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Biomedical subjects

H Oelschläger

Publications and source records attributed to H Oelschläger.

At least 19 recordsLinked to original sources

[In vitro investigations of phase I metabolism of the fomocaine derivative Oe 9000 with pig liver homogenates].

2,2'-[4-(4-Phenoxymethylphenyl)butylimino]diethanol (Oe 9000) is a new, highly potent local anaesthetic related to fomocaine. It displays a long duration of action, low toxicity and is superior to fomocaine with regard to aqueous solubility and efficacy. In view of the development of new application forms, e.g. for the treatment of postoperative pain, the elucidation of the biotransformation of the drug is required. Therefore, experiments with 10000 x g supernatants and microsomes from pig liver homogenates were conducted. Using specifically synthesized reference compounds six phase I metabolites could be identified by LC-MS. Apart from the predominating oxidative desamination of the compound, that led after redox reactions to the corresponding butyric acid and butanol derivatives, oxygenation of the exocycle, oxidative N-desalkylation, and N-oxidation were observed. Thus, with the exception of one compound only metabolites are generated, that are expected to have no local anaesthetic activity due to their reduced basicity.

Anesthetics, Local↗

Investigations on the thermal behavior of omeprazole and other sulfoxides.

Thermoanalytical and chromatographic investigations were performed to elucidate the reason for the uncommon thermal behavior of omeprazole prepared according to a newly developed route of synthesis. Differential scanning calorimetry revealed that the position of the melting endotherm of omeprazole strongly depended on the heating rate. High heating rates (20-30 degrees C/min) led to endothermic peaks at high temperatures (comparable to literature data), while lower rates induced a shift of the signal to lower temperatures. In thermogravimetric experiments weight loss was observed which started about 20 degrees C lower at the heating rate of 1 degrees C/min in comparison with the rate of 20 degrees C/min. Thermomicroscopic investigations indicated a decomposition prior to melting at low (1 degrees C/min) but not at high heating rates (20 degrees C/min). Investigation of the violet melt by HPLC and TLC showed that omeprazole was decomposed quantitatively. Decomposition started at 135 degrees C and depended on the rate of heating. The results indicate that eutectic behavior with decomposition products leads to a melting point depression of omeprazole upon slow heating. Similar behavior was observed for the related sulfoxides lansoprazole and pantoprazole which showed the same onset temperature for decomposition as omeprazole in chromatographic investigations. The heating rate dependent melting behavior was, however, much less pronounced for pantoprazole which has a melting range only slightly above the onset temperature for decomposition. In contrast, a constant value for the melting temperature could not be achieved for lansoprazole, the substance with the highest melting range under investigation, even at high heating rates up to 30 degrees C/min. In conclusion, a very dynamic method and exactly standardized measurement conditions, particularly with regards to heating rate, (e.g., in DSC) have to be employed to enable reliable determination of a melting point of these decomposable substances.

Anti-Ulcer Agents↗

[Studies on the recovery of pharmaceutical drug substances from surfaces made of defined stainless-steel alloys].

Facilities for the manufacturing of pharmaceutical drug substances on the pilot-plant and the industrial scale as well as chemical reactors and vessels used for chemical work-up mainly consist of alloyed stainless steel. The influence of the alloy composition and the surface condition, i.e. of the roughness of the stainless-steel materials, on the adsorption of structurally diverse steroidal substances and, hence, on the quality of the products was studied. In general, stainless-steel alloys with smooth, not so rough surfaces are to be favored as reactor material. However, it was demonstrated in this study that, on account of the weak interaction between active substances and steel materials, mechanically polished materials of a medium roughness up to approx. 0.4 microm can be employed instead of the considerably more cost-intensive electrochemically polished stainless-steel surfaces. The type of surface finishing up to a defined roughness, then, has no influence on the quality of these pharmaceutical products. Substances that, because of their molecular structure, can function as "anions" in the presence of polar solvents, are adsorbed on very smooth surfaces prepared by electrochemical methods, forming an amorphous surface film. For substances with this structural characteristics, the lower-cost mechanically polished reactor materials of a medium roughness up to approx. 0.5 microm should be used exclusively.

Algorithms↗

[New findings on the synthesis of the centrally acting muscle relaxant chlormezanone and its resolution of a gram scale using a Chiralcel OD column].

