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Biomedical subjects

J C Lindon

Publications and source records attributed to J C Lindon.

At least 73 records · Page 4Linked to original sources

Measurement of biomolecular diffusion coefficients in blood plasma using two-dimensional 1H-1H diffusion-edited total-correlation NMR spectroscopy.

The use of two-dimensional diffusion-edited total-correlation NMR spectroscopy (DETOCSY) to measure diffusion coefficients of molecules in biofluids is demonstrated. The method takes advantage of the increased peak dispersion in a two-dimensional spectrum and allows the measurement of diffusion coefficients of individual molecules in complex biofluid samples in a condition close to their natural state. The NMR spectra can be edited on the basis of diffusion coefficient, and hence, approximate molecular size and this provides a qualitative means of simplifying the spectra for assignment purposes. The use of two-dimensional DETOCSY NMR spectra increases the probability that the individual cross-peaks arise from single components and hence allows single-exponential fitting of the magnetic field gradient dependence of cross-peak volumes. Interpretation of the derived diffusion coefficients improves the NMR resonance assignment process in complex biofluid mixtures by giving additional information on the molecular size. The DETOCSY approach also provides information on small molecule-macromolecule interactions such as the binding of drugs or endogenous species to serum proteins such as albumin.

Diffusion↗

Direct observation of resolved intracellular and extracellular water signals in intact human red blood cells using 1H MAS NMR spectroscopy.

High resolution 400 MHz 1H NMR spectra of red blood cell suspensions when measured using magic angle spinning (MAS) show two water resonances separated by 15 Hz. Based on addition of a paramagnetic Mn-EDTA complex, measurement of relaxation times and variation of extracellular H2O/D2O ratios, these have been assigned as intracellular (linewidth 17.5 Hz) and extracellular water (linewidth 4.6 Hz). This is the first direct observation of intracellular water using NMR spectroscopy and the 1H MAS NMR spectroscopic approach offers the possibility of studying directly the compartmentation of substances in cells and kinetics of molecular transport.

Body Water↗

NMR and HPLC-NMR spectroscopic studies of futile deacetylation in paracetamol metabolites in rat and man.

HPLC-NMR spectroscopy has been used to investigate the level of deacetylation followed by reacetylation (futile deacetylation) of metabolites of paracetamol detected in human and rat urine. This has been achieved through the synthesis and administration of paracetamol isotopically labeled at the acetyl group with C2H3, 13CH3 and 13CO-13CH3. Using paracetamol-C2H3 it had been shown that in the rat the sulphate metabolite present in the urine shows 10-13% futile deacetylation depending on the dose, whereas for paracetamol-13CO-13CH3 the corresponding value was about 8%. After solid phase extraction, it was also possible to determine the level of futile deacetylation in the glucuronide metabolite using directly-coupled HPLC-NMR. This approach was facilitated by the use of acetonitrile-d3 as an HPLC eluent and the HPLC-NMR analyses showed that the level of futile deacetylation in the sulphate and glucuronide metabolites were equal at about 9%. The glucuronide of paracetamol-C2H3 was the predominant metabolite in man and following separation using HPLC-NMR, the level of futile deacetylation was shown to be 1% for the glucuronide and 2% for the sulphate, these values being equal within experimental error. This work demonstrates the utility of NMR and HPLC-NMR spectroscopy for isotope exchange studies.

Acetaminophen↗

Investigation of the feasibility of directly-coupled HPLC-NMR with 2H detection with application to the metabolism of N-dimethylformamide-d7.

The use of 2H NMR spectroscopy as a detector for HPLC has been investigated using the continuous flow method in which rat urine containing metabolites of N-dimethylformamide-d7 was employed as a test case. Three xenobiotic-related species, including DMF-d7 itself, were detected. It is shown that for small molecules which give relatively sharp 2H NMR resonances, 2H HPLC-NMR spectroscopy is a feasible technique. For larger molecules, the resulting broad lines are likely to preclude the determination of detailed structural information. However, extension of the approach is possible by the use of selectively 2H-labelled xenobiotics to determine HPLC retention times of metabolites with continuous-flow 2H NMR spectroscopy detection, followed by stop-flow 1H HPLC-NMR spectroscopy for structural characterisation.

Animals↗

750 MHz 1H NMR spectroscopy characterisation of the complex metabolic pattern of urine from patients with inborn errors of metabolism: 2-hydroxyglutaric aciduria and maple syrup urine disease.

