MASSENSPEKTROMETRISCHE UNTERSUCHUNGEN VON DIARYLMETHYLEN-BIS-XANTHOGENATEN UND DIARYL-DITHIOACETALEN: II

The mass spectral fragmentation patterns of some diarylmethylene-bis-xanthates have been investigated and are compared with those for the 1,1,α,α-dibenzyl-thioacetals 1,1-diphenylmethane. The formation of a sulphenium cation is characteristic for the bis-xanthates. Their subsequent fragmentation is similar to that of thioesters. Also noteworthy is the appearance of ions having thio-ketone-like structures, except in the case of 1,1,α,α-diphenyl thioacetal 1,1-diphenylmethane. This is compared with the pyrolytic behaviour. The intensity of various metastable decompositions leading to the [benzophenone]+. ion in the first field free region depends mostly on the excess thermal energy.     

Comparison of InGaN/GaN light emitting diodes grown on m ‐plane and a ‐plane bulk GaN substrates

InGaN/GaN‐based light emitting diodes (LEDs) grown on m ‐plane, a ‐plane and off‐axis between m ‐ and a ‐plane GaN bulk substrates were investigated. A smooth surface was obtained when a ‐plane substrate was applied; however, large amounts of defects were observed. Photoluminescence measurements of the LEDs with a well thickness of 2.5 nm revealed that all the LEDs showed the peak emission wavelength at 389 nm. The PL intensity of the a ‐plane LED is one order of magnitude lower than that of the m ‐plane LED. The a ‐plane LEDs showed significant lower electroluminescence output powers than m ‐plane LEDs, suggesting that excitons are trapped by the defects, which act as non‐radiative recombination centers. (© 2008 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Single atoms in an optical dipole trap: towards a deterministic source of cold atoms

We describe a simple experimental technique which allows us to store a small and deterministic number of neutral atoms in an optical dipole trap. The desired atom number is prepared in a magneto-optical trap overlapped with a single focused Nd:YAG laser beam. Dipole trap loading efficiency of 100% and storage times of about one minute have been achieved. We have also prepared atoms in a certain hyperfine state and demonstrated the feasibility of a state-selective detection via resonance fluorescence at the level of a few neutral atoms. A spin relaxation time of the polarized sample of 4.2+/-0.7 s has been measured. Possible applications are briefly discussed.     

Enhancement in MS-based peptide detection by microfluidic free-flow zone electrophoresis

Matrix components are known to significantly alter the ionization of a target analyte in ESI-based measurements particularly when working with complex biological samples. This issue however may be alleviated by extracting the analyte of interest from the original sample into a relatively simple matrix compatible with ESI mass-spectrometric analysis. In this article, we report a microfluidic device that enables such extraction of small peptide molecules into an ESI-compatible solvent stream significantly improving both the sensitivity and reproducibility of the measurements. The reported device realizes this analyte extraction capability based on the free-flow zone electrophoretic fractionation process using a set of internal electrodes placed across the width of the analysis channel. Employing lateral electric fields and separation distances of 75 V/cm and 600 µm, respectively, efficient extraction of the model peptide human angiotensin II was demonstrated allowing a reduction in its detection limit by one to three orders of magnitude using the ESI-MS method. The noted result was obtained in our experiments both for a relatively simple specimen comprising DNA strands and angiotensin II as well as for human serum samples spiked with the same model peptide.     

Fast and Efficient Method to Obtain Tagitinin F by Photocyclization of Tagitinin C

There is some evidence in the literature of the photocyclization reaction of Tagitinin C ( 1 ) to Tagitinin F ( 2 ). Compound 2 has high pharmacological potential, but it is not easy to obtain, while compound 1 is easily obtained from a widespread plant, Tithonia diversifolia. Among different reaction conditions monitored, one was found that allowed the cyclization of 1 into 2 in <15 min in a photo-dependent reaction. Scaling-up the photocyclization of the pure compound 1 into 2 demonstrated 100% yield, and the isolation of 2 from a UV-irradiated extract was eight-fold higher than the quantity isolated from the non-UV-irradiated extract. We were also able to better understand the process of photoconversion and determine methods to isolate and quantify these compounds, which are known for their important antitumoral activities among other important pharmacological properties.     

