Silver cluster interferences in matrix-assisted laser desorption/ionization (MALDI) mass spectrometry of nonpolar polymers

Potential difficulties associated with background silver salt clusters during matrix-assisted laser desorption/ionization mass spectrometry (MALDI-MS) of nonpolar polymers are reported. Silver salt cluster ions were observed from m/z 1500 to 7000 when acidic, polar matrices, such as 2,5-dihydroxybenzoic acid (DHB), all-trans-retinoic acid (RTA) or 2-(4-hydroxyphenylazo)benzoic acid (HABA), were used for the analysis of nonpolar polymers. These background signals could be greatly reduced or eliminated by the use of nonpolar matrices such as anthracene or pyrene. Representative examples of these background interferences are demonstrated during the analysis of low molecular weight nonpolar polymers including polybutadiene and polystyrene. Nonpolar polymers analyzed with acidic, polar matrices (e.g., RTA) and silver cationization reagents can yield lower quality mass spectral results when interferences due to silver clusters are present. Replacing the polar matrices with nonpolar matrices or the silver salts with copper salts substantially improved the quality of the analytical results. In addition, it was found that silver contamination cannot be completely removed from standard stainless steel sample plates, although the presence of silver contamination was greatly reduced after thorough cleaning of the sample plate with aluminum oxide grit. Carry-over silver may cationize polymer samples and complicate the interpretation of data obtained using nonpolar matrices in the absence of added cationization reagents.     

Enhanced selectivity and sensitivity for inorganic anions using an ion-pairing reagent and sample stacking in capillary zone electrophoresis with direct UV detection

In this paper, the use of an ion-pairing reagent to improve the separation selectivity of inorganic anions in CZE was demonstrated by the addition of tetramethylammonium hydroxide (TMAOH) to the electrolyte. The separation of inorganic anions (Cl(-), I(-), Br(-), NO(2)(-), NO(3)(-) and SCN(-)) was performed using co-electroosmotic flow (EOF) with direct UV detection at 185 nm. The parameters affecting the mobility of the tested anions and the EOF such as the electrolyte pH and concentration of TMAOH in the electrolyte were examined to optimise the separation conditions. In addition, sample-stacking techniques were investigated to improve detection sensitivity. Detection sensitivities were improved 5-13-fold using electrokinetic sample stacking. The detection limits ranged from 1-3 micro mol L(-1). Finally, the proposed method was used for the separation of anions in groundwaters.     

Magnetic susceptibility-induced alignment of proteins in reverse micelles

Proteins encapsulated within the aqueous core of reverse micelles are found to partially align in a magnetic field. The degree of alignment is sufficient to result in sizable residual 15N-1H dipolar couplings that can be easily measured. It is found that the magnetic susceptibility of the reverse micelle particle is not dominated by the encapsulated protein. The residual dipolar couplings are found to be structurally meaningful.     

A novel synthesis of 1,2-diphosphorylbenzenes

Synthesis of phosphorylchloroacetylenes, diphosphorylacetylenes and the Diels-Alder reactions of the latter to produce $\text{o}$-diphosphorylbenzenes are described.     

Determination of boron in geological materials by inductively-coupled plasma emission spectrometry

Determination of boron in international silicate reference materials with an argon plasma is demonstrated. Detection limits are about 5 ppm for rock samples.     

Polarization in inclusive reactions

A formalism for discussing the spin dependence of inclusive reactions is presented. The role of various constraints following from conservation of parity and angular momentum conservation is discussed. Expressions for specific single and double polarization observables are presented. Predictions of the triple-Regge model for these observables are given.     

Amplitude analyses of the reactions π+p → (ϱ0, ω) Δ++ at 7.1 GeV/c

New data are presented, in the form of statistical tensors, for the reactions π⁺p → (?⁰, ω)Δ⁺⁺ at 7.1 GeV/c. Using these data, two types of model-dependent amplitude analyses have been performed. Both analyses, though based on different sets of assumptions, yield results which are in agreement with each other. The structure observed in the magnitudes and phases of the extracted amplitudes is consistent with that expected on the basis of currently accepted phenomenological ideas.     

A study of inclusive vector meson production

Data are presented on the reactions π⁺n → ?⁰+X and $\text{K}{}^{\mathrm{?}}\text{p}\text{→}\text{K}{}^1\text{0}\text{(890)+}\text{X}\text{at 6.0}\text{and}\text{7.3}\text{GeV}\text{/c}$, respectively. Comparisons are made with related reactions at higher energies.     

Determination of therapeutic and toxic concentrations of doxepin and loxapine using gas-liquid chromatography with a nitrogen-sensitive detector, and gas chromatography-mass spectrometry of loxapine

A gas-liquid chromatographic procedure is presented for the determination of therapeutic and toxic serum levels of doxepin and loxapine, using a nitrogen-phosphorus-sensitive detector. Amitriptyline is used as the internal standard. The method is accurate, sensitive and specific with no derivatization required prior to analysis. An advantage of the procedure is the small serum sample size needed for analysis and the selectivity and sensitivity of the detector, with the limit of detection being 3 and 2 microgram/l for doxepin and loxapine, respectively. Nine cases of doxenin and loxapine misuse are presented. Serum doxepin concentrations ranged from 113 to 439 microgram/l, with a loxapine concentration of 192 microgram/l observed in one patient. The presence of the tricyclics was identified and confirmed by gas chromatography-mass spectrometry and the mass spectrum of loxapine is reported.