A new action photoelectron spectroscopy for anions

We present a new experimental approach, in which anion photodetachment spectroscopy is recorded with electrons of fixed kinetic energy. This approach circumvents some shortcomings of the zero electron kinetic energy method. Our method is based on a modified magnetic bottle photoelectron spectrometer (MBPES). A tunable laser is used to detach electrons from mass selected anions, drifting collinearly with the 40 cm MBPES drift tube. To avoid Doppler broadening, a low voltage pulse removes the velocity component of anions from the detached electrons. Spectra are recorded by collecting the wavelength dependence of electron-signal at a predetermined TOF window, corresponding to a specific electron-kinetic energy. We call this approach PEACE, denoting photoelectron action spectroscopy at constant kinetic energy. Our best resolution is 0.65 meV for 1.5 meV electrons. We present a PEACE spectrum of HgCl(-) together with the corresponding simulated theoretical spectrum. The method is similar in resolution and data collection rates to the slow electron velocity map imaging technique recently introduced by Neumark and co-workers.     

Mirror manifolds in higher dimension

We describe mirror manifolds in dimensions different from the familiar case of complex threefolds. We isolate certain simplifying features present only in dimension three, and supply alternative methods that do not rely on these special characteristics and hence can be generalized to other dimensions. Although the moduli spaces for Calabi-Yaud-folds are not special Kähler manifolds whend>3, they still have a restricted geometry, and we indicate the new geometrical structures which arise. We formulate and apply procedures which allow for the construction of mirror maps and the calculation of order-by-order instanton corrections to Yukawa couplings. Mathematically, these corrections are expected to correspond to calculating Chern classes of various parameter spaces (Hilbert schemes) for rational curves on Calabi-Yau manifolds. Our mirror-aided calculations agree with those Chern class calculations in the limited number of cases for which the latter can be carried out with current mathematical tools. Finally, we make explicit some striking relations between instanton corrections for various Yukawa couplings, derived from the associativity of the operator product algebra.     

In situ observation of the internal structure and composition of biomineralized Emiliania huxleyi calcite by solid-state NMR Spectroscopy

Biomineralization, particularly the formation of calcium carbonate structures by organisms under ambient conditions, is of vast fundamental and applied interest. Organisms finely control all aspects of the formation of the biomaterials: composition, polymorph, morphology, and macroscopic properties. While in situ molecular-level characterization of the resulting biominerals is a formidable task, solid-state magic angle spinning NMR is one of the most powerful analytical techniques for this purpose. It is employed in this study to elucidate the structure and composition of biogenic calcite formed by Emiliania huxleyi, a unicellular alga distinguished by its exquisitely sculptured calcite cell coverings known as coccoliths. Strain 371 (CCMP) was grown and harvested from (15)N- and (13)C-enriched growth medium, with biosynthetic labeling to enhance the sensitivity of the NMR measurements. Crystalline and interfacial calcite environments were selectively probed using direct and indirect (cross-polarized) (13)C excitation, respectively. Different crystalline environments, in particular structural defect sites at concentrations of up to 1.4% with P and N moieties incorporated, were identified using (13)C rotational-echo double-resonance (REDOR) NMR. REDOR-derived geometrical constraints show that the P and N atoms at the defect sites are 3.2 and 2.3 (+/-0.2) A apart from a crystalline carbon carbonate. The phosphorus and nitrogen moieties within the biogenic calcite are identified as small, non-protonated moieties, attributed to inorganic ions such as PO4(3-) and NO3(-). The carbonates adjacent to these defects are chemically indistinguishable from bulk crystalline carbonates, yet their immediate environments experience reduced rigidity, as reflected by substantial T1((13)CO3(2-)) shortening. Interfacial carbonates, on the other hand, reside in structurally/chemically perturbed environments, as reflected by heterogeneous line broadening. This study is the first to directly unravel evidence on the incorporation of P/N moieties as structural defects within E. huxleyi biogenic calcite, and on the state of the adjacent crystalline carbonates.     