2-(4-Chlorophenyl)-4-metathiazanone (2) is the intermediate product for the two step-synthesis of chlormezanone (1), a centrally acting muscle relaxant. The second step includes the oxidation of its sulfur atom. It has been found that the foregoing reaction of 4-chlorobenzaldehyde with methylamine forming the hemiaminale and the subsequent addition of beta-mercaptopropionic acid leads to a remarkable better yield (67% of th.) than the route via the hemimercaptale (42% of th.). 2 could be oxidized with sodium perborate superior to potassium permanganate. The racemic chlormezanone (1) is resolved quickly on a gram scale by preparative column chromatography on a Chiralcel OD column (tris(3,5-dimethyl-phenyl-carbamoyl)cellulose on silicagel). The resolution needed only 40 min, if flow rate, composition of the mobile phase and temperature as the most important factors are determined prior with an analytical column. Both dissociation constants could be determined for the first time with the aid of a log pKa-Titrator of the Sirius Co., which needs for the registration of the curves only 15-17 min in the pH range of 2-12. This speed outplayed the disturbing cleavage of the S-C bond of chlormezanone at strong acidic and alkaline pH values.

Chlormezanone↗

[Photometric determination of iron contamination of drugs and biological matrices].

The Ph. Eur. detects colorimetrically the limiting value of iron by formation of a complex with thioglycolic acid in ammoniacal solution. This reaction was rechecked by experiments. Contrary to the literature a solvated Fe(II)-complex will be formed due to the reduction of Fe(III) by the present thioglycolic acid. A supposed oxidation of the Fe(II)-complex by atmospheric oxygen does not occur. For the routine determination of traces of iron in medicinal substances and biological matrixes a VIS-method was developed based on the measurement of the absorption of the complex at 534 nm in the range of 10-100 ppm after graded oxidative decomposition with conc. sulfuric acid/H2O2 30%. This assay needs a calibration mixture or in the case of a higher demand of accuracy a calibration curve with at least five measuring points. Because of the contamination of commercially available reagents a blank value must be determined.

Biological Factors↗

[Simultaneous photometric determination of covalently bound fluorine and fluoride ion contamination adsorbed on drugs in the low ppm range after alkaline pulping].

The simultaneous determination of fluorine resulting from inorganic fluoride as well as fluorine-containing solvents adsorbed to drugs was achieved in the 0.1-30 ppm range by a combination of decomposition with magnesium oxide at 800 degrees C and steam distillation of the resulting fluoride followed by photometric measurement of the aminomethylalizarindiacetic acid-cerium(III) complex at 620 nm. The inevitable loss of fluoride occurring during the decomposition and distillation processes was corrected using factors derived from authorized calibrations. The method was validated using glucose contaminated with dexamethasone which contains 4.84% fluorine per molecule.

Alkalies↗

[3,5-Dinitrobenzoic acid anhydride as reagent for the characterization of drugs and for the activation of polarographically inactive compounds].

Drugs with primary or secondary amino groups react with 3,5-dinitrobenzoic acid anhydride under catalysis of pyridine derivatives almost quantitatively to yield the corresponding amides which are reducible at the dropping mercury electrode (DME). 3,5-Dinitrobenzoic acid will be separated by thin layer chromatography. The limit of detection by DPP is in the range of 10(-8) M. The electrode reaction is irreversible.

Anhydrides↗

[Physical chemical, pharmacological and toxicologic properties of fomocaine metabolites] .

Fomocaine (4-[3-(4-phenoxymethylphenyl)-propyl]-morpholine, CAS 17692-39-6) is a highly effective local anaesthetic of low toxicity. The drug, which causes no allergic response, was introduced in the German Extrapharmacopoeia (DAC). Fourteen metabolites are formed after oral administration to rat and beagle dog. Less than 5% fomocaine are excreted unchanged. The metabolites were synthesized and their physico-chemical properties were investigated. No metabolite caused a surface or conduction anaesthesia with the exception of 2-hydroxyfomocaine (O/Se 4). After topical and parenteral administration irritation could not be observed. All metabolites except O/Se 10 and O/Se 11 showed a lower toxicity than fomocaine. In both species O/Se 10 and O/Se 11 are formed only in a small amount and are detoxified by conjugation.

Anesthetics, Local↗

Local anaesthetic effectivity and toxicity of fomocaine, five N-free fomocaine metabolites and two chiralic fomocaine derivatives in rats compared with procaine.

