O,N,N-Pincer ligand effects on oxidatively induced carbon–chlorine coupling reactions at palladium

The syntheses of two families of sterically tuneable O,N,N pro-ligands are reported, namely the 2-(phenyl-2′-ol)-6-imine-pyridines, 2-(C6H4-2′-OH),6-(CMe[double bond, length as m-dash]NAr)C5H3N [Ar = 4-i-PrC6H4 (HL1a), 2,6-i-Pr2C6H3 (HL1b)] and the 2-(phenyl-2′-ol)-6-(amino-prop-2-yl)pyridines, 2-(C6H4-2′-OH),6-(CMe2NHAr)C5H3N [Ar = 4-i-PrC6H4 (HL2a), 2,6-i-Pr2C6H3 (HL2b)], using straightforward synthetic approaches and in reasonable overall yields. Interaction of HL1a/c and HL2a/b with palladium(II) acetate affords the O,N,N-pincer complexes, [{2-(C6H4-2′-O)-6-(CMe[double bond, length as m-dash]NAr)C5H3N}Pd(OAc)] (Ar = 4-i-PrC6H4 (1a), 2,6-i-Pr2C6H3 (1b)) and [{2-(C6H4-2′-O)-6-(CMe2NHAr)C5H3N}Pd(OAc)] (Ar = 4-i-PrC6H4 (2a), 2,6-i-Pr2C6H3 (2b)), which can be readily converted to their chloride derivatives, [{2-(C6H4-2′-O)-6-(CMe[double bond, length as m-dash]NAr)C5H3N}PdCl] (Ar = 4-i-PrC6H4 (3a), 2,6-i-Pr2C6H3 (3b)) and [{2-(C6H4-2′-O)-6-(CMe2NHAr)C5H3N}PdCl] (Ar = 4-i-PrC6H4 (4a), 2,6-i-Pr2C6H3 (4b)), respectively, on reaction with an aqueous sodium chloride solution. Treating each of 3a, 3b, 4a and 4b with two equivalents of di-p-tolyliodonium triflate at 100 °C in a toluene/acetonitrile mixture affords varying amounts of 4-chlorotoluene along with the 4-iodotoluene by-product with the conversions highly dependent on the steric and backbone properties of the pincer complex employed (viz.4a > 3a > 4b > 3b); notably, the least sterically bulky and most flexible amine-containing 4a reaches 90% conversion to 4-chlorotoluene in 15 h as opposed to 17% for imine-containing 3b. In the case of 3a, the inorganic palladium species recovered from the reaction has been identified as the Pd(II) salt [{2-(C6H4-2′-O)-6-(CMe[double bond, length as m-dash]N(4-i-PrC6H4)C5H3N}Pd(NCMe)][O3SCF3] (5a), which was independently prepared by the reaction of 3a with silver triflate in acetonitrile. Single crystal X-ray structures are reported for HL1a, HL2a, 1a, 1b, 2a, 2b, 3a and 5a

Organo-palladium(II) complexes bearing unsymmetrical N,N,N-pincer ligands: synthesis, structures and oxidatively induced coupling reactions

The 2-(2'-aniline)-6-imine-pyridines, 2-(C6H4--2'-NH2)-6-(CMe=NAr)C5H3 N (Ar = 4-i-PrC6H4 (HL1a), 2,6-i-Pr2C6H3 (HL1b)), have been synthesised via sequential Stille cross-coupling, deprotection and condensation steps from 6-tributylstannyl-2-(2-methyl-1,3-dioxolan-2-yl)pyridine and 2-bromonitrobenzene. The palladium(II) acetate N,N,N-pincer complexes, [{2-(C6H4-2'-NH)-6-(CMe=NAr)C5H3N}Pd(OAc)] (Ar = 4-i-PrC6H4 (1a), 2,6-i-Pr2C6H3 (1b)), can be prepared by reacting HL1 with Pd(OAc) 2 or, in the case of 1a , more conveniently by the template reaction of ketone 2-(C6H4-2'-NH2)-6-(CMe=O)C5H3N, Pd(OAc)2 and 4-isopropylaniline; ready conversion of 1 to their chloride analogues, [{2-(C6H4-2'-NH)-6-(CMe=NAr)C5H3N}PdCl] (Ar = 4-i-PrC6H4 (2a), 2,6-i-Pr2C6H3 (2b)), has been demonstrated. The phenyl-containing complexes, [{2-(C6H4-2'-NH)-6-(CMe=NAr)C5H3N}PdPh] (Ar = 4-i-PrC6H4 (3a), 2,6-i-Pr2C6H3 (3b)), can be obtained by treating HL1 with (PPh3)2 PdPh(Br) in the presence of NaH or with regard to 3a, by the salt elimination reaction of 2a with phenyllithium

