Use of a kinetic energy orifice as a probe of metastable dissociation in Fourier transform ion cyclotron resonance mass spectrometry

Although Fourier transform ion cyclotron resonance mass spectrometry is a powerful tool in the qualitative observation of gas phase reactions, ion detection is on the millisecond time scale, orders of magnitude longer than typically found when using a sector instrument. Observations of short-lived species such as chemically activated adduct ions can be accomplished using selective ion excitation as a probe of intermediate lifetime. Whereas ion elimination has been shown to be effective in monitoring ion lifetimes on the microsecond time scale, problems associated with detecting ions produced with high kinetic energies limits the technique. Use of a kinetic energy orifice as an ion skimmer effectively eliminates ions near the center of the ion cell at relatively low kinetic energies. By modifying a single section cell to include a kinetic energy orifice, the lifetimes of chemically activated adduct ions have been investigated.     

A Chemoenzymatic Total Synthesis of the Neurogenic Starfish Ganglioside LLG-3 Using an Engineered and Evolved Synthase

An LLG-3 oligosaccharide-fluoride can be assembled chemoenzymatically and readily coupled with various sphingosines by an engineered endoglycoceramidase glycosynthase. The lyso?ganglioside products are acylated to generate the individual isomers identified in the heterogeneous natural isolates, as well as modified glycosphingolipids.     

Influence of hydrogen bonding on excitonic coupling and hierarchal structure of a light-harvesting porphyrin aggregate

Helical porphyrin nanotubes of tetrakis(4-sulfonatophenyl)porphyrin (TSPP) were examined in DCl/D(2)O solution using resonance Raman and resonance light scattering spectroscopy to probe the influence of hydrogen bonding on the excitonic states. Atomic force microscopy reveals similar morphology for aggregates deposited from DCl/D(2)O and from HCl/H(2)O solution. Deuteration results in subtle changes to the aggregate absorption spectrum but large changes in the relative intensities of Raman modes in the J-band excited resonance Raman spectra, revealing relatively more reorganization along lower-frequency vibrational modes in the protiated aggregate. Depolarization ratio dispersion and changes in the relative Raman intensities for excitation wavelengths spanning the J-band demonstrate interference from overlapping excitonic transitions. Distinctly different Raman excitation profiles for the protiated and deuterated aggregates reveal that isotopic substitution influences the excitonic structure of the J-band. The deuterated aggregate exhibits a nearly two-fold increase in intensity of resonance light scattering as a result of an increase in the coherence number, attributed to decreased exciton-phonon scattering. We propose that strongly coupled cyclic N-mers, roughly independent of isotopic substitution, largely decide the optical absorption spectrum, while water-mediated hydrogen bonding influences the further coherent coupling among them when they are assembled into nanotubes. The results show that, similar to natural light-harvesting complexes such as chlorosomes, hydrogen bonding can have a critical influence on exciton dynamics.     

Mechanism and stereoselectivity of a dual amino-catalyzed robinson annulation: rare duumvirate stereocontrol

Computational study of the mechanisms and stereoselectivities of a dual amino-catalyzed synthesis of cyclohexenones containing all-carbon γ-quaternary and ?-tertiary stereocenters is reported. Extensive conformational search with density functional theory optimizations, the high-accuracy SCS-MP2/cc-pV∞Z energies, and PCM solvation corrections were used to characterize all intermediates and transition states. Six mechanisms were considered, all consistent with available experiments. The reaction proceeds via sequential Michael and Mannich conjugate additions whereby the primary amine activates the aldehyde and the catalyst activates the pentenone. We have discovered a rare duumvirate stereocontrol: the Michael reaction sets the enantioselectivity, but both the Michael and the Mannich reactions control the diastereoselectivity.     