750 MHz 1H NMR spectroscopy has been used to characterise in detail the abnormal low molecular weight metabolites of urine from two patients with inborn errors of metabolism. One case of the rare condition 2-hydroxyglutaric aciduria has been examined. There is at present no rapid routine method to detect this genetic defect, although NMR spectroscopy of urine is shown to provide a distinctive pattern of resonances. Assignment of a number of prominent urinary metabolites not normally seen in control urine could be made on the basis of their known NMR spectral parameters including the diagnostic marker 2-hydroxyglutaric acid, which served to confirm the condition. In addition, 750 MHz 1H NMR spectroscopy has been used to characterise further the abnormal metabolic profile of urine from a patient with maple syrup urine disease. This abnormality arises from a defect in branched chain keto-acid decarboxylase activity and results in a build up in the urine of high levels of branched chain oxo- and hydroxy-acids resulting from altered metabolism of the branched chain amino acids, valine, leucine and isoleucine. A number of previously undetected abnormal metabolites have been identified through the use of one-dimensional and two-dimensional J-resolved and COSY 750 MHz 1H NMR spectroscopy, including ethanol, 2-hydroxy-isovalerate, 2,3-dihydroxy-valerate, 2-oxo-3-methyl-n-valerate and 2-oxo-isocaproate. NMR spectroscopy of urine, particularly when combined with automatic data reduction and computer pattern recognition using a combination of biochemical markers, promises to provide an efficient alternative to other techniques for the diagnosis of inborn errors of metabolism.

Amino Acid Metabolism, Inborn Errors↗

750 MHz HPLC-NMR spectroscopic identification of rat microsomal metabolites of phenoxypyridines.

Directly coupled 750 MHz HPLC-1H NMR spectroscopy has been applied to the characterisation of low level metabolites of 3-amino-2-(2-fluorophenoxy)pyridine (AP) and 3-nitro-2-(2-fluorophenoxy)pyridine (NP) in rat microsomes. In stop-flow HPLC-NMR mode, the direct injection of microsomal extracts enabled the separation and characterisation of minor metabolites. NP is converted into AP to an extent of 93.4% and this is further metabolised to 4- and 6-hydroxy-AP (6 and 0.6% respectively). Unequivocal identification of these metabolites was achieved without the use of a radiolabel or synthetic standards and thus demonstrates the applicability of directly coupled HPLC-NMR to metabolite identification in in vitro systems. The potential exists for HPLC-NMR and HPLC-NMR-MS to provide rapid metabolic information within the timescale of high throughput lead optimisation exercises in drug discovery.

Animals↗

Characterisation of impurities in bulk drug batches of fluticasone propionate using directly coupled HPLC-NMR spectroscopy and HPLC-MS.

Directly coupled HPLC NMR spectroscopic and HPLC-MS approaches have been used to confirm the identity of four known dimeric impurities in a partially purified batch of fluticasone propionate each at levels of 0.06-0.9% of parent compound based on UV absorption. It is also shown that HPLC NMR spectroscopy of the main drug peak in the 'time-slice' mode of operation, in which the elution of the HPLC peak is sampled a short time intervals, can be used to investigate the purity profile of the single HPLC peak detected by UV absorption. These studies show that HPLC-NMR is of considerable value in rapidly assessing HPLC peak purity and hence will be of benefit in providing additional information to support submission for drug registration to regulatory agencies.

Androstadienes↗

NMR spectroscopic studies on the metabolism and futile deacetylation of phenacetin in the rat.

1. 1H-NMR spectroscopy of urine was used to determine the % deacetylation and re-acetylation of 2H-labelled (in the acetyl) phenacetin metabolites in the rat. 2. Male Sprague-Dawley rats were each dosed with either phenacetin or phenacetin-C2H3 at 50 mg kg-1. The total urinary recoveries for phenacetin and phenacetin-C2H3 were 47.6 +/- 16.7 and 50.1 +/- 16.2% respectively (not significantly different, p > 0.05). Paracetamol sulphate and glucuronide are the major urinary metabolites of both protio and deuteriophenacetin. 3. The futile deacetylation given by the urinary recovery of protio-acetyl metabolites of phenacetin-C2H3 was 29.6 +/- 0.9% for paracetamol sulphate and 36.6 +/- 3.1% for paracetamol glucuronide. These observations demonstrate a high level of futile deacetylation in the paracetamol conjugates formed by metabolism of phenacetin-C2H3 and this may indicate a high metabolic flux through the nephrotoxic intermediate 4-aminophenol. 4. The level of futile deacetylation for phenacetin was significantly higher than that found previously in studies of labelled paracetamol in rat or man, and may be important in understanding the higher nephrotoxicity of phenacetin as compared with paracetamol.

Acetaminophen↗

Uroscopy in the 21st century: high-field NMR spectroscopy.