Chandra observations of Cygnus OB2

Cygnus OB2 is the nearest example of a massive star forming region, containing over 50 O-type stars and hundreds of B-type stars. We have analyzed two Chandra pointings in Cyg OB2, detecting ~1700 X-ray sources, of which ~1450 are thought to be members of the association. Optical and near-IR photometry has been obtained for ~90% of these sources from recent deep Galactic plane surveys. We have performed isochrone fits to the near-IR color-magnitude diagram, deriving ages of 3.5(+0.75,-1.0) and 5.25(+1.5,-1.0) Myrs for sources in the two fields, both with considerable spreads around the pre-MS isochrones. The presence of a second population in the region, somewhat older than the present-day O-type stars, has been suggested by other authors and fits with the ages derived here. The fraction of sources with inner circumstellar disks (as traced by the K-band excess) is found to be very low, but appropriate for a population of age ~5 Myrs. We measure the stellar mass functions and find a power-law slope of Gamma = -1.09 +/- 0.13, in good agreement with the global mean value estimated by Kroupa. A steepening of the mass function at high masses is observed and we suggest this is due to the presence of the previous generation of stars that have lost their most massive members. Finally, combining our mass function and an estimate of the radial density profile of the association suggests a total mass of Cyg OB2 of ~30,000 Msun, similar to that of many of our Galaxy's most massive star forming regions.Comment: 6 pages, 4 figures, conference proceedings for JENAM 2010: Star Clusters in the Era of Large Surveys, Editors: A.Moitinho and J. Alve

Ensuring image integrity in the digital age

FEBS Open Bio and our fellow FEBS Press journals have a strong commitment to maintaining the integrity of the scientific literature. The life sciences, in particular, are suffering from an ongoing reproducibility crisis, and this may in part be fuelled by mistakes, manipulation or outright fabrication of the presented data. We were recently made aware of several articles published in FEBS Open Bio that appear to contain full or partial duplications of images from other published articles in a different scientific context. In most of these cases, the duplications were taken from previously published papers. After thorough investigation and subsequent discussion within FEBS Press and with Wiley's Integrity in Publishing Group, we have retracted most of these articles

Ten years of FEBS Open Bio

This month, FEBS Open Bio celebrates its 10th birthday. To celebrate the journal's first decade, we present this special anniversary issue, comprised of editorials, reviews, and research articles especially commissioned for the occasion. In this introductory editorial, we invite the reader to join us as we reminisce over the journal's past, celebrate its present, and look forward to its future

Entering the second decade: FEBS Open Bio in 2022

FEBS Open Bio continues to go from strength to strength, with 2021 perhaps marking its most exciting year. In this Editorial, the Editor-in-Chief Miguel A. De la Rosa looks back at all the new developments of 2021 and forecasts the outlook for 2022

A comparative study of experimental configurations in synchrotron pair distribution function

The identification and quantification of amorphous components and nanocrystalline phases with very small crystal sizes, smaller than ~3 nm, within samples containing crystalline phases is very challenging. However, this is important as there are several types of systems that contain these matrices: building materials, glass-ceramics, some alloys, etc. The total scattering synchrotron pair distribution function (PDF) can be used to characterize the local atomic order of the nanocrystalline components and to carry out quantitative analyses in complex mixtures. Although the resolution in momentum transfer space has been widely discussed, the resolution in the interatomic distance space has not been discussed to the best of our knowledge. Here, we report synchrotron PDF data collected at three beamlines in different experimental configurations and X-ray detectors. We not only discuss the effect of the resolution in Q-space, Qmax ins of the recorded data and Qmax of the processed data, but we also discuss the resolution in the interatomic distance (real) space. A thorough study of single-phase crystalline nickel used as standard was carried out. Then, selected cement-related samples including anhydrous tricalcium and dicalcium silicates, and pastes derived from the hydration of tricalcium silicate and ye’elimite with bassanite were analyzed.This work is part of the PhD of Mr. Jesus D. Zea-Garcia. This work was supported by Spanish MINECO and FEDER [BIA2017-82391-R research project and I3 [IEDI-2016-0079] program]

