Positive and negative ion mass spectrometry of benzophenones, the acid-hydrolysis products of benzodiazepines.

Positive electron impact (EI), positive chemical ionization (CI), and negative CI mass spectra of 14 benzophenones are presented. In the positive EI mode, intense molecular peaks appeared for most compounds; some other peaks due to splitting at both sides of the carbonyl group also appeared. In the positive CI mode, [M + 1]+ quasi-molecular ions together with [M + C2H5]+ peaks were observed for all compounds; some fragment peaks were common to those in the positive EI mode. In the negative CI mode, the spectra were much simpler than those in the positive EI or CI mode. In the 1 Torr negative CI mode, some spectra showed only single molecular anions; in the 0.01 Torr negative CI mode, halogen or nitro peaks appeared in addition to the molecular anions. An extraction procedure for benzophenones from human urine and plasma after heating in strong acid, and their separation by gas chromatography (GC) are also presented to serve for their actual identification by GC/mass spectrometry.

Positive- and negative-ion mass spectrometry of butyrophenones.

Positive-ion electron-impact (EI), positive-ion chemical ionization (CI) and medium-pressure negative-ion CI mass spectra of ten butyrophenones are presented. Low-pressure (0.01 Torr) negative CI spectra are also presented for some compounds. In the positive EI mode, a peak at m/z 42, which corresponded to the propyl group, appeared for all compounds; a peak at m/z 123 was also common to all compounds except for the two with a bis(fluorophenyl) group. Molecular ions were generally very small or missing in the positive EI mode. In the positive CI mode, strong [M+H]+ quasi-molecular peaks generally appeared together with [M+C2H5]+ peaks; [M-F]+ peaks appeared in many compounds and [M-OH]+ peaks also appeared for compounds having a hydroxypiperidinyl group. In the negative CI mode with a 1 Torr chamber pressure, their spectra were generally simple with [M-H]- quasi-molecular ions; anions of liberated halogens were not observed except for bromine at this pressure. In the negative CI mode at low pressure (0.01 Torr), some fragment peaks in the lower mass range appeared in addition to the quasi-molecular ions; halogen peaks (m/z 19 or 35) and anions at m/z 95, which corresponded to the fluorophenyl group, appeared in most spectra recorded at this pressure. An procedure for the extraction of butyrophenones from human urine and plasma and their separation by gas chromatography was also developed to serve for their identification in forensic science practice.

Positive and negative ion mass spectrometry of tricyclic antidepressants.

Positive electron impact (EI), positive chemical ionization (CI), and negative CI mass spectra of eight tricyclic antidepressants are presented. In the positive EI mode, peak(s) at m/z 193 and/or 195, which corresponded to the tricyclic nucleus, appeared for five compounds; a peak at m/z 58 was common to compounds having a gamma-dimethylaminopropyl group as their side chain. Molecular ions appeared for all compounds though they were very small in some compounds in the positive EI mode. In the positive CI mode, [M + H]+ quasi-molecular peaks appeared together with [M + C2H5]+ peaks in five compounds; the ion at m/z 196, which corresponded to the tricyclic nucleus also appeared in five compounds. In the negative CI mode with 1 Torr chamber pressure, [M - 1]- quasi-molecular ions were observed for all compounds except for lofepramine; [M + 43]- anions, which probably corresponded to [M + C3H4]-, appeared in five compounds; strong [M + Cl]- ions appeared in carpipramine and clocapramine. The anions due to the tricyclic nucleus also appeared in this mode. In the negative CI mode at low pressure (0.01 Torr), the spectra were generally similar to those in the 1 Torr negative CI mode. However, the cluster anions never appeared at the low pressure. Some data on extraction for some antidepressants from human urine and plasma, and their separation by gas chromatography, are also presented.

Thromboxane synthesizing system in rat liver.

Thromboxane B2 (TXB2), along with other primary prostaglandins, was synthesized when rat liver microsomes were incubated with radioactive arachidonic acid. TXB2 was identified directly by chemical ionization mass spectrometry and indirectly by using specific inhibitors of TX synthetase, viz., imidazole and OKY-1555 ((E)-3(4-(3-pyridyl-methyl) phenyl)-2 methyl acrylic acid HCl). The supernatant fraction obtained after centrifugation at 105,000 X g for 60 min contained a possible regulatory component that suppressed thromboxane synthesis. The regulatory influence is lost after partial hepatectomy.

