The structure of vincarodine

The structure of vincarodine has been determined to be 1 by an investigation of its IR.-, UV.-, ¹H- and ¹³C-NMR.- and mass spectra. A ¹³C-NMR. analysis has been performed on the bases vincamine ( 2 ), epivincine ( 9 ), 14, 15-dehydrovincine ( 7 ) and its 16-epimer ( 8 ).     

A theoretical study of three and four proton donors on linear HX···BeH2···HX and bifurcate BeH2···2HX trimolecular dihydrogen-bonded complexes with X?=?CN and NC

The interaction phenomenon H^−δ···H^+δ between two hydrogen atoms binding each other is well-known in dihydrogen-bonded complexes. Either by experimental or theoretical viewpoint, dihydrogen bonds are often known as directional or bifurcate interactions. Regarding the beryllium hydride BeH₂, its capacity to form bimolecular complexes with proton donors has been demonstrated, but in some cases, trimolecular complexes are also characterized in a minimum of the potential energy surface. As such, in this work is presented a theoretical study about the formation of trimolecular dihydrogen complexes with three hydrogen centers. By taking into account the beryllium hydride BeH₂ as proton acceptor, two classical proton donors were chosen, HCN and HNC. The great goal of this work is the analysis of two dihydrogen complexes types: bifurcate BeH₂···2HX and linear HX···BeH₂···HX. In these systems, it is discussed the capacity of one hydride H^−δ (H–Be–H^−δ) to interact simultaneously with two proton donors, as well as when two hydrides H^−δ (^−δH–Be–H^−δ) form linear dihydrogen bonds. In this context, the analysis of the vibrational harmonic spectrum at B3LYP/6-311 ++G(3d,3p) level of theory and the interpretation of the topological parameters derived from Quantum Theory of Atoms in Molecules (QTAIM) aided us to determine which is the most stable trimolecular complex, either bifurcate or linear. Moreover, quantification of charge transfer measured by the QTAIM formalism as well as by ChelpG calculations also were used with the purpose to justify infrared effects, such as red-shift and blue-shift stretch modes on donors (HCN and HNC) and acceptors (BeH₂) of protons.     

The minimal cardinality where the Reznichenko property fails

A topological spaceX has the Fréchet-Urysohn property if for each subsetA ofX and each elementx inĀ, there exists a countable sequence of elements ofA which converges tox. Reznichenko introduced a natural generalization of this property, where the converging sequence of elements is replaced by a sequence of disjoint finite sets which eventually intersect each neighborhood ofx. In [5], Kočinac and Scheepers conjecture: The minimal cardinality of a setX of real numbers such thatC _p(X) does not have the weak Fréchet-Urysohn property is equal to b. (b is the minimal cardinality of an unbounded family in the Baire space^Nℕ.) We prove the Kočinac-Scheepers conjecture by showing that ifC _p(X) has the Reznichenko property, then a continuous image ofX cannot be a subbase for a non-feeble filter on ℕ. The author is partially supported by the Golda Meir Fund and the Edmund Landau Center for Research in Mathematical Analysis and Related Areas, sponsored by the Minerva Foundation (Germany).     

Coiled to diffuse: brownian motion of a helical bacterium

We employ real-time three-dimensional confocal microscopy to follow the Brownian motion of a fixed helically shaped Leptospira interrogans (LI) bacterium. We extract from our measurements the translational and the rotational diffusion coefficients of this bacterium. A simple theoretical model is suggested, perfectly reproducing the experimental diffusion coefficients, with no tunable parameters. An older theoretical model, where edge effects are neglected, dramatically underestimates the observed rates of translation. Interestingly, the coiling of LI increases its rotational diffusion coefficient by a factor of 5, compared to a (hypothetical) rectified bacterium of the same contour length. Moreover, the translational diffusion coefficients would have decreased by a factor of ～1.5, if LI were rectified. This suggests that the spiral shape of the spirochaete bacteria, in addition to being employed for their active twisting motion, may also increase the ability of these bacteria to explore the surrounding fluid by passive Brownian diffusion.     

Electron ionization LC‐MS with supersonic molecular beams—the new concept,benefits and applications

A new type of electron ionization LC‐MS with supersonic molecular beams (EI‐LC‐MS with SMB) is described. This system and its operational methods are based on pneumatic spray formation of the LC liquid flow in a heated spray vaporization chamber, full sample thermal vaporization and subsequent electron ionization of vibrationally cold molecules in supersonic molecular beams. The vaporized sample compounds are transferred into a supersonic nozzle via a flow restrictor capillary. Consequently, while the pneumatic spray is formed and vaporized at above atmospheric pressure the supersonic nozzle backing pressure is about 0.15 Bar for the formation of supersonic molecular beams with vibrationally cold sample molecules without cluster formation with the solvent vapor. The sample compounds are ionized in a fly‐though EI ion source as vibrationally cold molecules in the SMB, resulting in ‘Cold EI’ (EI of vibrationally cold molecules) mass spectra that exhibit the standard EI fragments combined with enhanced molecular ions. We evaluated the EI‐LC‐MS with SMB system and demonstrated its effectiveness in NIST library sample identification which is complemented with the availability of enhanced molecular ions. The EI‐LC‐MS with SMB system is characterized by linear response of five orders of magnitude and uniform compound independent response including for non‐polar compounds. This feature improves sample quantitation that can be approximated without compound specific calibration. Cold EI, like EI, is free from ion suppression and/or enhancement effects (that plague ESI and/or APCI) which facilitate faster LC separation because full separation is not essential. The absence of ion suppression effects enables the exploration of fast flow injection MS‐MS as an alternative to lengthy LC‐MS analysis. These features are demonstrated in a few examples, and the analysis of the main ingredients of Cannabis on a few Cannabis flower extracts is demonstrated. Finally, the advantages of EI‐LC‐MS with SMB are listed and discussed. Copyright © 2015 John Wiley & Sons, Ltd.     

Sub-second 2D NMR spectroscopy at sub-millimolar concentrations

A recently proposed protocol enables the acquisition of two-dimensional nuclear magnetic resonance (2D NMR) spectra within a single scan. A promising application opened up by this new data acquisition mode concerns its combination with active nuclear polarization methods, whereby spectroscopy is carried out on analytes whose spin magnetizations have been significantly enhanced over their Boltzmann thermal values. The present paper explores the potential of such combination, with the acquisition of peptide and protein 2D NMR 1H correlation spectra recorded after the samples had been subject to laser-driven chemically induced dynamic nuclear polarization (CIDNP). It is demonstrated that the speed and sensitivity enhancement afforded by these combined processes enables the acquisition of quality 2D NMR data sets within a fraction of a second, at analyte concentrations that are under 1 mM.