Gas-phase deprotonation of arylalkylamines. A collision-induced dissociation study

The collision-induced dissociation (CID) of deprotonated arylalkylamines of general formula R(1)C(6)H(4)CHR(2)CH(2)NR(3)(2) (where R(1) = H, OH, F or NO(2); R(2) = H or OH; R(3) = H or CH(3)) generated by negative chemical ionization with H(2)O and D(2)O as ionizing reagents, is discussed. The negative chemical ionization mass spectra show that, in the absence of a hydroxy group in the aromatic ring, deprotonation takes place at the benzylic position whereas the proton is lost from the OH group when present. The nitro compound forms only M(-.) ions. The CID spectra of the deprotonated molecules show that fragmentations are strongly dependent on the structural features of the molecules, namely the presence or absence of substituents in the aromatic ring or aliphatic chain. Copyright 1999 John Wiley & Sons, Ltd.     

The onset of coulomb explosions in polyatomic molecules

With the development of high intensity femtosecond lasers, the ionisation and dissociation dynamics of molecules has become an area of considerable interest. Using the technique of femtosecond laser mass spectrometry (FLMS), the molecules carbon disulphide, pyrimidine, toluene, cyclohexanone and benzaldehyde are studied with pulse widths of 50 fs in the near infrared (IR) wavelength region (790 nm). Results are presented and contrasted for laser beam intensities around 10(15) and 10(16) W cm(-2). For the lower intensities, the mass spectra yield dominant singly charged parent ions. Additionally, the appearance of doubly charged parent ions is evident for carbon disulphide, toluene and benzaldehyde with envelopes of doubly charged satellite species existing in these local regions. Carbon disulphide also reveals a small triply charged component. Such atomic-like features are thought to be a strong fingerprint of FLMS at these intensities. However, upon increasing the laser intensity to approximately 10(16) W cm(-2), parent ion dominance decreases and the appearance of multiply charged atomic species occurs, particularly carbon. This phenomenon has been attributed to Coulomb explosions in which the fast absorption of many photons may produce transient highly ionised parent species which can subsequently blow apart. Copyright 1999 John Wiley & Sons, Ltd.     

Uniform molecular analysis using femtosecond laser mass spectrometry

The potential of femtosecond laser time-of-flight mass spectrometry (FLMS) for uniform quantitative analysis of molecules has been investigated. Various samples of molecular gases and vapours have been studied, using ultra-fast ( approximately 50 fs) laser pulses with very high intensity (up to 1.6 x 10(16) Wcm(-2)) for non-resonant multiphoton ionisation/tunnel ionisation. Some of these molecules have high ionisation potentials, requiring up to ten photons for non-resonant ionisation. The relative sensitivity factors (RSF) have been determined as a function of the laser intensity and it has been demonstrated that for molecules with very different masses and ionisation potentials, uniform ionisation has been achieved at the highest laser intensities. Quantitative laser mass spectrometry of molecules is therefore a distinct possibility. Copyright 1999 John Wiley & Sons, Ltd.     

Effects of consonant manner and vowel height on intraoral pressure and articulatory contact at voicing offset and onset for voiceless obstruents

In obstruent consonants, a major constriction in the upper vocal tract yields an increase in intraoral pressure (P(io)). Phonation requires that subglottal pressure (P(sub)) exceed P(io) by a threshold value, so as the transglottal pressure reaches the threshold, phonation will cease. This work investigates how P(io) levels at phonation offset and onset vary before and after different German voiceless obstruents (stop, fricative, affricates, clusters), and with following high vs low vowels. Articulatory contacts, measured using electropalatography, were recorded simultaneously with P(io) to clarify how supraglottal constrictions affect P(io). Effects of consonant type on phonation thresholds could be explained mainly in terms of the magnitude and timing of vocal-fold abduction. Phonation offset occurred at lower values of P(io) before fricative-initial sequences than stop-initial sequences, and onset occurred at higher levels of P(io) following the unaspirated stops of clusters compared to fricatives, affricates, and aspirated stops. The vowel effects were somewhat surprising: High vowels had an inhibitory effect at voicing offset (phonation ceasing at lower values of P(io)) in short-duration consonant sequences, but a facilitating effect on phonation onset that was consistent across consonantal contexts. The vowel influences appear to reflect a combination of vocal-fold characteristics and vocal-tract impedance.     