From the experiments described, it can be seen that there are different research approaches that can be taken and these are summarized in Table 1. Whereas much scientific research is principally hypothesis led, there remains, nevertheless, an important place for exploratory research. High resolution NMR can measure, directly and simultaneously, a wide range of endogenous metabolites in biological fluids and has the unique capability of providing structural information on the metabolites detected. It has proved to be a powerful research tool with which to study inherited metabolic diseases, renal disease, drug metabolism, and toxicity, and can be used to monitor the effects of drug therapy. For instance, by using a library of experimental toxins one can map the metabolic profile of site-specific nephron injury. With this approach in man one could eventually take an unknown disease such as Balkan nephropathy and predict the initial site of tubular injury, the mode of injury and therefore the kind of toxin capable of producing that injury. NMR spectroscopic techniques are still advancing rapidly, with ever increasing sensitivity and sophistication of NMR pulse sequences to enhance structural elucidation in complex mixtures. Given the advances in directly coupled HPLC-NMR and even HPLC-NMR-mass spectroscopy it is likely that these technologies in conjunction with pattern recognition will make major contribution to our understanding of renal processes and provide new diagnostic insights in the 21st century.

Forecasting↗

Combined HPLC, NMR spectroscopy, and ion-trap mass spectrometry with application to the detection and characterization of xenobiotic and endogenous metabolites in human urine.

The direct coupling of HPLC with NMR spectroscopy has been extended by splitting the HPLC eluent after conventional UV detection and sending part to a NMR spectrometer and part to an ion-trap mass spectrometer in a "triplehyphenated" HPLC-NMR-MS system. Combined UV, 1H NMR, and positive-ion electrospray MS detection was achieved in the continuous-flow mode using whole human urine from a subject dosed with acetaminophen. By means of HPLC-NMR-MS, the structural information available from the complementary spectroscopic techniques provided rapid confirmation of the identity of the acetaminophen glucuronide and sulfate metabolites, together with a number of endogenous metabolites. In particular, the HPLC-NMR-MS approach allowed the unequivocal identification of phenylacetylglutamine in human urine, an endogenous metabolite not previously observed in 1H NMR spectra of urine because of extensive overlap with resonances from other metabolites. The analytical advantages and complementarity of NMR and MS techniques in direct hyphenation with HPLC are discussed. The new technique of HPLC-NMR-MS will provide the scope for more comprehensive and fully automated analysis of biofluids and other complex mixtures than was previously available from single hyphenation of these instruments.

Acetaminophen↗

Development of a simple liquid chromatographic method for the separation of mixtures of positional isomers and anomers of synthetic 2-, 3- and 4-fluorobenzoic acid glucuronides formed via acyl migration reactions.

Many drugs containing carboxylate groups form beta-1-O-acyl glucuronides as their major phase II metabolites in vivo. These ester glucuronides are potentially reactive due to the susceptibility of the acyl group to nucleophilic reactions resulting in hydrolysis, acyl migration or covalent adduct formation. In the present study, a number of synthetic fluorobenzoic acid glucuronide conjugates were chosen as models for chromatographic studies. A high-performance liquid chromatography method is presented for the simultaneous determination of the 1-, 2-, 3- and 4-positional isomers of the acyl glucuronides, and their alpha- and beta-anomers for the 2-, 3- and 4-fluorobenzoic acids as well as each aglycone formed as a result of hydrolysis. The same elution order was found for the acyl migrated glucuronide isomers of the three fluorobenzoic acids in their equilibrium mixtures. The alpha-4-O-acyl isomer eluted first followed by the beta-4-O-acyl isomer, then the beta-1-O-acyl, the beta-3-O-acyl, the alpha-3-O-acyl, the alpha-2-O-acyl and finally the beta-2-O-acyl isomer eluted. The method was used to determine the overall degradation rates, the acyl migration rates and the hydrolysis rates of 1-O-(2-fluorobenzoyl)-beta-D-glucopyranuronic acid 1-O-(3-fluorobenzoyl)-beta-D-glucopyranuronic acid and 1-O-(4-flurobenzoyl)-beta-D-glucopyranuronic acid in a buffer system pH 7.4 at 25 degrees C. It was found that the order of beta-1-glucuronide acyl migration rates was 2-fluorobenzoyl > 3-fluorobenzoyl > 4-fluorobenzoyl. Both the acyl migration rates and the elution order were interpreted in terms of electronic effect of the fluorine substituent on the carbonyl carbon.

Acylation↗

High-resolution diffusion and relaxation edited one- and two-dimensional 1H NMR spectroscopy of biological fluids.

