Exploring subsurface fluid flow and active dewatering along the oceanic plate boundary between Africa and Eurasia (Gloria Fault)

R/V Meteor cruise M162 was conducted as a systematic continuation of ongoing work dedicated to understand if and howfluid flow through crust and sedimentscontinues along transform-type plate boundaries and fracture zones away from mid-ocean ridges and continental margins. Central target was the Gloria Fault in the central Northeast Atlantic. Previous findings along the eastern continuation of the Gloria Fault revealed fault-controlled fluid advection and mud volcanism along strike-slip faults in the Horseshoe Abyssal Plain and the Gulf of Cadiz, where fluid geochemistry revealed the admixture of fluids from deeply buried oceanic crust and oldest sediments on top of it. TheGloria Fault itselfis an old, reactivated, and seismically active oceanic fracture zone. During M162 a systematic survey along the main trace of the Gloria Fault between the Azores Plateau and the Madeira-Tore Rise was carried out, including sub-bottom profiler surveys, heat flow transects, gravity corer sampling, as well as video-guided CTD and multicorer deployments. In accordance to recently recorded seismic activity along the fault, there isevidence for tectonic motion both in sub-bottom profiler records and sediment cores. Heat flow measurements revealed values significantly elevated above the background in many places, predominantly along the main fault trace and other active faults.Ina number of placesfluid geochemistry revealed enhanced diagenetic processes in the sediments, implying the potential relation to upward-directed fluid flow. In summary, cruise M162revealed the first complementary data set on heat flow and fluid geochemistry along an oceanic fault zone, which will further our understanding on themes like the alteration of oceanic lithosphere and crust-ocean element exchange

Superelectrophilic Tetrakis(carbonyl)palladium(II)- and -platinum(II) Undecafluorodiantimonate(V), [Pd(CO)₄][Sb₂F₁₁]₂ and [Pt(CO)₄][Sb₂F₁₁]₂: Syntheses, Physical and Spectroscopic Properties, Their Crystal, Molecular, and Extended Structures, and Density Functional Calculations: An Experimental, Computational, and Comparative Study

The salts [M(CO)4][Sb2F11]2, M = Pd, Pt, are prepared by reductive carbonylation of Pd[Pd(SO3F)6], Pt(SO3F)6 or PtF6 in liquid SbF5, or HF−SbF5. The resulting moisture-sensitive, colorless solids are thermally stable up to 140 °C (M = Pd) or 200 °C (M = Pt). Their thermal decompositions are studied by differential scanning calorimetry (DSC). Single crystals of both salts are suitable for an X-ray diffraction study at 180 K. Both isostructural salts crystallize in the monoclinic space group P21/c (No. 14). The unit cell volume of [Pt(CO)4][Sb2F11]2 is smaller than that of [Pd(CO)4][Sb2F11]2 by about 0.4%. The cations [M(CO)4]2+, M = Pd, Pt, are square planar with only very slight angular and out-of-plane deviations from D4h symmetry. The interatomic distances and bond angles for both cations are essentially identical. The [Sb2F11]- anions in [M(CO)4][Sb2F11]2, M = Pd, Pt, are not symmetry-related, and both pairs differ in their Sb−F−Sb bridge angles and their dihedral angles. There are in each salt four to five secondary interionic C- -F contacts per CO group. Of these, two contacts per CO group are significantly shorter than the sum of the van der Waals radii by 0.58 − 0.37 Å. In addition, structural, and spectroscopic details of recently synthesized [Rh(CO)4][Al2Cl7] are reported. The cations [Rh(CO)4]+ and [M(CO)4]2+, M = Pd, Pt, are characterized by IR and Raman spectroscopy. Of the 16 vibrational modes (13 observable, 3 inactive) 10 (Pd, Pt) or 9 (Rh), respectively, are found experimentally. The vibrational assignments are supported by DFT calculations, which provide in addition to band positions also intensities of IR bands and Raman signals as well as internal force constants for the cations. 13C NMR measurements complete the characterization of the square planar metal carbonyl cations. The extensive characterization of [M(CO)4][Sb2F11]2, M = Pd, Pt, reported here, allows a comparison to linear and octahedral [M(CO)n][Sb2F11]2 salts [M = Hg (n = 2); Fe, Ru, Os (n = 6)] and their derivatives, which permit a deeper understanding of M−CO bonding in the solid state for superelectrophilic cations with [Sb2F11]- or [SbF6]- as anions

Synthesis of Indofulvin Pseudo-Natural Products Yields a New Autophagy Inhibitor Chemotype

Abstract Chemical and biological limitations in bioactive compound design based on natural product (NP) structure can be overcome by the combination of NP‐derived fragments in unprecedented arrangements to afford “pseudo‐natural products” (pseudo‐NPs). A new pseudo‐NP design principle is described, i.e., the combination of NP‐fragments by transformations that are not part of current biosynthesis pathways. A collection of indofulvin pseudo‐NPs is obtained from 2‐hydroxyethyl‐indoles and ketones derived from the fragment‐sized NP griseofulvin by means of an iso‐oxa‐Pictet‐Spengler reaction. Cheminformatic analysis indicates that the indofulvins reside in an area of chemical space sparsely covered by NPs, drugs, and drug‐like compounds and they may combine favorable properties of these compound classes. Biological evaluation of the compound collection in different cell‐based assays and the unbiased high content cell painting assay reveal that the indofulvins define a new autophagy inhibitor chemotype that targets mitochondrial respiration