Until now, no optimal local anaesthetic drug with long lasting effect and low toxicity has been developed. Fomocaine (CAS 17692-39-6), introduced in the German extrapharmacopoela (DAC) in 1979, is a local anaesthetic, which is largely in accordance with these aspects. Now the basic ether fomocaine, its metabolites O/Se 9 (CAS 3006-96-0), O/Se 10 (CAS 31719-76-3), O/Se 11, O/Se 12 (CAS 64264-21-7) and M5 and its chiralic derivatives O/G 3 and O/G 5 were compared with procaine (CAS 59-46-1) and characterised more in detail in rats. The metabolism of fomocaine was investigated earlier with 14C-fomocaine in rats and beagle dogs. Rac-O/G 3 and Rac-O/G 5 could be separated into the enantiomers via the diastereomeric salts. Basing on standard methods for the testing of the local anaesthetic effects (estimation of infiltration and conduction anaesthesia in rat tail, measurement of corneal anaesthesia) and using a couple of tests characterising the side effects and toxicity of local anaesthetic (paresis of the N. ischiadicus, tissue irritation, determination of the approximative i.p. LD50) it can be concluded that: a) The very good surface anaesthesia caused by fomocaine could be stated, but, as expected, concerning conduction anaesthesia, procaine is better qualified for clinical use. b) Fomocaine is much more effective in conduction and surface anaesthesia than its chiralic derivatives O/G 3 and O/G 5. c) Differences between the two enantiomers of the O/G-substances have been found, but these little discrepancies are without practical relevance. In the case of O/G 5, agonistic effects of both enantiomers could be shown. d) Fomocaine undergoes extensive biotransformation with subsequent formation of 14 metabolites. Five of them (O/Se 9-O/Se 12; M5) are N-free and do not show any pharmacological activity. e) Compared to other local anaesthetics, fomocaine is relatively non-toxic (nearly no tissue irritation, high approximative LD50), however, surprisingly the toxicity of the reference substance procaine has been found to be lower after i.p. administration instead of i.v. administration in comparison with fomocaine.

Anesthesia, Conduction↗

[Synthesis and pharmacologic action of chiral fomocaine ((4-[2-methyl-3-(morpholin-4-yl)propyl)benzyl)-phenyl-ether and (4-(1-methyl-3-(morpholin-4-yl)propyl]benzyl)-phenyl-ether). 13. Synthesis of new compounds with local anesthetic action].

The syntheses of two chiral fomocaines namely rac ((4-[2-methyl-3-(morpholin-4-yl)propyl]-benzyl)-phenyl-ether (O/G 3) and rac (4-[1-methyl-3-(morpholin-4-yl)propyl]benzyl)-phenyl-ether) (O/G 5) are reported. These compounds are part of a new research program concerning the relation between chirality and local anaesthetic activity in the group of fomocaines. The yield over five steps is in the range of 9% (O/G 3) up to 19.2% (O/G 5). The racemates were resoluted via the diastereomeric salts formed with (+)- or (-)-camphersulfonic acid. The chromatographic resolution in analytical scale is successful using a Daicel OD-column. The enantiomers are stable. The surface anaesthesia of the racemates as well as of the enantiomeres is weaker in comparison with fomocaine. The rate of tissue irritation is higher. The LD50 (mouse i.v.) is in the range between 290-390 mg/kg, while fomocaine shows a LD50 value of 175 mg/kg.

Anesthetics, Local↗

[Important pharmaceutical-chemical characteristics of the central muscle relaxant chlormezanone].

The enantinomers of chlormezanone (1) may be achieved by enantioselective HPLC separation with a yield of 98% using a OD-Daicel column. Both enantiomers bind to human serum albumin (HSA) at pH 7.4 to a range of 11-12%. Binding to the globuline fractions is much less (2-4%, equilibrium dialysis, validation by ultrafiltration). It could be demonstrated by means of 1H-NMR spectroscopy that 1 binds to HSA with the benzene ring as well as with the thiazanone ring. The velocity of racemization could be measured for the first time using a BSA column. The enantiomers undergo racemization at pH 7.4 and 37 degrees C with a halflife of approx. 20.5 h.

Chlormezanone↗

Ciprofibrate--racemate and enantiomers: effects of a four-week treatment on male inbred Fischer rats. A biochemical and morphological study.

