Beitrag zur Anwendung der Infrarotspektroskopie für Untersuchungen von Farberden kulturhistorischer Objekte im Vergleich mit rezenten europäischen Lagerstätten

Various iron oxide pigments have been analysed by means of infra-red spectroscopy and 10 characteristic minerals have been found, which are utilized for distinguishing and classifying the pigments. In case of paintings certain difficulties arise because of the possible admixture of other pigments and fillers.     

Prediction of programmed temperature retention times on linked capillary columns of different polarity

Systems formed by serial connection of capillary columns of different polarity were studied with methods previously used to predict the behavior of linked capillary columns under isothermal conditions and to obtain programmed temperature gas chromatography (PTGC) retention times of the individual columns starting from isothermal data. The two calculation methods were simultaneously applied in order to predict PTGC retention times of the series system starting from isothermal data obtained on the two individual columns. Experimental retention values measured using different temperature programs on the individual columns and on the series systems were found to agree with those calculated.     

Tailoring the mobility of a 3D molecule adsorbed on a metal surface

Because of its tetrahedral structure, spirobifluorene is an innovative molecule for molecular mechanics studies by means of scanning tunneling microscopy. On Cu(100), it was observed only anchored at defects because of its mobility at room temperature. To frustrate its diffusion, it was functionalized with phenyl and thiophene groups. Tetraphenylspirobifluorene is also mobile on Cu(100), whereas tetrathienylspirobifluorene is fixed in the middle of the terraces. This very different behavior is an original and unexpected result because both benzene and thiophene are reported to be weakly bound to Cu(100) with almost the same adsorption energy.     

Unified molecular picture of the surfaces of aqueous acid, base, and salt solutions

The molecular structure of the interfacial regions of aqueous electrolytes is poorly understood, despite its crucial importance in many biological, technological, and atmospheric processes. A long-term controversy pertains between the standard picture of an ion-free surface layer and the strongly ion specific behavior indicating in many cases significant propensities of simple inorganic ions for the interface. Here, we present a unified and consistent view of the structure of the air/solution interface of aqueous electrolytes containing monovalent inorganic ions. Molecular dynamics calculations show that in salt solutions and bases the positively charged ions, such as alkali cations, are repelled from the interface, whereas the anions, such as halides or hydroxide, exhibit a varying surface propensity, correlated primarily with the ion polarizability and size. The behavior of acids is different due to a significant propensity of hydronium cations for the air/solution interface. Therefore, both cations and anions exhibit enhanced concentrations at the surface and, consequently, these acids (unlike bases and salts) reduce the surface tension of water. The results of the simulations are supported by surface selective nonlinear vibrational spectroscopy, which reveals among other things that the hydronium cations are present at the air/solution interface. The ion specific propensities for the air/solution interface have important implications for a whole range of heterogeneous physical and chemical processes, including atmospheric chemistry of aerosols, corrosion processes, and bubble coalescence.     

The Binding Pocket at the Interface of Multimeric Telomere G-quadruplexes: Myth or Reality?

Human telomeric DNA with hundreds of repeats of the 5’-TTAGGG-3’ motif plays a crucial role in several biological processes. It folds into G-quadruplex (G4) structures and features a pocket at the interface of two contiguous G4 blocks. Up to now no structural NMR and crystallographic data are available for ligands interacting with contiguous G4s. Naphthalene diimide monomers and dyads were investigated as ligands of a dimeric G4 of human telomeric DNA comparing the results with those of the model monomeric G4. Time-resolved fluorescence, circular dichroism, isothermal titration calorimetry and molecular modeling were used to elucidate binding features. Ligand fluorescence lifetime and induced circular dichroism unveiled occupancy of the binding site at the interface. Thermodynamic parameters confirmed the hypothesis as they remarkably change for the dyad complexes of the monomeric and dimeric telomeric G4. The bi-functional ligand structure of the dyads is a fundamental requisite for binding at the G4 interface as only the dyads engage in complexes with 1 : 1 stoichiometry, lodging in the pocket at the interface and establishing multiple interactions with the DNA skeleton. In the absence of NMR and crystallographic data, our study affords important proofs of binding at the interface pocket and clues on the role played by the ligand structure.     

NMR Analysis and Regiochemical Structure of Some Selectively 13C‐Enriched Poly(propylene)s

Summary: The regiochemical structures of poly(propylene)s obtained in the presence of three single‐site catalysts, Cp*Ti(CH₃)₃ + B(C₆F₅)₃ (I + III), CpTi(CH₃)₃ + B(C₆F₅)₃ (II + III), and VCl₄ + anisole + Al(C₂H₅)₂Cl (V + A), are investigated by ¹³C NMR analysis. Polymer 1 , obtained in the presence of I + III is, seemingly, fully regioregular, while, surprisingly, polymer 2 , obtained in the presence of II + III, appears to be alternating sequence of primary and secondary regioblocks, very much like polymer 3 , obtained in the presence of V + A. The stereochemical structure of the polymer obtained in the presence of I + III is in excellent agreement with a Bernoullian statistical model of the stereoselective propagation, while those of the other two polymers possibly require a Coleman‐Fox model.

¹³C NMR spectra of 10%‐enriched poly[(2‐¹³C)propylene], 1′ and 2′ , prepared under the conditions reported in Table 1 for the corresponding poly(propylene)s, 1 and 2 . The resonances of the tertiary carbons are diagnostic of the regioblock structure of sample 2′ .     

A Solvent-Exposed Cysteine Forms a Peculiar NiII-Binding Site in the Metallochaperone CooT from Rhodospirillum rubrum

In Rhodospirillum rubrum, the maturation of carbon monoxide dehydrogenase (CODH) requires three nickel chaperones, namely RrCooC, RrCooT and RrCooJ. Recently, the biophysical characterisation of the RrCooT homodimer and the X-ray structure of its apo form revealed the existence of a solvent-exposed Ni^II-binding site at the dimer interface, involving the strictly conserved Cys2. Here, a multifaceted approach that used NMR and X-ray absorption spectroscopies, complemented with structural bio-modelling methodologies, was used to characterise the binding mode of Ni^II in RrCooT. This study suggests that Ni^II adopts a square-planar geometry through a N₂S₂ coordinating environment that comprises the two thiolate and amidate groups of both Cys2 residues at the dimer interface. The existence of a diamagnetic mononuclear Ni^II centre with bis-amidate/bis-thiolate ligands, coordinated by a single-cysteine motif, is unprecedented in biology and raises the question of its role in the activation of CODH at the molecular level.