Silyl- and Germyl-Substituted Diorganophosphonites

Reactions of metalated diorganophosphonite boranes with triorganosilyl and -germyl halides provided borane adducts of diorgano(tetryl)phosphonites. Further treatment with excess Et₃N or DABCO yielded the borane-free species (RO)₂P-ER′₃ (E=Si, Ge; R, R′=alkyl, aryl). The products of all reactions were characterized by elemental analyses and NMR data, and in selected cases by MS and single-crystal XRD studies. Reactions of selected ligands with Ni(CO)₄ and selenium were shown to produce Ni(CO)₃-complexes or diorgano(tetryl) phosphonoselenoates (RO)₂(R′₃E)P=Se, respectively, which were identified spectroscopically but could not be isolated. Evaluation of the TEP and ¹J_PSe coupling constants were used for a first assessment of the electron donor properties of the new molecules.     

Comparison of sustained off-resonance irradiation collisionally activated dissociation and multipole storage-assisted dissociation for top-down protein analysis

Tandem mass spectrometric data acquired for small (8-18 kDa) intact proteins by sustained off-resonance irradiation collisionally activated dissociation (SORI-CAD) and multipole storage-assisted dissociation (MSAD) were compared, and the results indicate that the two activation methods do not always provide the same fragmentation patterns. In MSAD experiments, the charge state distribution made available by the ionization conditions may dictate the range of fragment ions that can be generated. In addition, conditions of high space charge within the hexapole impair transmission and/or trapping of high m/z species, which can result in loss of important precursor and product ions. Finally, the non-resonant nature of activation in MSAD can provide access to secondary dissociation processes that are not available by SORI. Because of these considerations, MSAD is less reliable than SORI for generating sequence tag data. However, it appears that MSAD samples 'preferred' cleavage processes (i.e. those occurring at D and P residues) just as well as SORI, which implies that MSAD data may be somewhat more compatible with search algorithms that utilize unprocessed fragment ion masses.     

Generation of a superposition of odd photon number states for quantum information networks

We report on the experimental observation of quantum-network-compatible light described by a nonpositive Wigner function. The state is generated by photon subtraction from a squeezed vacuum state produced by a continuous wave optical parametric amplifier. Ideally, the state is a coherent superposition of odd photon number states, closely resembling a superposition of weak coherent states |alpha > - |-alpha >. In the limit of low squeezing the state is basically a single photon state. Light is generated with about 10,000 and more events per second in a nearly perfect spatial mode with a Fourier-limited frequency bandwidth which matches well atomic quantum memory requirements. The generated state of light is an excellent input state for testing quantum memories, quantum repeaters, and linear optics quantum computers.     

Kriterien zweiter Ordnung für lokal beste Approximationen

Summary Consider the problem of approximating (in the Chebyshev-norm) a real-valued functionf(x) on a compact subsetX of ^m ,m1, by an element of a set of functionsa(p, x), pP,P ⁿ an open set. Both necessary and sufficient conditions of the second order for ana(p ⁰,x) to be a locally best approximation are derived. Apart from conditions on the differentiability off anda, onX, and on the error functionf(x)–a(p ⁰,x) we impose no restrictions on the problem. This makes the results applicable to a broad class of problems.     

Spacer Length Effect on the Photoinduced Electron Transfer Fluorescent Probe for Alkali Metal Ions

Abstract— We have synthesized four derivatives of aikyi pyrene covalently bonded to aza-lS-crown-6 at the nitrogen position, Py(CH₂)_n, (n = 1–4), to study the effect of spacer length on the emission properties of pyrene fluorophore upon complication of alkali metal ions by the crown moiety. In the absence of alkali metal ions, the parent molecule is weakly fluorescent because its emission is partially quenched by photoinduced electron transfer (PET) from nitrogen lone pairs to the excited singlet state of pyrene. Complication of alkali metal ions (e.g. K⁺) by the crown moiety prevents the nitrogen lone pair from participating in PET and results in an enhancement in the observed emission from pyrene (fluorescent turn on). Because the PET effect could be exerted through bonds as well as space, its magnitude may show a dependence on chain length. We have examined the fluorescence behavior of these pyrene aza-crown ether derivatives in the presence of alkali metal ions to determine the magnitude of such an effect and its impact on the sensitivity of the fluorescent probe for detection purposes. Our results indicate that maximum efficiency for PET between the pyrene moiety and aza-crown ether is achieved when n ≤ 3.     

Investigation of UV matrix-assisted laser desorption fourier transform mass spectrometry for peptides

Analytical Chemistry Division, Oak Ridge National Laboratory, Oak Ridge, Tennessee, USA Ultraviolet matrix-assisted laser desorption can be used to enhance formation of [M + H]⁺, [M + Na]⁺, and [M + K)⁺ ions from small peptides for Fourier transform mass spectrometry (FTMS). In accord with laser desorption (LD) time-of-flight experiments, matrices such as nicotinic acid and 2-pyrazinecarboxylic acid exhibit strong enhancement effects (i.e., formation of abundant protonated and cationized molecules for the analyte with virtually no fragment ions) for 266 nm LD/FTMS, whereas pyrazinedicarboxylic acid provides no matrix enhancement at this wavelength. Both sinapinic acid and coumarin-120 provide strong matrix enhancement effects for the 355-nm LD of peptides. For the small peptides examined in this study, no significant differences in the abundance of fragment ions were observed between the 266- and 355-nm wavelengths. Matrix-assisted LD/FTMS is useful for the generation and characterization of ions corresponding to protonated and cationized molecules from virtually all biological compounds with molecular weights up to 2000. The lack of observation of biological ions with m/ z > 2500 may be related to inefficient trapping of these laser-desorbed ions or instrumental detection limitations of FTMS and is under further investigation.