Aqueous Solution Equilibria and Spectral Features of Copper Complexes with Tripeptides Containing Glycine or Sarcosine and Leucine or Phenylalanine

Copper(II) complexes of glycyl-L-leucyl-L-histidine (GLH), sarcosyl-L-leucyl-L-histidine (Sar-LH), glycyl-L-phenylalanyl-L-histidine (GFH) and sarcosyl-L-phenylalanyl-L-histidine (Sar-FH) have potential anti-inflammatory activity, which can help to alleviate the symptoms associated with rheumatoid arthritis (RA). From pH 2–11, the MLH, ML, MLH-1 and MLH-2 species formed. The combination of species for each ligand was different, except at the physiological pH, where CuLH-2 predominated for all ligands. The prevalence of this species was supported by EPR, ultraviolet-visible spectrophotometry, and mass spectrometry, which suggested a square planar CuN4 coordination. All ligands have the same basicity for the amine and imidazole-N, but the methyl group of sarcosine decreased the stability of MLH and MLH-2 by 0.1–0.34 and 0.46–0.48 log units, respectively. Phenylalanine increased the stability of MLH and MLH-2 by 0.05–0.29 and 1.19–1.21 log units, respectively. For all ligands, 1H NMR identified two coordination modes for MLH, where copper(II) coordinates via the amine-N and neighboring carbonyl-O, as well as via the imidazole-N and carboxyl-O. EPR spectroscopy identified the MLH, ML and MLH-2 species for Cu-Sar-LH and suggested a CuN2O2 chromophore for ML. DFT calculations with water as a solvent confirmed the proposed coordination modes of each species at the B3LYP level combined with 6-31++G**

Oxovanadium(IV) coordination compounds with kojic acid derivatives in aqueous solution

Hydroxypyrone derivatives have a good bioavailability in rats and mice and have been used in drug development. Moreover, they show chelating properties towards vanadyl cation that could be used in insulin-mimetic compound development. In this work, the formation of coordination compounds of oxovanadium(IV) with four kojic acid (5-hydroxy-2-(hydroxymethyl)-4-pyrone) derivatives was studied. The synthetized studied ligands (S2, S3, S4, and SC) have two or three kojic acid units linked through diamines or tris(2-aminoethyl)amine chains, respectively. The chemical systems were studied by potentiometry (25 °C, ionic strength 0.1 mol L-1 with KCl), and UV-visible and EPR spectroscopy. The experimental data were analyzed by a thermodynamic and a chemometric (Multivariate Curve Resolution-Alternating Least Squares) approach. Chemical coordination models were proposed, together with the species formation constants and the pure estimated UV-vis and EPR spectra. In all systems, the coordination of the oxovanadium(IV) starts already under acidic conditions (the cation is totally bound at pH higher than 3-4) and the metal species remain stable even at pH 8. Ligands S3, S4, and SC form three coordination species. Two of them are probably due to the successive insertion of the kojate units in the coordination shell, whereas the third is most likely a hydrolytic species

Regional geomorphology and history of Titan's Xanadu province

Titan’s enigmatic Xanadu province has been seen in some detail with instruments from the Cassini spacecraft. The region contains some of the most rugged, mountainous terrain on Titan, with relief over 2000 m. Xanadu contains evolved and integrated river channels, impact craters, and dry basins filled with smooth, radar-dark material, perhaps sediments from past lake beds. Arcuate and aligned mountain chains give evidence of compressional tectonism, yet the overall elevation of Xanadu is puzzlingly low compared to surrounding sand seas. Lineations associated with mountain fronts and valley floors give evidence of extension that probably contributed to this regional lowering. Several locations on Xanadu’s western and southern margins contain flow-like features that may be cryovolcanic in origin, perhaps ascended from lithospheric faults related to regional downdropping late in its history. Radiometry and scatterometry observations are consistent with a water–ice or water–ammonia–ice composition to its exposed, eroded, fractured bedrock; both microwave and visible to near-infrared (v-nIR) data indicate a thin overcoating of organics, likely derived from the atmosphere. We suggest Xanadu is one of the oldest terrains on Titan and that its origin and evolution have been controlled and shaped by compressional and then extensional tectonism in the icy crust and ongoing erosion by methane rainfall

Thermochronological and Geochronological Constraints on Late Cretaceous Unroofing and Proximal Sedimentation in the Sevier Orogenic Belt, Utah

A source-to-sink analysis incorporating geochronometric and thermochronometric data from the Sevier fold-thrust belt (SFTB) and proximal synorogenic strata of the Canyon Range Conglomerate (CRC) and Indianola Group (IG) provides new insights into orogenic exhumation, erosional unroofing, and the interplay between thrusting and coarse clastic deposition in the Cretaceous Cordilleran foreland basin of western North America. Zircon (U-Th)/He ages from the Pavant and Nebo thrust sheets record significant Cenomanian cooling indicative of synchronous exhumation and thrusting along a large segment of the SFTB in central and northern Utah. Detrital zircon (U-Th)/He (DZHe) ages indistinguishable from depositional ages from the Cenomanian Dakota Formation and lower CRC also record rapid unroofing of the SFTB and synchronous deposition. DZHe data from wedge-top deposits of the CRC record two significant unroofing episodes: Albo-Cenomanian exhumation of the Pavant thrust and progressive unroofing of the Canyon Range culmination. For the IG, the presence of Paleozoic DZHe ages along with Paleozoic-Mesozoic DZ U-Pb ages in the Cenomanian Sanpete Formation suggests derivation from Paleozoic to Jurassic strata exhumed in the frontal Pavant and Nebo thrust sheets. After the Cenomanian episode of rapid exhumation, proximal foredeep strata recorded a widespread DZ provenance shift in the Turonian. Short DZHe lag time values from Campanian CRC and IG deposits reveal rapid exhumation of the SFTB during the Campanian. The synchroneity of major shortening and Campanian and Cenomanian changes in foreland basin architecture and provenance supports models proposing that active shortening in the fold-thrust belt coincides with coarse clastic influx in foreland basins.6 month embargo; first published: 23 May 2020This item from the UA Faculty Publications collection is made available by the University of Arizona with support from the University of Arizona Libraries. If you have questions, please contact us at [email protected]