Maleimide-activated aryl diazonium salts for electrode surface functionalization with biological and redox-active molecules

A versatile and simple method is introduced for formation of maleimide-functionalized surfaces using maleimide-activated aryl diazonium salts. We show for the first time electrodeposition of N-(4-diazophenyl)maleimide tetrafluoroborate on gold and carbon electrodes which was characterized via voltammetry, grazing angle FTIR, and ellipsometry. Electrodeposition conditions were used to control film thickness and yielded submonolayer-to-multilayer grafting. The resulting phenylmaleimide surfaces served as effective coupling agents for electrode functionalization with ferrocene and the redox-active protein cytochrome c. The utility of phenylmaleimide diazonium toward formation of a diazonium-activated conjugate, followed by direct electrodeposition of the diazonium-modified DNA onto the electrode surface, was also demonstrated. Effective electron transfer was obtained between immobilized molecules and the electrodes. This novel application of N-phenylmaleimide diazonium may facilitate the development of bioelectronic devices including biofuel cells, biosensors, and DNA and protein microarrays.     

Further studies on heterocyclic arene imines. Preparation of 1a,9b-dihydroazirino[f][1,7]phenanthroline, 3b,4a-dihydroazirino-[2,3]phenaleno[1,9-g,h]quinoline and 1a,13b-dihydrodibenzo[1,2:6,7]phenazino[1,2-b]azirine

The syntheses of the K-imine derivatives of 1,7-phenanthroline, phenaleno[1,9-g,h]quinoline, and dibenzo[a,h]phenazine are described. The parent heterocyclic compounds 4, 9 and 14 were oxidized to the corresponding K-oxides, 5, 10 and 15 , which in turn were reacted with sodium azide in aqueous acetone. The resulting trans-azido alcohols were then cyclized with tributylphosphine to the title compounds 6, 11 and 16 .     

Scheduling charter aircraft

We present a system that is used for scheduling charter aircraft. At the core of the system is an elastic set partitioning model that is embedded in a decision support system. The model assigns a set of flights that have to be performed to the available fleets of aircraft at minimal cost while satisfying all operational requirements. Flights that cannot be accommodated by the available fleets are sold off to other operators. The minimised costs include the cost of flying the aircraft, the cost of selling off flights, and penalties on violations of soft constraints. The system has been in daily operation for almost a year, and it provides high quality schedules and saves numerous hours to the schedulers.     

Braess's paradox for the spectral gap in random graphs and delocalization of eigenvectors

We study how the spectral gap of the normalized Laplacian of a random graph changes when an edge is added to or removed from the graph. There are known examples of graphs where, perhaps counter‐intuitively, adding an edge can decrease the spectral gap, a phenomenon that is analogous to Braess's paradox in traffic networks. We show that this is often the case in random graphs in a strong sense. More precisely, we show that for typical instances of Erd?s‐Rényi random graphs G (n, p ) with constant edge density , the addition of a random edge will decrease the spectral gap with positive probability, strictly bounded away from zero. To do this, we prove a new delocalization result for eigenvectors of the Laplacian of G (n, p ), which might be of independent interest. © 2016 Wiley Periodicals, Inc. Random Struct. Alg., 50, 584–611, 2017     

Kinetic bromine isotope effect: example from the microbial debromination of brominated phenols

The increasing use of kinetic isotope effects for environmental studies has motivated the development of new compound-specific isotope analysis techniques for emerging pollutants. Recently, high-precision bromine isotope analysis in individual brominated organic compounds was proposed, by the coupling of gas chromatography to a multi-collector inductively coupled plasma mass spectrometer using strontium as an external spike for instrumental bias correction. The present study, for the first time, demonstrates an application of this technique for determining bromine kinetic isotope effects during biological reaction, focusing on the reductive debromination of brominated phenols under anaerobic conditions. Results show bromine isotope enrichment factors (ε) of ?0.76?±?0.08, ?0.46?±?0.19, and ?0.20?±?0.06?‰ for the debromination of 4-bromophenol, 2,4-dibromophenol, and 2,4,6-tribromophenol, respectively. These values are rather low, yet still high enough to be obtained with satisfying certainty. This further implies that the analytical method may be also appropriate for future environmental applications.