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Part 1 Chapters of general nature: Emergency toxicology, Schmidt, Roth Therapeutic drug monitoring, Fraser Special aspects of forensic toxicology, Brandenberger Analytical of doping in sports, de Boer et al Pharmacokinetics as applied to drug and doping research, Vree The future of immuno-chemical drug analysis, Takatori, Nagao The future of instrumental analysis in toxicology, Brandenberger. Part 2 Chapters concerned with special poison classes: Natural gases and vapours, Brandenberger Carbon monoxide, Kojima Determination of alcohol levels in the body, Brandenberger et al Volatile hydrocarbons, Nagata, Kimura Volatile halogenated compounds, Flanagan Pesticides, Geldmacher et al Glycols, Roth Inorganic anions, Roth Non-metals of the group 16, Roth, Pelletier Metals of toxicological significance, Brandenberger, Roth. Part 3 Toxicological drug analysis: Barbiturates, Brandenberger Benzodiazepines. Schutz Hypnotics and sedatives not belonging to the classes of barbiturates and benzodiazepines, Brandenberger Anticonvulsants not belonging to the classes of barbiturates and benzodiazepines, Kulpmann Neuroleptics, Whelpton Antidepressants, Braithwaite Beta-blocking drugs, Leloux Analgesics, Antipyretics and non-steroidal anti-inflammatory agents, Widdop Antihistamines, Brandenberger Volatiles used or abused as anaesthetics, Brandenberger Digitalis (=cardiac) glycosides, Hallbach, Vogel Cyclosporins, Holt Anticoagulants, Geldmacher, Mallinckrodt Stimulants, de Boer et al Designer drugs, Henderson. Part 4 Blood level data, Uges

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. Language: en

Negative ion mass spectra for 3 aliphatic and 4 aromatic isocyanates have been obtained by low pressure chemical ionization, using CH4, CO2 and N2O as reagent gases. All compounds furnished intense anions at m/z 42. With CH4, quasi-molecular anions were observed at m/z M+1 for aliphatic and m/z M+1 and M−1 for aromatic isocyanates. With N2O, anionic substitution products at m/z M+15 and M+30 were observed, and with CO2 and N2O, peaks at m/z M−12 could be detected for all aromatic isocyanates. Studies with 13CO2 and C18O2 as reagent gases showed that the anions at m/z M−12 and M+15 correspond to [M−CO+O]− and [M−H+O]−, respectively.

Negative ion mass spectra of underivatized flavonoid O- and C-glycosides were recorded using desorption chemical ionization (DCI) at a low reagent gas pressure. Advantages and limitations of the method for the characterization of the mono-, di- and triglycosides are discussed. For all O-glycosides investigated, the aglycone moieties are found to be base anions. The molecular masses of the glycosides are indicated by the presence of [M]−. ions with fairly high abundances for monoglycosides, lower abundances for diglycosides and a very low intensity for triglycosides. In addition to the sugar moiety losses, anions which resulted from the stepwise elimination of water from the sugar moiety were also observed at m/z 290 or 306 in 1 6 linked bioses, m/z 127, 145 and 163 in deoxyhexose as well as m/z 161 and 143 in hexose. Those ions except ions due to the molecule and the retro-Diels–Alder cleavage of the aglycone moiety could not be found in electron ionization mass spectra. Consequently, information concerning the structure of the aglycone moiety could be obtained using the EI technique and of sugar moiety using the negative ion DCI technique; also the combined positive and negative ion was shown to be a good approach for the structural characterization of flavonoid glycosides.

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.

1. 1. Methods for the separation for isotopic analysis of the atoms of the uric acid carbon chain 4-5-6 have been investigated in order to determine the magnitude of contamination by carbon from other positions in the molecule. 2. 2. The differences in the calculation of the complete isotope distribution in carbon-labelled uric acids, due to the choice of degradation procedure of uric acid to glycine (direct acid hydrolysis or alkaline hydrolysis after degradation to allantoin and hydantoin), are discussed.

The rate of enzymatic hydrolysis of o-carboxy-phenyl-phosphate (I) has been compared with that of other substrates commonly used for phosphatase determinations. An acid phosphatase from wheat germ hydrolysed I faster than β-glycero-phosphate, phenyl-phosphate and phenolphtalein-diphosphate. Two alkaline phosphatases decomposed I somewhat more slowly than β-glycero-phosphate, but still over 10 times faster than phenolphtalein-diphosphate. Even in cases where another substrate is hydrolysed faster, the use of I is recommended because of the high accuracy and simplicity of the spectro-photometric determination described in an earlier communication.

The use of cellulose as an adsorbent for the proteins of plasma in aqueous solution has been investigated.

