Complexes in polymers IV. FTIR microscopic characterization of thin organic polymer films containing embedded transition-metal carbonyl complexes

Thin films of polystyrene (PS), poly(methyl methacrylate) (PMMA) and polystyrene-polyacrylonitrile copolymer (PS-AN), containing various embedded transition-metal complexes, have been studied by FTIR microscopy. The spatial distributions of the transition-metal carbonyl complexes throughout the thin organic polymer films have been determined by a two-dimensional IR mapping procedure. The spectral variations observed in the distribution of the metal carbonyls throughout the different polymer films are discussed. The IR data show that the technique used to prepare the organometallic-embedded thin films (viz. freeze-drying of solutions followed by hot mechanical pressing of the residues) does in general lead to homogeneous films which may eventually find industrial application, e.g. as membrane sensors for small molecules.     

Steady-state electrolysis at a grooved or ridged plane

This study concerns an infinite plane whose smoothness is marred by a single defect: either a groove or a ridge. The blemished plane serves as an electrode supporting a diffusion-controlled steady-state process. By using a convenient coordinate transformation, the local current density at all points on the surface is determined exactly. The results are found to confirm intuitive expectations. Thus, compared with normal values on the plane remote from a groove, the electron transfer rate is diminished within the groove but enhanced along its margins. Similarly, an abnormally large transfer rate is encountered high on the ridge but the rate is subnormal on its lower flanks. The total current is demonstrated to be unchanged by the presence of the blemish. Received: 27 September 1996 / Accepted: 11 March 1997     

Systematic Errors Associated with the CPMG Pulse Sequence and Their Effect on Motional Analysis of Biomolecules

A theoretical approach to calculate the time evolution of magnetization during a CPMG pulse sequence of arbitrary parameter settings is developed and verified by experiment. The analysis reveals that off-resonance effects can cause systematic reductions in measured peak amplitudes that commonly lie in the range 5–25%, reaching 50% in unfavorable circumstances. These errors, which are finely dependent upon frequency offset and CPMG parameter settings, are subsequently transferred into erroneousT₂values obtained by curve fitting, where they are reduced or amplified depending upon the magnitude of the relaxation time. Subsequent transfer to Lipari–Szabo model analysis can produce significant errors in derived motional parameters, with τ_einternal correlation times being affected somewhat more thanS²order parameters. A hazard of this off-resonance phenomenon is its oscillatory nature, so that strongly affected and unaffected signals can be found at various frequencies within a CPMG spectrum. Methods for the reduction of the systematic error are discussed. Relaxation studies on biomolecules, especially at high field strengths, should take account of potential off-resonance contributions.     

The potential of pyrolysis/gas chromatography/mass spectrometry for determining the progress of lignification: An investigation of maturing asparagus sclerenchyma tissue

Sclerenchyma tissues from semi-mature and mature asparagus spears were analysed by pyrolysis/gas chromatography/mass spectrometry and by conventional chemical methods in order to determine the degree of lignification and compare analytical techniques. The pyrolysis data are similar to those obtained by a chemical method involving alkaline extraction at 70°C followed by spectrophotometric determination of phenolic content. The pyrolysis method was more rapid, sensitive and informative than the chemical technique and shows considerable potential for studying the chemical basis of the textural development of plant foods.     

The use of combined LC-GC for the analysis of fuel products: A review

A review of the analysis of petroleum fuels, oils, tars and engine exhaust particulate extracts by on-line coupled LC-GC is presented.     

Catalytic air oxidation of ambient temperature hydrocarbons

Catalytic air oxidation of the aliphatic hydrocarbons n-decane, hexanes, gasoline and diesel fuel was conducted at ambient temperature with novel iron catalysts. The concentration of n-decane in water was reduced from 1.42 g in 100 ml to 0.07 g in 100 ml in 5 h at room temperature forming carbon monoxide and water by means of intermediate aldehydes. Results of FT–IR and GC–MS analyses demonstrated formation of aldehydes and unsaturated alcohols. Carbon monoxide was detected on catalyst residues and in the vapor phase. The indicated catalytic reaction mechanisms are discussed.