A new approach to the characterization of biomolecules in whole biological fluids is presented based on simplification of 1H NMR spectra by utilizing differences in molecular diffusion coefficients alone and combinations of relaxation and diffusion parameters. New NMR pulse sequences incorporating both spectral editing features together with solvent water resonance elimination are presented. The methods are exemplified using whole human blood plasma, and it is shown that it is possible to obtain NMR spectra of the slowly diffusing species (generally large molecules) by diffusion editing, the slowly relaxing species (generally small molecules) by spin relaxation editing, or spectra showing any range of molecular mobility using a combination of the two methods. The diffusion-based editing methods are also applicable to the selection of resonances in two-dimensional NMR spectroscopy of biofluids, and we show this for the first time by the production of 1H-1H diffusion-edited TOCSY spectra of human blood plasma where the resonance intensities are weighted according to the molecular diffusion coefficient. In this case, by measuring a diffusion-edited 1H-1H TOCSY NMR spectrum of plasma, it is possible to obtain signals from only the macromolecular components, and this may be of benefit in the analysis of blood lipoproteins. In complex biofluids, the combination of diffusion and relaxation editing brings about considerable spectral simplification leading to an easier resonance assignment process. We also demonstrate the production of 1H NMR spectra with intensities corresponding to diffusion coefficient rather than number of protons, and this opens up new possibilities for pattern recognition classification of samples based on altered molecular mobility features of biofluid components.

Blood↗

Direct characterization of drug glucuronide isomers in human urine by HPLC-NMR spectroscopy: application to the positional isomers of 6,11-dihydro-11-oxodibenz[b,e]oxepin-2-acetic acid glucuronide.

In this work, 400 and 600 MHz 1H HPLC-NMR spectroscopic methods were developed and applied to separate and identify the positional glucuronide isomers and anomers of the model nonsteroidal antiinflammatory drug, 6,11-dihydro-11-oxodibenz[b,e]oxepin-2-acetic acid, in whole human urine. The HPLC methods utilized either an isocratic system, comprising 30% acetonitrile in water at pH 2.5, or a gradient elution system increasing from 30% to 60% acetonitrile, in order to achieve improved separation of the 2-, 3-, and 4-O-acylglucuronide isomers from the faster eluting endogenous urinary metabolites. Directly coupled stop-flow 1H HPLC-NMR spectroscopic measurements were made at the retention times indicated by the UV-monitored chromatographic peaks. The glucuronide isomers were identified from the 1H NMR spectra on the basis of their chemical shifts and spin-spin coupling patterns. The elution order was 4-O-acyl-, 3-O-acyl-, and finally 2-O-acylglucuronide, with tR values of 10.04, 11.68, and 12.64 min, respectively. Although the alpha- and beta-anomers of each of the positional isomers could not be separated in these solvent systems, they could be identified in the individual 1H NMR spectra. This work shows for the first time that directly coupled HPLC-NMR spectroscopy can be used directly to isolate and characterize acyl-migrated isomers of drug glucuronides in whole urine. This approach will be of value in the study of glucuronide acyl migration reactions of nonsteroidal antiinflammatory drugs and other xenobiotic ester glucuronides in whole biofluids.

Acetates↗

750 MHz HPLC-NMR spectroscopic studies on the separation and characterization of the positional isomers of the glucuronides of 6,11-dihydro-11-oxodibenz[b,e]oxepin-2-acetic acid.

Ester glucuronides (beta-1-O-acyl-D-glucopyranuronates) of many drugs can undergo a series of acyl migration reactions, resulting in positional isomers and anomers which can react with serum proteins with possible toxicological consequences. We have investigated the acyl migration of the ester glucuronides of the model drug 6,-11-dihydro-11-oxodibenz[b,e]oxepin-2-acetic acid in pH 7.4 buffer using directly coupled 750 MHz stopped-flow HPLC-NMR spectroscopy. Using a reversed phase isocratic HPLC method with 21% acetonitrile and 79% D2O in the mobile phase, it was possible to separate and hence identify the individual positional isomers of the model drug glucuronide by 750 MHz HPLC-NMR. The order of elution of the isomers from the C18 column was 4alpha-, 4beta-, aglycon, 1beta-, 3beta-, 3alpha-, 2alpha-, 2beta- (alpha- and beta- referring to the anomerization state at C1 on the glucuronide ring and the numbers referring to the carbon number on the glucuronide ring to which the drug moiety has migrated). It is shown that directly coupled ultra-high-field HPLC-NMR spectroscopy offers a unique analytical advantage for obtaining structural information of interconverting compounds in equilibrium mixtures, and this method will be of value in the study of reactive drug glucuronides of toxicological importance.