Ciprofibrates (racemate and both enantiomers, Raccip, R- and Scip) were administered orally in doses of 1 and 10 mg/kg once daily over 28 days to male inbred Fischer 344 rats, age 90-110 days at the beginning of the experiment. Body mass gain was observed in all groups. The 1 mg groups showed almost no difference to the control group. The 10 mg groups exhibited less body mass gain, most pronounced in the Scip group. Liver masses were increased in a dose dependent manner up to more than 200%, only the 10 mg Scip group was not significantly different from the 1 mg group which exhibited an increase in liver weight to about 175%. Also the kidney weights increased to 130%, whereas thymus and spleen weights were decreased in the high dose groups. Liver microsomal cytochromes P450 (P450) concentrations were not altered in the 1 mg groups and distinctly lowered in the 10 mg groups. Ethoxyresorufin and ethoxycoumarin O-deethylations were lowered in all experimental groups in a dose dependent manner, after administration of the high doses down to 30% of the control levels or less. Pentoxyresorufin O-depentylation, however, was increased in all 1 mg groups. In the high dose groups it was not altered. Ethylmorphine N-demethylation was decreased after administration of the high doses by about 50%, but only Scip decreased this reaction also after administration of the low dose. NADPH/Fe2+-stimulated microsomal luminol and lucigenin amplified chemiluminescence was increased, whereas hydrogen peroxide formation was depressed even by the low doses to 50% of the normal values, to about 25% by the high doses. Microsomal lipid peroxidation, however, was only slightly or not influenced. Glutathion concentrations (in the reduced and the oxidized form) were increased in a dose dependent manner by about 20 to 30%, the concentration of lipid peroxides was not significantly influenced. Thus, the effects of the enantiomers were not different and were similar to those of the racemate. In serum, cholesterol and triglycerides were only moderately lowered. Albumin concentrations were significantly enhanced in all groups, total proteins after 1 mg/kg Raccip only. Serum bilirubins were not altered, and among the indicator enzymes for liver damage only ALAT, alkaline phosphatase and the dehydrogenases were increased, in no case higher than twofold. Histologically distinct effects were seen after administration of both doses, more pronounced after 10 mg/kg, but with no differences between the enantiomers and Raccip: marked hypertrophy of the hepatocytes, reduced staining of the nuclei, strongly acidophilic granulated cytoplama, no basophilia of the cell bodies, loss of glycogen. These changes were most pronounced around the central veins. Hepatocyte apoptoses also were observed. By immunohistochemistry an increased staining was seen for all P450 isoforms tested (1A1, 2B1, 2E1, 3A2 and 4A1), predominantly perivenously and most pronounced after administration of the high doses without differences between Rcip, Scip or Raccip (preliminary results). By electron microscopy a moderate proliferation of peroxisomes after treatment with 1 mg/kg Cips with a ratio between mitochondria and peroxisomes of about 1:1 (controls: 10:1) was observed, and the peroxisomes were a more heterogeneous population. The relative portions of glycogen and both forms of the ER decreased. Treatment with 10 mg/kg Rcip, Scip or Raccip led to a strong increase in the number of peroxisomes, in some hepatocytes the ratio between mitochondria and peroxisomes was 1:3 with an increased heterogeneity among the peroxisomes evidenced by a broad range of electron densities. Most peroxisomes lacked a nucleoid. Thus, the biochemical effects differed only slightly and the morphological effects of the enantiomers were not different and were similar to those of the racemate.

Administration, Oral↗

Chromatographic resolution of ciprofibrate and interaction of the racemate and both enantiomers with rat liver microsomes in vitro.

The enantiomers of ciprofibrate may be achieved by enantioselective HPLC separation of its methylesters using a OD - Daicel column. Ciprofibrates (racemate and both enantiomers) bind to oxidized cytochrome P-450 in rat liver microsomes according type II like aniline or most probably as inversed type I, but less pronounced and with a general shift to the left. Ethylmorphine N-demethylation, ethoxycoumarin and ethoxyresorufin O-deethylation are all inhibited by the ciprofibrates, most effectively ethoxyresorufin O-deethylation by S(-)-ciprofibrate even in microM concentrations. Microsomal luminol and lucigenin amplified chemiluminescence indicating the formation of reactive oxygen species, microsomal hydrogen peroxide formation and NADPH/Fe stimulated lipid peroxidation were inhibited in a concentration dependent manner in concentration ranges between mM and microM. This might be due to distinct scavenger activities of all 3 compounds: the zymosan stimulated chemiluminescence of whole blood was completely inhibited in mM concentrations and influenced significantly down to concentrations of 10 microM, whereas burst and phagocytosis tests with human polynuclear leucocytes were not influenced.

Aniline Compounds↗

[Cleavage and biotransformation of the central muscle relaxant chlormezanone].

Chlormezanone, a chiral centrally acting muscle relaxant, will be cleaved at its S-C-1 bond by an autoprotolytic process. The optimum of chemical stability exists between pH 2 up to pH 9 with a maximum at pH 7.4. The plasma half life at 37 degrees C is 76 h. Enzymes do attack the products of cleavage namely 4-chlorobenzaldehyde and 2-carboxyethane-sulfinic-acid-N-methyl-amide. The main metabolite in urine is 4-chlorohippuric acid in the range of up to 70% of the oral administered dose to humans. No cytochrome P-450 is engaged in the cleavage of the S-C-bond.

Biotransformation↗

[Fast thin-layer densitometric determination of the nootropic piracetam in biological material].

After oral doses of piracetam this drug is detectable in serum as well as in urine after formation of the red Fe(III)-hydroxamatecomplex by thin-layer densitometry. Detection in serum requires extraction with a mixture of dichloromethane/ methanol, while urine can be used directly after dilution. The limit of quantification in urine is 100 micrograms/ml and in serum 4.0 micrograms/ml. The new method was validated by HPLC. The coefficient of correlation was 0.9999% for determination in urine and 0.9986% for determination in serum.

Adult↗