Synthesis and X-ray crystal structure of a five-coordinate d8 complex: [Pt((Me2NN)(PMe2)(PPh2))2Cl][Cl]

C₃₆H₅₀Cl₂N₆P₄Pt·2 MeCN,2, triclinic P¯1,a=11.720(2),b=12.153(2),c=16.196(3),=76.74(1),=84.90(1),=88.13(1),Z=2,R=0.051,Rw=0.051. Interaction of Me₂NN(PMe₂)(PPh₂),1, with Pt(COD)Cl₂, COD=1,5 cyclooctadiene, in THF yields the title compound,2, in quantitative yield. Compound2 was characterized spectroscopically as well as via an X-ray diffraction study.     

Temporal decline of masking and comodulation masking release.

Masking sounds can be continuously present, gated simultaneously with the signal, or gated somewhat prior to the signal. This continuum of relative onset times was explored using waveforms of the sort commonly employed in studies of comodulation masking release (CMR). There was a 50-Hz masker band centered on the 1250-Hz tonal signal, and four 50-Hz flanker bands centered at 850, 1050, 1450, and 1650 Hz. In some conditions, all four flanker bands had the same temporal envelope, and the masker band either had that same envelope (correlated presentations) or a different envelope (uncorrelated presentations). In other conditions, all five bands had different temporal envelopes (all-uncorrelated presentations). The masker band and/or the four flanker bands were either gated nearly simultaneously with the signal (burst conditions) or were gated prior to the signal by a duration that was systematically varied (fringed conditions). The eight listeners could be partitioned into three groups on the basis of their response to these fringing manipulations. Two listeners (the large fringers) showed a gradual improvement in detectability with increasing fringe duration (called a temporal decline of masking), while three others (the small fringers) showed little improvement in detectability. For the remaining three subjects, there was evidence of a "learning" effect that changed them from large fringers to small fringers over a 10-week period of listening. When present, the temporal decline of masking was greater for the correlated than for the uncorrelated comodulation condition; as a consequence, the difference in detectability between them (the comodulation masking release or CMR) increased with fringe duration. By fringing the masker and flanker bands separately and in combination, it was revealed that the temporal declines of masking were primarily attributable to the fringing of the flanker bands. In contrast, large CMRs required long fringes on both the masker and flanker bands. The above results were obtained with 50-ms signals, but generally similar data were obtained with a signal duration of 240 ms. The difficulties raised for experimentalists and theorists by such long-term practice effects are discussed.     

New Dolabellane Derivatives from the Brown Alga Dictyota pardalis

Reinvestigation of the brown alga Dictyota pardalis f. pseudohamata CRIBB led to the crystallization of 1 and to the isolation of the two new dolabellane derivatives 2 and 3 . X-Ray analysis of 1 and 2 , together with detailed 1D-and 2D-NMR studies on 2 and 3 , allowed their structures to be elucidated as (1R*,3S*,7S*,11R*,4Z)-dolabella-4,8(17), 12(18)-triene-3,7-diol ( 1 ), (1R*,3S*,4S*,7S*,8S*,11R*,14R*,12E)-3,4:7,8-diepoxydolabe11-12-ene-14, 18-diol ( 2 ), and (1R*,3S*,4S*,7S*,8S*,11R*,14R*)-3,4:7,8-diepoxy-l,4,8,12,12-pentamethylbicyclo[9. 3. 0]tetra-decan-14-ol( 3 ).     

The interaction of an osmium-carbon triple bond with copper(I), silver(I) and gold(I) to give mixed dimetallocyclopropene species and the structures of Os(AgCl) (CR) Cl(CO) (PPh3)2

The osmium carbyne complex, Os(CR)Cl(CO)(PPh₃)₂, (R  p-tolyl) reacts with Group I halides to form the mixed dimetallocyclopropene species, $\text{Os(Cul)(C}$R)Cl(CO)(PPh₃)₂, $\text{Os(AgCl)(C}$R)Cl(CO)(PPh₃)₂, $\text{Os(AuCl)(C}$R)Cl(CO)(PPh₃)₂, and [$\text{Os[Ag(OClO}{}_3\text{)](C}$R)Cl(CO)(MeCN)(PPh₃)₂] ClO₄ X-ray crystal structure determination of $\text{Os(AgCl)(C}$R)Cl(CO)(PPh₃)₂ confirms the presence of a three-membered ring and the structure can be viewed as the “acetylene-like” interaction of an osmium—carbon triple bond with AgCl. In acid solution AgCl is precipitated and an alkylidene complex results from proton addition to the carbyne ligand.     