Syntheses, structures, spectroscopy, and chromotropism of new complexes arising from the reaction of nickel(II) nitrate with diphenyl(dipyrazolyl)methane

The complexes [(dpdpm)Ni(2-NO3)2] (1), [(dpdpm)Ni(2-NO3)(1-NO3)(CH3CN)] (2), [(dpdpm)2Ni(1-NO3)(H2O)]NO3 (3), and [(dpdpm)2Ni(H2O)2][NO3]2 (4) (dpdpm = diphenyl(dipyrazolyl)methane, Ph2C(C3N2H3)2), have been prepared and characterized by IR and UV-vis-NIR spectroscopy and X-ray diffraction studies. X-ray studies have confirmed that complexes 1-4 all adopt variously distorted octahedral structures in the solid state, the largest distortions arising from the small bite-angle of the bidentate nitrate ligand in 1 and 2. Magnetic moment measurements indicate that these solids are paramagnetic with two unpaired electrons. The solution 1H NMR data show that the paramagnetism is maintained in solution. Absorption spectra of 1-4 show three main bands in the region of 350-1000 nm representing spin allowed (d-d) transitions from the ground state 3A2g to the excited states 3T2g, 3T1g(3F), and 3T1g(3P). A weak shoulder was also detected at about 700-800 nm in most spectra, representing spin-forbidden transitions 3A2g 1Eg. A comparison of the crystal field parameters 10Dq and B for 1-4 to the corresponding values for related complexes indicated that these parameters are fairly insensitive to structural variations within this family of complexes. The 10Dq/B ratios show greater variations, but no clear correlations are apparent between 10Dq/B and such structural features as the nature of ligator atoms (N:O ratio), the bonding mode of the nitrate ligand, or the overall charge. Complexes 1 (green) and 2 (blue) interconvert as a function of temperature (solutions and solid samples), concentration of CH3CN (solutions), or CH3CN vapor pressure (solid samples).     

Fusion: a general framework for hierarchical tilings of \mathbb{R }^d

We introduce a formalism for handling general spaces of hierarchical tilings, a category that includes substitution tilings, Bratteli–Vershik systems, S-adic transformations, and multi-dimensional cut-and-stack transformations. We explore ergodic, spectral and topological properties of these spaces. We show that familiar properties of substitution tilings carry over under appropriate assumptions, and give counter-examples where these assumptions are not met. For instance, we exhibit a minimal tiling space that is not uniquely ergodic, with one ergodic measure having pure point spectrum and another ergodic measure having mixed spectrum. We also exhibit a 2-dimensional tiling space that has pure point measure-theoretic spectrum but is topologically weakly mixing.     

Frankl–Füredi–Kalai Inequalities on the γ-Vectors of Flag Nestohedra

For any flag nestohedron, we define a flag simplicial complex whose f-vector is the γ-vector of the nestohedron. This proves that the γ-vector of any flag nestohedron satisfies the Frankl–Füredi–Kalai inequalities, partially solving a conjecture by Nevo and Petersen (Discrete Comput. Geom. 45:503–521, 2010). We also compare these complexes to those defined by Nevo and Petersen (Discrete Comput. Geom. 45:503–521, 2010) for particular flag nestohedra.     

Towards a quantal dynamical simulation of the neutron star’s crust

We present a novel method to study the dynamics of bulk fermion systems such as the neutron star’s crust. By introducing periodic boundary conditions into Fermionic Molecular Dynamics, it becomes possible to examine the long-range many-body correlations induced by antisymmetrisation in bulk fermion systems. The presented technique treats the spins and the fermionic nature of the nucleons explicitly and permits investigating the dynamics of the system. Despite the increased complexity related to the periodic boundary conditions, the proposed formalism remains computationally feasible.     

A tetrapyridine ligand with a rigid tetrahedral core forms metal-organic frameworks with PtS type architecture

A new tetradentate, pyridine ligand with a rigid tetrahedral core can be prepared in good yield by a cross-coupling methodology. Two metal organic framework structures of Cu(II) with PtS-type topology having a carbon atom as the tetrahedral node have been characterized utilising this ligand.