Fast tunable coupler for superconducting qubits

A major challenge in the field of quantum computing is the construction of scalable qubit coupling architectures. Here, we demonstrate a novel tunable coupling circuit that allows superconducting qubits to be coupled over long distances. We show that the interqubit coupling strength can be arbitrarily tuned over nanosecond time scales within a sequence that mimics actual use in an algorithm. The coupler has a measured on/off ratio of 1000. The design is self-contained and physically separate from the qubits, allowing the coupler to be used as a module to connect a variety of elements such as qubits, resonators, amplifiers, and readout circuitry over distances much larger than nearest-neighbor. Such design flexibility is likely to be useful for a scalable quantum computer.     

Incorporation of silver/carbon nanoparticles into poly(methyl methacrylate) via in situ miniemulsion polymerization and its influence on the glass‐transition temperature

Silver/carbon nanoparticles (9 nm) were incorporated, as reinforcements, into a matrix of poly(methyl methacrylate) via in situ miniemulsion polymerization. It was found by differential scanning calorimetry that the glass‐transition temperature of the poly(methyl methacrylate) showed an improvement of 14 °C with only 0.5 wt % nanoparticles in comparison with a pure poly(methyl methacrylate) control, which was also obtained by miniemulsion polymerization under the same conditions. This increase was related to a polymer chain mobility restriction due to a combination of bound plastic and joint plastic shell effects at the interphase and the surrounding regions. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 511–518, 2007.     

High-fidelity gates in a single josephson qubit

We demonstrate new experimental procedures for measuring small errors in a superconducting quantum bit (qubit). By carefully separating out gate and measurement errors, we construct a complete error budget and demonstrate single qubit gate fidelities of 0.98, limited by energy relaxation. We also introduce a new metrology tool-- Ramsey interference error filter-that can measure the occupation probability of the state |2> which is outside the computational basis, down to 10{-4}, thereby confirming that our quantum system stays within the qubit manifold during single qubit logic operations.     

Synthesis,spectroscopic characterization and fungicidal activity of triphenyltin derivatives of N,N-dimethylglycine: Crystal structure of [dimethyl(carboxylatomethyl)ammonium]-chlorotriphenylstannate

The new triorganotin complexes formulated as Me₂HNCH₂COO · Ph₃SnX, X = Cl, NCS were prepared and spectroscopically characterized, and their fungicidal properties against Ceratocystis ulmi were determined. An X-ray structure for [dimethyl(carboxylatomethyl)ammonium] chlorotriphenylstannate is also reported.     

Stereochemistry of nucleophilic substitution reactions depending upon substituent: evidence for electrostatic stabilization of pseudoaxial conformers of oxocarbenium ions by heteroatom substituents

Lewis acid-mediated nucleophilic substitution reactions of substituted tetrahydropyran acetates reveal that the conformational preferences of six-membered-ring cations depend significantly upon the electronic nature of the substituent. Nucleophilic substitutions of C-3 and C-4 alkyl-substituted tetrahydropyran acetates proceeded via pseudoequatorially substituted oxocarbenium ions, as would be expected by consideration of steric effects. Substitutions of C-3 and C-4 alkoxy-substituted tetrahydropyran acetates, however, proceeded via pseudoaxially oriented oxocarbenium ions. The unusual selectivities controlled by the alkoxy groups were demonstrated for a range of other heteroatom substituents, including nitrogen, fluorine, chlorine, and bromine. It is believed that the pseudoaxial conformation is preferred in the ground state of the cation because of an electrostatic attraction between the cationic carbon center of the oxocarbenium ion and the heteroatom substituent. This analysis is supported by the observation that selectivity diminishes down the halogen series, which is inconsistent with electron donation as might be expected during anchimeric assistance. The C-2 heteroatom-substituted systems gave moderately high 1,2-cis selectivity, while small alkyl substituents showed no selectivity. Only in the case of the tert-butyl group at C-2 was high 1,2-trans selectivity observed. These studies reinforce the idea that ground-state conformational effects need to be considered along with steric approach considerations.