Sea water desalination by dynamic layer melt crystallization: Parametric study of the freezing and sweating steps

This work aims at developing a dynamic layer crystallizer operated batchwise, for freezing desalination of sea water. The experiments were performed with water/NaCl solutions and with samples of sea water from Nice, Rabat and Marseille. The pilot crystallizer consists of a cooled tube immersed in a cylindrical double jacketed tank. The solution is poured into the tank and the crystallization takes place on the external surface of the tube, by applying a cooling ramp in the tube. The solution is agitated by air bubbling. The whole process involves the freezing step, leading to the crystallization of the ice layer and the sweating step, which consists of purifying in depth the ice layer by melting the impure zones. A parametric study on the effect of the operating parameters has allowed quantifying the role of the different key parameters of the freezing and sweating steps. Three experiments allowed reaching salinities lower than 0.5 g/kg, satisfying the standards of drinking water. The duration of the whole process dropped to only 8 h (5 h for freezing and 3 h for sweating), with a yield of sweating equal to about 50%, provided severe conditions were applied for sweating. Higher yields required longer times. Overall, the results show the feasibility of the technique.     

Continuous horizontally rigid functions of two variables are affine

Cain, Clark and Rose defined a function ${{f\colon\mathbb{R}^n \to \mathbb{R}}}$ to be vertically rigid if graph(cf) is isometric to graph(f) for every c ≠?0. It is horizontally rigid if graph ${(f(c \vec{x}))}$ is isometric to graph(f) for every c ≠?0 (see Cain et?al., Real Anal. Exch. 31:515–518, 2005/2006). In Balka and Elekes (J. Math. Anal. Appl. 345:880–888, 2008) the authors of the present paper settled Jankovi?’s conjecture by showing that a continuous function of one variable is vertically rigid if and only if it is of the form a?+?bx or ${{a+be^{kx} (a,b,k \in \mathbb{R})}}$ . Later they proved in Balka and Elekes (Real. Anal. Exch. 35:139–156, 2009) that a continuous function of two variables is vertically rigid if and only if after a suitable rotation around the z-axis it is of the form ${a + bx + dy, a +s(y)e^{kx}}$ or ${{a + be^{kx} + dy (a,b,d,k \in \mathbb{R}, k \neq 0, s\colon \mathbb{R}\to \mathbb{R}\,{\rm is\, continuous})}}$ . The problem remained open in higher dimensions. The characterization in the case of horizontal rigidity is surprisingly simpler. Richter (Real Anal. Exch. 35:343–354, 2009) proved that a continuous function of one variable is horizontally rigid if and only if it is of the form ${{a+bx (a,b\in \mathbb{R})}}$ . The goal of the present paper is to prove that a continuous function of two variables is horizontally rigid if and only if it is of the form ${{a+ bx + dy (a,b,d \in \mathbb{R})}}$ . This problem also remains open in higher dimensions. The main new ingredient of the present paper is the use of functional equations.     

Thom polynomials, symmetries and incidences of singularities

As an application of the generalized Pontryagin-Thom construction [RSz] here we introduce a new method to compute cohomological obstructions of removing singularities — i.e. Thom polynomials [T]. With the aid of this method we compute some sample results, such as the Thom polynomials associated to all stable singularities of codimension ≤8 between equal dimensional manifolds, and some other Thom polynomials associated to singularities of maps N ⁿ ?P ^n+k for k>0. We also give an application by reproving a weak form of the multiple point formulas of Herbert and Ronga ([H], [Ro2]). As a byproduct of the theory we define the incidence class of singularities, which — the author believes — may turn to be an interesting, useful and simple tool to study incidences of singularities. Oblatum 4-II-1999 & 19-VII-2000?Published online: 30 October 2000     

Acyclic Stereocontrol in the Additions of Nucleophilic Alkenes to α-Chiral N-Sulfonyl Imines

Diastereoselective Lewis acid-mediated additions of nucleophilic alkenes to N-sulfonyl imines are reported. The canonical polar Felkin–Anh model describing additions to carbonyls does not adequately describe analogous additions to N-sulfonyl imines. Herein, we describe the development of conditions to produce both syn and anti products with high diastereoselectivity and good yields. A stereoelectronic model consistent with experimental outcomes is also proposed.