Stereochemistry of retro-diel-salder fragmentation in gas-phase ions formed by chemical ionization

Retro Diels Alder fragmentation is highly stereospecific in the diones 1 under chemical ionization conditions, both with methane and isobutane as the reagent gases. Only the cis-isomers yield abundant protonated diene and quinone ions. The isotope effect indicates preferential protonation on a CO oxygen, and a subsequent H-migration prior to the formation of the protonated diene cations in the cis isomers.     

Mass spectral fragmentation pathways in 2,4,6-trinitroaromatic compounds. A tandem mass spectrometric collision induced dissociation study

A collision induced dissociation study of a series of 2,4,6-trinitroaromatic compounds was carried out using a tandem BB mass spectrometer. Fragmentation pathways of the compounds were determined in the electron impact mode. It was found that dominant fragmentation pathways include loss of OH˙ due to an ortho effect and loss of NO˙ due to the formation of resonance-stabilized products.     

The role of intraoperative magnetic resonance imaging in complex meningioma surgery

Intraoperative magnetic resonance imaging (iMRI) has gained importance in the treatment of gliomas and sellar tumors. In intracranial meningiomas, the extent of surgical tumor removal is one of the most important factors in the prevention of tumor recurrence and patient survival. Complex meningiomas located at the skull base or near eloquent brain regions show higher recurrence rates, morbidity and mortality. The aim of this study was to evaluate whether iMRI contributes to more extensive surgical resection in these tumors. Patients undergoing complex meningioma resection using iMRI from January 2007 to January 2011 were included in this study. The indication for iMRI-guided tumor resection included patients presenting with meningiomas located in the skull base or compressing eloquent brain areas in whom a radical resection was considered to be difficult. Intraoperative 0.15-T MRI scan (PoleStar; Medtronic Navigation, Louisville, CO, USA) was performed before and after maximal possible resection using standard microsurgical and neuronavigation techniques. All patients underwent fluorescence-guided resection. The following data were analyzed: tumor localization, histological grade, Simpson resection grade, duration of the procedure, iMRI scan time, iMRI findings, resection extent based on postresection iMRI, hospitalization time, surgical complications and outcome, and MRI follow-up 2–27 months postoperation. Twenty-seven consecutive patients undergoing complex meningioma resection using iMRI were included. In this series, only one patient (3.4%) underwent resection of tumor remnant after iMRI, although without improvement of the Simpson resection grade. Temporary neurologic deficits were found in 8 patients (27.6%) postoperatively, whereas 11 patients (37.9%) had permanent postoperative neurologic deficits. In one case (3.4%), fatal postoperative bleeding occurred which was not detected by iMRI. Our results show that iMRI has no influence on intraoperative strategy in terms of resection grade or detection of early postoperative complications. The benefits of iMRI in complex meningioma surgery are therefore doubtful; however, it may still prove to be effective in certain subsets of complex meningiomas.     

CHARGE TRANSFER COMPLEXES BETWEEN POLYENES AND AROMATIC ACCEPTORS

Abstract. Both the cone pair electron donating ability of a polyene Schiff base and the strength of the bond formed indicate a weakening of the complex formed with increase in the conjugated double bond system.     

Identification of nitrate ester explosives by liquid chromatography-electrospray ionization and atmospheric pressure chemical ionization mass spectrometry

A new continuous chromatographic process (VARICOL) has been presented recently. The basic principle of the new VARICOL process consists of an asynchronous shift of the inlet/outlet lines in a multi-column system on a recycle loop. This process has been used to perform the separation of the optical isomers of the SB-553261 racemate. In this paper, we illustrate that for this specific separation, the VARICOL process is more efficient than the well-known SMB process.     

Reduction of trinitroaromatic compounds in water by chemical ionization mass spectrometry

A reduction process was found to occur in the ion source when observing the chemical ionization mass spectra of a series of trinitroaromatic compounds, using water as reagent. The [MH–30]⁺ ions in the CI mass spectra were due mainly to the reduction of the compounds to their corresponding amines. This was proved by using D₂O as reagent: the [MH–30]⁺ ions were shifted to [MD–28]⁺ ions. The trinitroaromatic compounds investigated included 1,3,5-trinitrobenzene, 2,4,6-trinitrotoluene, 2,4,6-trinitro-m-cresol, 2,4,6-trinitroaniline (picramide) and 2,4,6-trinitrophenol (picric acid).     

Electron impact,chemical ionization and negative chemical ionization mass spectra,and mass-analysed ion kinetic energy spectrometry–collision-induced dissociation fragmentation pathways of some deuterated 2,4,6-trinitrotoluene (TNT) derivatives

Mass-analysed ion kinetic energy spectrometry (MIKES) with collision-induced dissociation (CID) has been used to study the fragmentation processes of a series of deuterated 2,4,6-trinitrotoluene (TNT) and deuterated 2,4,6-trinitrobenzylchloride (TNTCI) derivatives. Typical fragment ions observed in both groups were due to loss of OR′ (R′ = H or D) and NO. In TNT, additional fragment ibns are due to the loss of R₂′O and 3NO₂, whilst in TNTCI fragment ions are formed by the loss of OCI and R₂′OCI. The TNTCI derivatives did not produce molecular ions. In chemical ionization (Cl) of both groups. MH⁺ ions were observed, with [M – OR′]⁺ fragments in TNT and [M – OCI]⁺ fragments in TNTCI. In negative chemical ionization (NCI) TNT derivatives produced M^?′, [M–R′]^?, [M–OR′]^? and [M–NO]^? ions, while TNTCI derivatives produced [M–R]^?, [M–Cl]^? and [M – NO₂]^? fragment ions without a molecular ion.     

High pressure mass spectrometry of some liquid chromatographic mass spectrometric reagents

Pressure dependence of several reversed phase liquid chromatographic solvents, including methanol, acetonitrile and mixtures of methanol: water and acetonitrile: water has been investigated. Typical ions, [MH]⁺, [2M+H]⁺ and [3M+H]⁺, were recorded as function of source pressure and as a function of the amount of water in the mixture. Ion formation processes in methanol: water and acetonitrile: water are discussed. The influence of liquid chromatographic mass spectrometric solvent pressure on the mass spectra of samples has been demonstrated on an amino acid sample.     

PRIMARY PHOTOCHEMICAL PRODUCTS OF DITHIOGLYCOLIC ACID IN AQUEOUS SOLUTION

Abstract— The photochemistry of dithioglycolic acid at 254 nm was investigated in deaerated aqueous solutions in the pH range 1.4–7.3. Initial yields of the primary photochemical products H₂S,–SH and aldehyde-(probably glyoxylic acid) were determined. The complex pH dependence of these simultaneously formed first stable products is interpreted in terms of the ground-state ionic equilibria, and in addition pH-dependent processes occurring in the excited state and labile intermediate sequence.
It is suggested that the photochemical mechanism involves two parallel pathways: one a hydrolytic splitting of S - S leading to H₂S formation (unaffected by the presence of O₂ or isopropanol), the other a free radical mechanism via C–S breakage, which is affected by the presence of O₂ or isopropanol.