Trennung isomerer Alkohole mittels der Gas-Flüssig-Chromatographie, 1. Mitt.: Trennung der gesättigten C5-Alkohole

Zusammenfassung Unter geeigneten Bedingungen können Mischungen, welche alle acht möglichen C₅-Alkohole enthalten, sowiet aufgetrennt werden, daß vom Schreiber sieben Verbindungen angezeigt werden. Einfachere Mischungen können noch bessere Resultate geben. Das Paar 2-methyl- und 3-Methyl-butanol-(1) konnte bisher nicht aufgetrennt werden. Die Retentionszeiten in der Mischung stimmen nicht genau mit denen der Reinstoffe überein.Mit 1 Abbildung     

Computer assisted clinical chemical diagnosis,pattern cognition and recognition by cluster analysis

Cluster analysis is a good tool for finding and defining groupings of patients with similar patterns of clinical chemical data. The same algorithm (k-means) used for pattern cognition can be employed for pattern recognition.     

2′-O-Trifluoromethylated RNA – a powerful modification for RNA chemistry and NMR spectroscopy

New RNA modifications are needed to advance our toolbox for targeted manipulation of RNA. In particular, the development of high-performance reporter groups facilitating spectroscopic analysis of RNA structure and dynamics, and of RNA–ligand interactions has attracted considerable interest. To this end, fluorine labeling in conjunction with ¹⁹F-NMR spectroscopy has emerged as a powerful strategy. Appropriate probes for RNA previously focused on single fluorine atoms attached to the 5-position of pyrimidine nucleobases or at the ribose 2′-position. To increase NMR sensitivity, trifluoromethyl labeling approaches have been developed, with the ribose 2′-SCF₃ modification being the most prominent one. A major drawback of the 2′-SCF₃ group, however, is its strong impact on RNA base pairing stability. Interestingly, RNA containing the structurally related 2′-OCF₃ modification has not yet been reported. Therefore, we set out to overcome the synthetic challenges toward 2′-OCF₃ labeled RNA and to investigate the impact of this modification. We present the syntheses of 2′-OCF₃ adenosine and cytidine phosphoramidites and their incorporation into oligoribonucleotides by solid-phase synthesis. Importantly, it turns out that the 2′-OCF₃ group has only a slight destabilizing effect when located in double helical regions which is consistent with the preferential C3′-endo conformation of the 2′-OCF₃ ribose as reflected in the ³J (H1′–H2′) coupling constants. Furthermore, we demonstrate the exceptionally high sensitivity of the new label in ¹⁹F-NMR analysis of RNA structure equilibria and of RNA–small molecule interactions. The study is complemented by a crystal structure at 0.9 Å resolution of a 27 nt hairpin RNA containing a single 2′-OCF₃ group that well integrates into the minor groove. The new label carries high potential to outcompete currently applied fluorine labels for nucleic acid NMR spectroscopy because of its significantly advanced performance.

The new 2′-OCF₃ label for nucleic acid NMR spectroscopy carries high potential to outcompete currently applied fluorine labels because of significantly advanced performance.     

Chelatkomplexe von Rheniumtetrachlorid. Die Kristallstrukturen von ReCl4(DME) und ReCl4(DPPE) · Tolan

Chelate Complexes of Rhenium Tetrachloride. The Crystal Structures of ReCl₄(DME) and ReCl₄(DPPE) · Tolan Bright green crystals of ReCl₄(DME) have been prepared by the reaction of rhenium pentachloride with dimethoxyethane (DME) in dichloromethane. ReCl₄(DPPE) · tolan was obtained in form of red crystals by the reaction of the alkyne complex [ReCl₄(Ph? C?C? Ph)(POCl₃)] with bis(diphenylphosphino)ethane (DPPE) in dichloromethane. The complexes were characterized by X-ray structure determinations. ReCl₄(DME): Space group I4 2d, Z = 8, 829 observed unique reflexions, R = 0.022. Lattice dimensions at 19.5°C: a = b = 960.60(6), c = 2337.2(6) pm. The complex forms monomeric molecules with DME as chelating ligand; the Re? O bond lengths are 213.1 pm. The chlorine atoms, arranged in trans position to the chelating ligand, have slightly shorter Re? Cl bonds than the chlorine atoms in cis position (232,1 pm). ReCl₄(DPPE) · tolan: Space group P2₁/n, Z = 4,4313 observed unique reflexions, R = 0.040. Lattice dimensions at ?80°C: a = 1095.7(1), b = 1764.2(2), c = 1898.0(2) pm, β = 99.229(8)°. The compound consists in form of monomeric molecules [ReCl₄(DPPE)] and diphenylacetylene molecules, which are incorporated in the lattice. The two phenyl rings of the tolan molecules are twisted towards each other along the C? C axis with a dihedral angle of 21°. The DPPE molecules are bonded to the rhenium atom in a chelating fashion with medium Re? P lengths of 250.4 pm. The chlorine atoms, arranged in trans position to this ligand, with Re? Cl bond lengths of 234.5 pm are slightly longer than the Re? Cl bonds in cis position with 232.3 pm.     