Effect of viscosity on stationary phase stability in capillary column gas chromatography

With recent advances in column technology it is now possible to prepare highly efficient, very inert, and thermally stable capillary columns coated with nonpolar polysiloxane stationary phases. Unfortunately, the same degree of success has not been achieved for some of the more polar polysiloxane phases. A parameter that has been studied little in the past in relation to stationary phase film stability is the viscosity of the stationary phase. In this paper the efficiency and stability of coated columns are correlated to the viscosity of the phase. Due to their structure, the viscosity of the phenyl-containing polysiloxanes change rapidly with temperature and hence, thin-film coatings are not stable at elevated temperatures. By using high viscosity phenyl-containing methylphenylpolysiloxanes which were recently synthesized, efficient and stable columns have been prepared.     

High-speed peak matching algorithm for retention time alignment of gas chromatographic data for chemometric analysis

A rapid retention time alignment algorithm was developed as a preprocessing utility to be used prior to chemometric analysis of large datasets of diesel fuel profiles obtained using gas chromatography (GC). Retention time variation from chromatogram-to-chromatogram has been a significant impediment against the use of chemometric techniques in the analysis of chromatographic data due to the inability of current chemometric techniques to correctly model information that shifts from variable to variable within a dataset. The alignment algorithm developed is shown to increase the efficacy of pattern recognition methods applied to diesel fuel chromatograms by retaining chemical selectivity while reducing chromatogram-to-chromatogram retention time variations and to do so on a time scale that makes analysis of large sets of chromatographic data practical. Two sets of diesel fuel gas chromatograms were studied using the novel alignment algorithm followed by principal component analysis (PCA). In the first study, retention times for corresponding chromatographic peaks in 60 chromatograms varied by as much as 300 ms between chromatograms before alignment. In the second study of 42 chromatograms, the retention time shifting exhibited was on the order of 10 s between corresponding chromatographic peaks, and required a coarse retention time correction prior to alignment with the algorithm. In both cases, an increase in retention time precision afforded by the algorithm was clearly visible in plots of overlaid chromatograms before and then after applying the retention time alignment algorithm. Using the alignment algorithm, the standard deviation for corresponding peak retention times following alignment was 17 ms throughout a given chromatogram, corresponding to a relative standard deviation of 0.003% at an average retention time of 8 min. This level of retention time precision is a 5-fold improvement over the retention time precision initially provided by a state-of-the-art GC instrument equipped with electronic pressure control and was critical to the performance of the chemometric analysis. This increase in retention time precision does not come at the expense of chemical selectivity, since the PCA results suggest that essentially all of the chemical selectivity is preserved. Cluster resolution between dissimilar groups of diesel fuel chromatograms in a two-dimensional scores space generated with PCA is shown to substantially increase after alignment. The alignment method is robust against missing or extra peaks relative to a target chromatogram used in the alignment, and operates at high speed, requiring roughly 1 s of computation time per GC chromatogram.     

Approaches to dioxin analysis by HRGC-HRMS and hybrid HRGC-MS-MS

A hybrid mass spectrometer with an EBQQ configuration was used to investigate two approaches to trace dioxin analysis: high resolution gas chromatography – high resolution mass spectrometry (HRGC-HRMS) and high resolution gas chromatography – mass spectrometry – mass spectrometry (HRGC-MS-MS). It is shown that selected ion monitoring (SIM) HRGC-HRMS exhibits better selectivity for dioxins separated on a cyanopropyl column than is otherwise obtained under medium resolution mass spectrometry (3,000 resolution), while optimization of conditions for HRGC-MS-MS allowed the observation of 350 femtograms of the highly toxic 2,3,7,8-TCDF at a S/N ratio of 5:1. Both methods were applied to environmental samples with good results.     

Lorentz covariance and kinetic charge

There is a one-to-one correspondence between inequivalent covariant displaced Fock representations of the free relativistic field and the 1-cohomology of the Poincaré group with coefficients in the 1-particle space.Representations with positive energy are obtained from cocycles with finite energy which have particle-like properties and are interpreted as condensed states of matter without a sharply defined mass.The 1-cohomology groups ofP ₊ are calculated. These are trivial in 3- or 4-dimensional space-time, or if the mass is non-zero. Non-trivial cocycles for subgroups lead to representations in whichP-invariance is spontaneously broken. We recoverP-invariance in a direct integral representation possessing a gauge group, and a superselection structure labelled by the velocities of the condensed states of matter which are the cocycles determining each irreducible component of the representation. A model in 4-dimensional space-time is constructed.