The Presence of Weak Active Galactic Nuclei in High Redshift Star Forming Galaxies

We present [OIII 5007A] observations of the star forming galaxy HDF-BMZ1299 (z=1.598) using Keck Observatory's Adaptive Optics system with the near-infrared integral field spectrograph OSIRIS. Using previous Halpha and [NII] measurements of the same source, we are able for the first time to use spatially resolved observations to place a high-redshift galaxy's substructure on a traditional HII diagnostic diagram. We find that HDF-BMZ1299's spatially concentrated nebular ratios in the central ~1.5 kiloparsec (0."2) are best explained by the presence of an AGN: log([NII]/Halpha)=-0.22+/-0.05 and 2sigma limit of log([OIII]/Hbeta)>0.26. The dominant energy source of this galaxy is star formation, and integrating a single aperture across the galaxy yields nebular ratios that are composite spectra from both AGN and HII regions. The presence of an embedded AGN in HDF-BMZ1299 may suggest a potential contamination in a fraction of other high-redshift star forming galaxies, and we suggest that this may be a source of the "elevated" nebular ratios previously seen in seeing-limited metallicity studies. HDF-BMZ1299's estimated AGN luminosity is L_Halpha = 3.7e41 erg/s and L_[OIII] = 5.8e41 erg/s, making it one of the lowest luminosity AGN discovered at this early epoch.Comment: 15 pages, 4 figures, ApJ Accepted, new version to be published (updated text, figures, and table

Response of Phytoplankton Photophysiology to Varying Environmental Conditions in the Sub-Antarctic and Polar Frontal Zone

Climate-driven changes are expected to alter the hydrography of the Sub-Antarctic Zone (SAZ) and Polar Frontal Zone (PFZ) south of Australia, in which distinct regional environments are believed to be responsible for the differences in phytoplankton biomass in these regions. Here, we report how the dynamic influences of light, iron and temperature, which are responsible for the photophysiological differences between phytoplankton in the SAZ and PFZ, contribute to the biomass differences in these regions. High effective photochemical efficiency of photosystem II (F 0 q/F 0 mw0.4), maximum photosynthesis rate (PB max), light-saturation intensity (Ek), maximum rate of photosynthetic electron transport (1/tPSII), and low photoprotective pigment concentrations observed in the SAZ correspond to high chlorophyll a and iron concentrations. In contrast, phytoplankton in the PFZ exhibits low F 0 q/F 0 m (* 0.2) and high concentrations of photoprotective pigments under low light environment. Strong negative relationships between iron, temperature, and photoprotective pigments demonstrate that cells were producing more photoprotective pigments under low temperature and iron conditions, and are responsible for the low biomass and low productivity measured in the PFZ. As warming and enhanced iron input is expected in this region, this could probably increase phytoplankton photosynthesis in this region. However, complex interactions between the biogeochemical processes (e.g. stratification caused by warming could prevent mixing of nutrients), which control phytoplankton biomass and productivity, remain uncertain

Effects of Destriping Errors on CMB Polarisation Power Spectra and and Pixel Noise Covariances

Low frequency detector noise in CMB experiments must be corrected to produce faithful maps of the temperature and polarization anisotropies. For a Planck-type experiment the low frequency noise corrections lead to residual stripes in the maps. Here I show that for a ring torus and idealised detector geometry it is possible to calculate analytically the effects of destriping errors on the temperature and polarization power spectra. It is also possible to compute the pixel-pixel noise covariances for maps of arbitrary resolution. The analytic model is compared to numerical simulations using a realistic detector and scanning geometries. We show that Planck polarization maps at 143 GHz should be signal dominated on large scales. Destriping errors are the dominant source of noise for the temperature and polarization power spectra at multipoles ell < 10. A fast Monte-Carlo method for characterising noise, including destriping errors, is described that can be applied to Planck. This Monte-Carlo method can be used to quantify pixel-pixel noise covariances and to remove noise biases in power spectrum estimates.Comment: 19 pages submitted to MNRA