Acetates↗

NMR spectroscopic and theoretical chemistry studies on the internal acyl migration reactions of the 1-O-acyl-beta-D-glucopyranuronate conjugates of 2-, 3-, and 4-(trifluoromethyl) benzoic acids.

High resolution 19F NMR spectroscopy has been used to investigate the kinetics of internal acyl migration and hydrolysis of the synthetic beta -1-O-acyl-D-glucopyranuronates of 2-, 3-, and 4-(trifluoromethyl) benzoic acids (TFMBAs) in phosphate buffer solutions at 30 degrees C as models of drug ester glucuronides. Apparent first-order degradation of the 1-O-acyl glucuronide and the sequential appearance of 2-, 3-, and 4-O-acyl isomers as both alpha- and beta-anomeric forms were observed for each TFMBA isomer. The overall degradation rate constants of the 2-, 3-, and 4-TFMBA 1-O-acyl isomers were 0.065 h-1, 0.25 h-1, and 0.52 h-1. In order to probe the reasons for these differences in reactivity, theoretical structural and electronic parameters for the beta-anomers of the 1-O-acyl glucuronides, their beta-2-O-acyl isomers, and both structures of the postulated ortho-acid ester intermediate were computed using semiempirical molecular orbital (AM1 and PM3) methods. The distinction between the slowly reacting 2-TFMBA glucuronide and the much faster reacting 3- and 4-TFMBA glucuronides could be observed by calculation of the relative bond order of the C-O bonds in the ortho-acid ester intermediates. The slow internal acyl migration rate of the 2-TFMBA isomer was also partly attributed to the high degree of steric hindrance of the trifluoromethyl group obstructing attack by the glucuronic acid 2-hydroxy group on the carbonyl carbon to form the ortho-acid ester intermediate. Some calculated molecular orbital properties, namely, dipole moment, energy of the lowest unoccupied molecular orbital (LUMO), LUMO density, and nucleophilic frontier density on the carbonyl carbon, were also shown to be related to the measured half-lives. This work gives insight into the molecular physicochemical properties that influence the acyl migration kinetics of simple model drug glucuronides and is of potential importance in understanding more complex drug glucuronide acyl migration reactions of toxicological interest.

Acylation↗

Nuclear magnetic resonance and high-performance liquid chromatography-nuclear magnetic resonance studies on the toxicity and metabolism of ifosfamide.

A combination of high-resolution nuclear magnetic resonance (NMR) and high-performance liquid chromatography (HPLC)-NMR spectroscopic methods has been used to analyse urine from humans and rats treated with the anticancer drug ifosfamide. It was possible to detect a range of abnormal endogenous metabolites in urine after ifosfamide administration to human subjects undergoing cancer therapy and to relate the metabolic perturbations to the nephrotoxic effects of the drug. Changes observed by 1H NMR included increases in levels of urinary glucose, glycine, alanine, histidine, lactate, acetate, succinate, and trimethylamine-N-oxide and decreases in the levels of hippurate and citrate. Additional evidence was gained that ifosfamide-induced nephrotoxicity might be related to the level of oxidation of the coadministered drug mesna. By using both directly coupled continuous-flow 31P HPLC-NMR spectroscopy to determine the retention times of the phosphorus-containing metabolites and, subsequently, stop-flow 1H HPLC-NMR of the urine, it was possible to isolate and identify on-line the metabolites ifosfamide mustard, 4-hydroxy-ifosfamide, 2-dechloroethylifosfamide, and the parent compound itself. These studies illustrate the potential of combining 1H NMR spectroscopy of biofluids and HPLC-NMR spectroscopy for the investigation of drug metabolism and toxicity in humans and animals.

Animals↗

Characterization of in vitro metabolites from human liver microsomes using directly coupled hplc-nmr: application to a phenoxathiin monoamine oxidase-A inhibitor.

1. The metabolism of 1-ethylphenoxathiin-10,10-dioxide (BW1370U87), an experimental compound designed as an inhibitor of monoamine oxidase-A for use as a possible anti-depression agent, has been studied in a human liver microsome preparation. 2. The identities of the metabolites have been determined using directly coupled hplc-1H nmr at 600 MHz in the stop-flow mode in this first study of in vitro xenobiotic metabolism using hplc-nmr. 3. The xenobiotic substances that were identified comprised the parent compound BW1370U87 (with -CH2CH3 at C1) together with sidechain-oxidized metabolites with C1 substituents of -CHOH.CH3, -CH2.CH2OH, -CHOH.CH2OH and -CH2.COOH, plus the unsubstituted phenoxathiin-10,10-dioxide.

Biotransformation↗