1. Polyfunctional isocyanates, insoluble in the common solvents, have been prepared by acid as well as by alkaline phosgenation of a solid polyamino-polystyrene. The light brown powders are identical in appearance with the starting material; they exhibit, however, a strong sharp IR.-absorption band at 2260 cm−1 (4.43 μ), and show no absorption peaks due to the presence of primary amino groups.

The mechanisms of the alkaline oxidations of uric acid with H2O2 and KMnO4 have been investigated using isotopically labeled uric acids. The structures of the oxidation products have been examined by means of the isotope experiments and ultraviolet and infrared spectra. The following conclusions can be drawn: 1 Oxonic acid (allantoxanic acid) (III), allantoxaidine (IV) and their derivatives are 2,4-dihydroxy-1,3,5-triazines, not imidazolidones (I and II). 2 The s-triazine rings contain uric acid carbon atoms 2, 4 and 8 and nitrogen atoms 3 and 9. The third nitrogen of the ring is derived 50–50 from the former positions 1 and 7, the additional carboxyl group of oxonic acid from the uric acid carbon 5. 3 It has been shown for the first time in the case of uric acid itself that, during formation of allantoin, the imidazolidone rings of hydroxy-acetylene-diureido-carboxylic acid (XI) split at the former uric acid position 5 and not at 4. On further degradation of allantoin, cleavage of the five-membered ring occurs again at the former uric acid carbon 5.

Eine Reihe biologisch interessanter primarer Amine mit Phenylathylamin-Struktur last sich in einer auserst einfachen Reaktion in ihre Isothiocyanate uberfuhren, wobei vorhandene Hydroxyle im gleichen Arbeitsgang silyliert werden konnen. Die Derivate lassen sich gut gas-chromatographieren. Sie liefern bei der Elektronenstos-Ionisation meist nur wenige und dafur intensive Ionen, die sich als Tracer fur die hochempfindliche massenspezifische Detektion der Verbindungen vorzuglich eignen. Arbeitet man mit niedriger Elektronenenergie (die von Fall zu Fall in Vorversuchen bestimmt werden mus), so ist das Molekul oft das Basision. Bei gleichzeitiger Erfassung seiner Isotopenionen kommt dem Verfahren eine besonders hohe Spezifitat zu.

A rapid and very sensitive spectrophotometric method for the determination of the acid and alkaline phosphatases is given, using o-carboxyphenyl-phosphate as a substrate. This compound has been purified and characterized by its melting point and absorption spectra in aqueous solutions of different pH. Hydrolysis of the ester can be followed continuously by measuring the increase of extinction at 298 mm.

Using isotopic tracer methods, we have established which C and N atoms of the uric acid molecule are incorporated into oxonic acid (allantoxanic acid) and allantoxaidine. These two alkaline oxidation products do not contain the original imidazole ring of uric acid. Symmetrical triazine structures are proposed to replace the generally accepted imidazolidine formulas.

Mass spectra of seven N-nitrosamines and five alkyl nitrites, the O-nitroso compounds, have been obtained by low pressure negative chemical ionization with CO2 as reagent gas. Intense anions were observed at m/z M−32 for N-nitrosamines and at m/z M−30 for alkyl nitrites. Addition products were found at m/z M+12 and M+43 for N-nitrosamines and at m/z M+14 for alkyl nitrites. By using isotopically labeled CO2, it could be shown that the anions at m/z M+12, M+14 and M+43 correspond to [M - H2NO + CO2 −, [M − NO + CO2]−, and [M − H + CO2]−, respectively.

The poisoning effect of hydroxy-s-triazines on Pt-catalyst was observed using the system PtO2, triazine-derivative, 3,4,5-trimethoxy-cinnamic acid and H2 in alcohol. The dihydroxy-s-triazines I and II resulting from alkaline oxidation of uric acid, their dihydro-derivatives III and IV, and trihydroxy-s-triazine cyanuric acid (VI) inhibit the hydrogenation as has previously been found for the unsubstituted s-triazine V.

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.

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 HC1). 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.

1. 1. Using isotropic tracer methods, the alkaline oxidation of uric acid to oxonic acid (allantoxanic acid) and allantoxaidine has been investigated. These two compounds do not contain the imidazole ring of uric acid, as is generally believed. They are formed from carbon atoms 2, 4 and 8, and nitrogens 3 and 9 of uric acid. The third nitrogen originates 50-50 from positions 1 and 7. In addition, oxonic acid contains the former carbon 5 as a carboxyl group. 2. 2. Symmetrical triazine structures are proposed for oxonic acid, allantoxaidine, and their derivatives to replace the generally accepted imidazolidine formulas. 3. 3. An indirect method is given for the calculation of the complete N- and C-isotope distribution in labelled uric acids. It is based on isotope determinations of uric acid and simple degradation products which are easily obtained in good yield and a very pure state.