[Tricyclic antidepressants (TAD) as a cause of unexpected death (author's transl)]. / Aussergewöhnliche Todesfälle durch trizyclische Antidepressiva.

This study points to the controversy over the anti-depressant efficacy of tricyclic antidepressant drugs (TAD) and emphasize their cardiotoxicity. The number of lethal poisoning cases--from the Swiss federal statistics on the cause of death--amounted to 54 for the period from 1967 to 1976. Ten of these 54 cases occurred in children who had ingested the drug accidentally; the remaining cases concerned adults who took an overdose of the drug intentionally. In addition, the authors reviewed the forensic medical examinations performed on 11 cases of unexpected death due to lethal poisoning with TAD. Our data indicated that fatality can follow drug intake quite rapidly. Autoptical and histological findings were not specific. To confirm a poisoning diagnosis, levels of TAD and their metabolites were therefore determined in nine cases in various organ tissues and body fluids. Poisoning was due to imipramine (3 cases), opipramol (2 cases), dibenzepine (3 cases), and amitriptyline (3 cases).

Negative ion mass spectrometry of phenothiazines.

Mass spectra of a number of phenothiazines have been obtained by negative chemical ionization and compared with the corresponding mass spectra by positive chemical ionization and conventional electron impact. NH3, CH4, and N2O were used as reagent gases for negative chemical ionization, iso-C4H10 and CH4 for positive chemical ionization. The negative chemical ionization technique gives significant information regarding the molecular weight and the ring system of this group of compounds. As a complementary method to positive electron impact, negative chemical ionization is more informative than positive chemical ionization. Phenothiazines with two, but not three, methylene groups between the ring and the sidechain nitrogens given an intense rearrangement anion due to loss of the substituted nitrogen in the sidechain and two additional hydrogens. A 5-membered ring structure is postulated for this anion, which is formed with the reagents NH3 and CH4. but not with N2O. Apart from this peculiarity, the negative chemical ionization spectra are easy to understand. With NH3 as reagent, the anions representing the ring system and [M -- 1]- dominate the anion current. With CH4, both quasimolecular ions [M + 1]- and [M -- 1]- can be detected along with the much more intense ring anion. The reagent N2O yields cluster anions by oxidation of the ring and the molecule with the negatively charged oxygen formed in the ion source.

Hemodialysis in a patient with acute mercuric cyanide intoxication. Concentrations of mercury in blood, dialysate, urine, vomitus, and feces.

The effectiveness of hemodialysis in removing mercury was examined in a 14-year-old boy with acute renal failure due to intoxication by 1.5 gm of mercuric cyanide. Mercury concentrations in blood, dialysate, urine, vomitus, and feces were measured. In some materials, the total mercury and the "free" mercury (inorganic and weakly bound) were determined separately. With the first hemodialysis, 1.4 mg of mercury was removed, but this amount decreased rapidly with subsequent dialyses. Fecal mercury excretion, on the other hand, was approximately 1 mg daily during the first two weeks. Excretion of mercury in urine did not exceed 126 microgram/day even during the polyuric phase. Losses in vomitus were insignificant. It is concluded that hemodialysis is of little use in elimination of mercury, even if performed after administration of dimercaprol.

[The use of combined spectroscopy in analytical toxicology (author's transl)]. / Einsatz der kombinierten Spektroskopie in der toxikologischen Analytik

The combined application of the four spectrometric techniques UV, IR, NMR and MS is an important analytical tool for the identification of the increasing number of potential poisons with which the analysts in the fields of forensic sciences and toxicology are confronted. Some of the contributions of these techniques to toxicological analyses are reviewed and illustrated by a few examples. Furthermore, the incorporation of the four methods into the analytical scheme, the requirements with respect to quantity and purity of the unkown substances, as well as the different possibilities for the combination of separation and identification techniques are outlined.