Investigation of thin surface films by microprobe analysis

The electron microprobe has been applied to study thin films on metallic substrates. The intensities of the characteristic X-rays emitted by thin films of various elements and thicknesses on sublayers of different materials were measured. Two different theoretical approaches (Bishop and Poole, as well as Yakowitz and Newbury) were applied to interpet the X-ray intensities and to determine the film thickness from the intensity measurements. The effect of backscattering from the substrate, resulting in an increase of the intensity of characteristic X-rays of the film, is being described on the basis of a theory given by Hutchins. The corresponding equation for the backscattering factor has been modified to take into account the transmission of the electrons through the film, depending on the mass thickness of the film and the electron energy. The results obtained from theory and experiment are in good agreement for the different experimental parameters applied, except for very thick layers of high atomic numbers measured at low energies where the absorption of electrons in the film plays a dominant role.     

The enthalpies of formation of two dibenzocyclooctadienones

The standard molar enthalpies of formation (Δ_fH_m⁰(s)/kJmol⁻¹) for 2,3:6,7-dibenzocycloocta-2,6-dien-1-one and 2,3:7,8-dibenzocycloocta-2,7-dien-1-one [6H-11,12-dihydro-dibenzo[a,e]cycloocten-5-one (ketone 1) and 10H-11,12-dihydrodibenzo[a,d]-cycloocten-5-one (ketone 2), respectively] were derived from enthalpies of combustion, measured by means of a microbomb calorimeter. The fusion and vaporization enthalpies of these compounds were obtained from DSC and correlation gas chromatography measurements. The standard molar enthalpies of formation in the gas phase were calculated by combining the condensed phase standard molar enthalpies of formation with the fusion and vaporization enthalpies adjusted to 298.15 K. Values for Δ_fH_m⁰(g) of (−39.9±5.5) and (−14.8±5.3) kJ mol⁻¹ were obtained for 2,3:6,7-dibenzocycloocta-2,6-dien-1-one and 2,3:7,8-dibenzocycloocta-2,7-dien-1-one, respectively. Quantum chemical calculations are reported for the compounds investigated experimentally and an additional four isomers. Isomerization enthalpies are derived from computed energies. The enthalpies of formation are also calculated by group additivity, compared with the experimental values and then correlated with the structure of the molecules investigated. The X-ray analysis of ketone 1 is also reported.     

Cooperative melting in caged dimers of rigid small molecule-DNA hybrids

Rigid small-molecule DNA hybrids (rSMDHs) have been synthesized with three DNA strands attached to a rigid tris(phenylacetylene) core. When combined under dilute conditions, complementary rSMDHs form cage dimers that melt at >10 degrees C higher and much sharper than either unmodified DNA duplexes or rSMDH aggregates formed at higher concentrations. With a 2.97 average number of cooperative duplexes, these caged dimers constitute the first example of cooperative melting in well-defined DNA-small-molecule structures, demonstrating the important roles that local geometry and ion concentration play in the hybridization/dehybridization of DNA-based materials.     

Cellular Cations Control Conformational Switching of Inositol Pyrophosphate Analogues

The inositol pyrophosphate messengers (PP‐InsPs) are emerging as an important class of cellular regulators. These molecules have been linked to numerous biological processes, including insulin secretion and cancer cell migration, but how they trigger such a wide range of cellular responses has remained unanswered in many cases. Here, we show that the PP‐InsPs exhibit complex speciation behaviour and propose that a unique conformational switching mechanism could contribute to their multifunctional effects. We synthesised non‐hydrolysable bisphosphonate analogues and crystallised the analogues in complex with mammalian PPIP5K2 kinase. Subsequently, the bisphosphonate analogues were used to investigate the protonation sequence, metal‐coordination properties, and conformation in solution. Remarkably, the presence of potassium and magnesium ions enabled the analogues to adopt two different conformations near physiological pH. Understanding how the intrinsic chemical properties of the PP‐InsPs can contribute to their complex signalling outputs will be essential to elucidate their regulatory functions.     

Delivery of myo-Inositol Hexakisphosphate to the Cell Nucleus with a Proline-Based Cell-Penetrating Peptide

Inositol hexakisphosphate (InsP₆) is a central member of the inositol phosphate messengers in eukaryotic cells. Tools to manipulate the level of InsP₆, particularly with compartment selectivity, are needed to enable functional cellular studies. We present cationic octa-(4S)guanidiniumproline ( Z8 ) for the delivery of InsP₆ into the cell nucleus. CD spectroscopy, binding affinity, dynamic light scattering, and computational studies revealed that Z8 binds tightly to InsP₆ and upon binding undergoes a conformational change from a PPII-helical structure to a structure that forms aggregates. The unique conformational features of the cationic oligoproline enable complex formation and cellular delivery of InsP₆ with considerably greater efficacy than the flexible counterpart octaarginine.