Mass spectra of transition metal π-complexes. VI—The metastable ion mass spectrum of (η1-Toluene)-tricarbonylchromium

First field free region metastable fragmentations of (η⁶-PhCH₃)Cr(CO)₃ have been examined by means of the linked scan technique. The molecular ion is shown to fragment exclusively by single and multiple CO loss. The ion [C₇H₈Cr(CO)₂]⁺? also fragments directly to [C₇H₈Cr]⁺?.     

Thermal oxidative degradation of additive-free polypropylene pellets investigated by multichannel Fourier-transform chemiluminescence spectroscopy

Thermal oxidative degradation of additive-free polypropylene pellets heated isothermally in dry air at 150 and 180 °C (below and above the melting point of 163 °C) was investigated by multichannel Fourier-transform chemiluminescence spectroscopy. The initial peak wavelength of chemiluminescence emission at 490 nm remained constant during the early stages of thermal degradation, but new emissions developed with time in the red spectral region over an extended oxidation period. The time-dependent luminescence spectra were deconvoluted into three emission bands by least-squares fitting using Gaussian curves. We concluded that at least three groups of luminescent species (luminophores), having different conjugation lengths, were generated by thermal oxidation over extended periods and show luminescence around 490, 660, and 740 nm.     

Quantifizierung organischer Substanzen in Aktivkohleextrakten mit Hilfe der Gas-Chromatographie/Massenspektrometrie

Summary Use of activated carbon plays a significant role in water technology and analytical chemistry. Therefore determination of substances adsorbed on activated carbon is of special interest. As an example, granulated activated carbon (GAC) from a water treatment plant was serially extracted with different organic solvents. Quantitative determination of some selected compounds in the combined extracts was done by gas chromatography/mass spectrometry. The method of internal standard addition and calibration by response factors was used. The determined compounds (all of substituted benzene type) were extracted from the GAC in the concentration range from 0.2 mg/100 g (m-dichlorobenzene) to 5 mg/100 g (nitrobenzene). Relative standard deviation for double determination of five independent samples from the GAC filter was less than ±20%Spike experiments were performed to determine recovery efficiences. As expected, substance specific differences appeared and the recoveries were between 36% (m-dichlorobenzene) and 80% (nitrobenzene). A significant limitation for quantitative determination results from lack of available substances for calibration.     

The effect of dyes on photo-induced chemiluminescence emission from polymers

Weak photo-induced chemiluminescence (PICL) emission is observed when polymers are exposed to UVA or visible light. The presence of dyes can either increase PICL intensity via Type I photosensitisation which generates polymer free radicals, or reduce it via photo-protection. PICL studies on the eight Blue Wool Standards (BWSs) that are used commercially as lightfastness standards show higher PICL intensity from the least photostable BWSs that use triphenylmethane dyes and lower intensity from more photostable BWSs using UVA and visible wavelengths. The relative PICL intensities do not correlate in a stepwise manner with lightfastness ratings of the BWSs. However dye/polymer combinations that emit high levels of PICL relative to the undyed material are unlikely to have acceptable lightfastness. The xanthene dyes fluorescein and eosin Y are more strongly photosensitising than triphenylmethane dyes on wool and both produce higher PICL emission than undyed wool when irradiated with visible light.     

Effects of different composition ratio on the dielectric relaxation and dynamic mechanical properties of poly(ω‐dodecalactam‐co‐ε‐caprolactam‐co‐propylene oxide) copolymers

The molecular dynamics of new poly (ω‐dodecalactam‐co‐ε‐caprolactam‐co‐propylene oxide) copolymers (DL/CL/PAC) has been investigated by using dynamic mechanical thermal analysis (DMTA) and dielectric relaxation spectroscopy (DRS) measurements. The copolymers were synthesized via anionic polymerization of relevant lactams activated with carbamoyl derivatives of telechelic hydroxyl terminated polypropylene oxide with isophorone diisocyanate (PAC). The calorimetric, X‐ray diffraction, and DMTA measurements were performed to recognize the influence of the composition ratio and the type of PAC on the physical, thermal, and mechanical properties of the synthesized copolymers. The DRS was used to study the frequency dependence of the dielectric permittivity of some isotherms from ?110 to 145 °C. Copolymerization of ε‐caprolactam with about 10 wt % ω‐dodecalactam results in a copolymer that has lower water absorption, a melting point close to that of polyamide 6 and has a high enough degree of crystallinity in respect to high storage modulus. Five dielectric relaxations have been observed in the dielectric spectra, three at lower temperature and two at higher temperature. The copolymers have two glass transition temperatures for polyamide segments and polyether blocks, indicating microphase separation in the copolymers. Other studies directed toward molecular dynamics of polyamide DL/CL/PAC copolymers have not been reported. © 2010 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2010     

Application of continuous-flow liquid chromatography/fast-atom bombardment mass spectrometry to the analysis of diagnostic acylcarnitines in human urine

Acylcarnitine profiles of diagnostic value were generated from the equivalent of 0.1 microL of raw urine using the continuous-flow liquid chromatography/fast-atom bombardment mass spectrometry (LC/FAB-MS) interface for sample introduction. Further analysis was accomplished by gradient LC/MS using a commercially available packed fused-silica microbore column.     

The laser-induced fluorescence spectrum of chromyl fluoride (chromium dioxidedifluoride) in a seeded molecular beam

We habe obtained part of the laser-induced fluorescence spectrum of chromyl fluoride in a free jet expansion at an instrumental resolution of better than 0.001 cm^?1. This spectrum (together with that of the dispersed fluorescence) allows the identification of the (0,0) band or the absorption spectrum and of several progressions in the lowest bending frequency.     

Improved dansylation procedure for the determination of ketosteroids by liquid chromatography

Summary A new procedure for derivatizing ketosteroids with dansyl hydrazine, a fluorogenic tagging agent, is reported. Termed “evaporative-derivatization”, this technique employs simultaneous heating and evaporation for the derivatization step. Presumably, as the evaporation approaches completion, the analyte is exposed to an infinite concentration of dansyl reagent. The impact of this work provides for a short reaction time (10min), low temperature (60°C), and almost complete derivatization. The short derivatization time enables labile steroids to be tragged with little decomposition. While the prior dansylation techniques tag only the 3-position, this new procedure also tags the sterically hindered 20-position forming a bis-dansyl derivative. The bis-derivative exhibits significantly greater chromatographic retention, which means that chromatographic interferences are less likely when complex matrices, such as extracts of blood plasma are analyzed. Presented at the 15th International Symposium on Chromatography, Nürnberg, October 1984