Thermal decompositions of N-methylpyridinium,quinolinium, isoquinolinium and phenanthridinium salts in a mass spectrometer. Evidence for a specific HI elimination and for an oxidation to amides

The mass spectra of some N-methylpyridinium, quinolinium, isoquinolinium and phenanthridinium salts (R⁺X^?)

1 The salt will be represented by R⁺X^? or RX, R⁺ being the organic moiety, with its associated mass and X- the inorganic anion.

are analyzed (X^? = I^? or ClO₄^?). For X^? = I^?, thermal decomposition gives rise mainly to the superimposed spectra of CH₃I and the free base. Hence, iodide salts cannot be determined specifically by their mass spectra. When an α-methyl group is present, e.g. 2-methylpyridinium methiodide, elimination of HI becomes an important thermal process. For X^? = ClO₄^?, the same pattern is observed, but in addition a generally important peak at [R + 15] is present. This peak is due to the oxidation, mainly α to the nitrogen of the organic moiety by the ClO₄^? ion, giving rise to the corresponding amide. In some cases, chlorination of the organic moiety has been observed as well as double oxidation. The thermal processes for the perchlorate salts are characteristic and are useful in the elucidation of the quaternary structure.     

Dispersion phenomena in reactors for flow analysis

Both coiled open tubular reactors and packed-bed reactors can be used in flow analysis. Band broadening and pressure drop in these reactors are discussed. Theoretical analysis shows that packed-bed reactors are to be preferred. It is shown that for a given residence time and equal band-broadening values the pressure drop over a packed-bed reactor is lower than over a coiled open tubular reactor. Rules for optimal design are given for coiled tubular reactors and packed-bed reactors. The application of both reactors is shown for the spectrophotometric determination of phosphate with a vanadomolybdate reagent yielding a yellow colour.     

Strategies for multi-site GLP studies

 A GLP study can be performed at more than one site. This is called a multi-site study. Although, the study is performed at different sites, it is still one study and must completely comply with the GLP principles. The fact that different activities are conducted at different sites implies that the planning, the organization and the communication are crucial for the success of the study. This means that all the staff involved should know their responsibilities and should have the knowledge and skills to realize all the phases of the study according to the GLP principles. To achieve a well managed multi-site study, several strategies for setting up such a study can be followed. This paper focuses on the responsibilities, communication, and collaboration of the personnel, which are involved in a multi-site study. Several case studies are highlighted, and we concluded that the basic communication triangle in a single-site GLP study between test facility management, study director, and the quality assurance unit should be extended to the communication among test facility and test site management, study director, principle investigator(s), and the quality assurance units at the test sites. Introduction Received: 14 August 2002 Accepted: 26 November 2002     

A microwave-assisted click chemistry synthesis of 1,4-disubstituted 1,2,3-triazoles via a copper(I)-catalyzed three-component reaction

A microwave-assisted three-component reaction was used to prepare a series of 1,4-disubstituted-1,2,3-triazoles from corresponding alkyl halides, sodium azide, and alkynes. This procedure eliminates the need to handle organic azides, as they are generated in situ, making this already powerful click process even more user-friendly and safe.     

Conformational analysis of dimethylmethylphosphonate

The results of a CNDO/2 conformation analysis on dimethylmethylphosphonate are reported. Six stable conformers were found; their relative stabilities can be understood in terms of steric hindrance and gauche effect. Calculated barriers to internal rotation around P—O and O—C bonds are tabulated.     

Occurrence of chain folding in micelles : A C NMR relaxation and photophysical study

¹³CT₁ relaxation times for the different carbons of the sodium dodecyl sulphate chain in micellar systems have been measured, using Gd³⁺ as a paramagnetic relaxation reagent. The fluorescence decay of ω-(-naphthyl) dodecanoic acid, solubflized in the sodium dodecyl sulphate micelles was obtained in the presence of various amounts of counterion quencher Both series of experiments point to the occurrence of chain folding and to the fact that the terminal group can approach the Stern region of the micelle.     

The molecular structure of gaseous methyl vinyl ether at room temperature, studied by molecular orbital constrained electron diffraction and microwave spectroscopy

The gas phase molecular structure of methyl vinyl ether at room temperature has been studied by joint analysis of electron diffraction and microwave data. Constraints on geometrical and thermal parameters were derived from the geometry and force field of the s-cis form, obtained by ab-initio calculations (4–21 G basis set) after complete geometry relaxation. A range of models was investigated that fits all available data (infrared, microwave and electron diffraction). The following r_g/r-parameters were obtained: C=C: 1.337 Å, C(sp²)---O: 1.359 Å, C(sp³)---O: 1.427 Å, : 1.102 Å C=C---O : 127.3° and COC: 116.8°. Experimental r_g---r_e (ab initio) corrections are given for C=C, C(sp²)---O and Csp³)---O.

This investigation demonstrates that molecular orbital constrained electron diffraction is sufficiently reliable and in such a manner that it can be applied to more complicated problems.     

Mass spectrometric analysis of ceramide perturbations in brain and fibroblasts of mice and human patients with peroxisomal disorders

In this study, the levels and composition of ceramides in brains of newborn mice lacking peroxisomes (Pex5-/-, Zellweger mice) were analyzed using normal-phase high-performance liquid chromatography/atmospheric pressure chemical ionization mass spectrometry (HPLC/APCI-MS). Total ceramide compositions were found to be comparable to that of control animals. However, a minor ceramide species, containing hexacosanoic/hexacosenoic acid as the amide fatty acid, was 9-fold increased. Also, in the sphingomyelin-derived ceramides this species was elevated. Subsequent analysis of extracts from fibroblasts of Pex5-/- mice and mice with a defective peroxisomal beta-oxidation (lacking D-specific multifunctional protein 2 (MFP2)), revealed, again, a similar rise in this particular ceramide. Further, this ceramide was elevated in human X-ALD fibroblasts as well. Whether C26:1/0-ceramide is linked to some of the pathology seen in Zellweger syndrome remains to be investigated. However, an increase in this sphingolipid can be considered as a diagnostic criterion for diseases caused by defects in peroxisome biogenesis or peroxisomal beta-oxidation.     

Novel analogues of 3-substituted-2,3-dihydro-1,4-dioxino[2,3-b]pyridines: modifications in the dioxane ring

The synthesis of a series of novel analogues of the 3-substituted-2,3-dihydro-1,4-dioxino[2,3-b]pyridine core, modified in the non-aromatic ring, is described. Due to the presence of a versatile hydroxymethyl group in their structure, these novel scaffolds are attractive intermediates for the preparation of potential new therapeutic agents.     

Perfluormethyl-Element-Liganden. XXIX. Darstellung und spektroskopische Untersuchungen von M(CO)4L2-Komplexen (M = Cr,Mo, W; L = Me2PSMe,Me2PSeMe, (CF3)2PSMe, (CF3)2PSeMe)

Perfluoromethyl Element Ligands. XXIX. Preparation and Spectroscopic Investigation of M(CO)₄L₂ Complexes (M ? Cr, Mo, W; L ? Me₂PSMe, Me₂PSeMe, (CF₃)₂PSMe, (CF₃)₂PSMe) The complexes M(CO)₄L₂ (see Inhaltsübersicht) have been prepared by the reaction of tetracarbonyl norbornadiene metal compounds M(CO)₄NBD with L at room temperature or 35°C, respectively. The cis-complexes formed in the first step undergo rearrangement to trans-isomers at higher temperatures. New compounds have been characterized by analytical and spectroscopic (IR, NMR, MS) methods.