-centrifugally launched jets. High-resolution AMR MHD simulations (using the AstroBEAR code) provide insights into the underlying physics of magnetic towers and help us constrain models of their propagation. Our simulations have been designed to explore the effects of thermal energy losses and rotation on both tower flows and their hydro counterparts. We find these parameters have significant effects on the stability of magnetic towers, but mild effects on the stability of hydro jets. Current-driven perturbations in the Poynting Flux Dominated (PDF) towers are shown to be amplified in both the cooling and rotating cases. Our studies of the long term evolution of the towers show that the formation of weakly magnetized central jets within the tower are broken up by these instabilities becoming a series of collimated clumps which magnetization properties vary over time. In addition to discussing these results in light of laboratory experiments, we address their relevance to astrophysical observations of young star jets and outflow from highly evolved solar type stars.     

ESI‐MS/MS of expanded porphyrins: a look into their structure and aromaticity

Electrospray mass spectrometry/mass spectrometry was used to investigate the gas‐phase properties of protonated expanded porphyrins, in order to correlate those with their structure and conformation. We have selected five expanded meso‐pentafluorophenyl porphyrins, respectively, a pair of oxidized/reduced fused pentaphyrins (22 and 24 π electrons), a pair of oxidized/reduced regular hexaphyrins (26 and 28 π electrons) and a regular doubly N‐fused hexaphyrin (28 π electrons). The gas‐phase behavior of the protonated species of oxidized and reduced expanded porphyrins is different. The oxidized species (aromatic Hückel systems) fragment more extensively, mainly by the loss of two HF molecules. The reduced species (Möbius aromatic or Möbius‐like aromatic systems) fragment less than their oxidized counterparts because of their increased flexibility. The protonated regular doubly fused hexaphyrin (non‐aromatic Hückel system) shows the least fragmentation even at higher collision energies. In general, cyclization through losses of HF molecules decreases from the aromatic Hückel systems to Möbius aromatic or Möbius‐like aromatic systems to non‐aromatic Hückel systems and is related to an increase in conformational distortion. Copyright © 2016 John Wiley & Sons, Ltd.     

Genetically encoded tetrazine amino acid directs rapid site-specific in vivo bioorthogonal ligation with trans-cyclooctenes

Bioorthogonal ligation methods with improved reaction rates and less obtrusive components are needed for site-specifically labeling proteins without catalysts. Currently no general method exists for in vivo site-specific labeling of proteins that combines fast reaction rate with stable, nontoxic, and chemoselective reagents. To overcome these limitations, we have developed a tetrazine-containing amino acid, 1, that is stable inside living cells. We have site-specifically genetically encoded this unique amino acid in response to an amber codon allowing a single 1 to be placed at any location in a protein. We have demonstrated that protein containing 1 can be ligated to a conformationally strained trans-cyclooctene in vitro and in vivo with reaction rates significantly faster than most commonly used labeling methods.     

A new series of potentially hexadentate ligands derived from 2,2′-bipyridine

Reaction of 2,2′-bipyridine-6-carboxaldehyde with the appropriate aliphatic diamine in MeOH and subsequent reduction with NaBH₄ gives the new, potentially hexadentate, ligands N,N′-bis(2,2′-bipyridin-6-ylmethyl)ethane-1,2-diamine (bmet), N,N′-bis(2,2′-bipyridin-6-ylmethyl)propane-1,3-diamine (bmpp) and N,N′-bis(2,2′-bipyridin-6-ylmethyl)hexane-1,6-diamine (bmhx). The syntheses and characterisation of these ligands are reported; the ligands are isolated as the hydrochloride salts, with purification effected by either recrystallisation or cation exchange chromatography. [Co(bmet)](ClO₄)₃ · H₂O is obtained on reaction of bmet · 4.25HCl · 2.5H₂O with Na₃[Co(O₂CO)₃] · 3H₂O, and X-ray structural analysis shows this to have a pair of very short Co–N bonds. The synthesis and characterisation of the first coordination complex containing 6-(aminomethyl)-2,2′-bipyridine (amb) is also described.     

Molecular clouds,colliding flows and HEDLA experiments: Star formation with the AstroBEAR AMR code

In this contribution we present new simulations of colliding flows relevant to star formation studies which may also be relevant to future HEDLA experiments. We first discuss AstroBEAR a multi-physics MHD AMR code whose functionality and parallel performance make it a highly useful tool for star formation studies. We then present the results of two simulations of colliding flows that only differed with regards to the degree of inhomogeneity. One flow was completely uniform (Smooth), while the other contained many small over-densities in a lighter background (Clumpy) though with the same mean density, mass flux, & ram pressure. Despite these similarities, the two runs differed significantly with regards to their overall evolution, mixing, and core formation. The Smooth run formed cores early on throughout the cloud – while the inhomogeneities present in the Clumpy run drove a higher degree of small scale turbulence which seemed able to prevent local collapse. The Clumpy run did form cores but only after global collapse had ensued at around 20 Myr. The Smooth run managed to avoid global collapse for the duration of the simulation due to the increased splashing of material radially outwards as well as the higher pressure of the incoming material due to the details of the heating/cooling curve. In the final section we comment on possible applications of these studies to future HEDLA experiments. We conclude that key aspects of the flow evolution before gravitational collapse sets in may be amenable to laboratory studies.     

Enantiospecific formal total syntheses of (-)-salicylihalamides A and B from D-glucose and L-rhamnose

[reaction: see text] Two formal chiral pool syntheses of the (-)-salicylihalamides A and B were achieved from commercially available 1,2,5,6-diacetone-d-glucose and l-rhamnose.