Determination of diastereomeric purity of tranylcypromine sulfate by proton magnetic resonance spectroscopy with lanthanide shift reagent

Use of proton nuclear magnetic resonance spectroscopy and the lanthanide shift reagent, Eu(hfc)3, resulted in a simple and reliable method for determination of the diastereomeric purity of trans-2-phenylcyclopropylamine sulfate (tranylcypromine sulfate). Eu(hfc)3 effectively simplified the complex overlapping pattern of the 5 non-equivalent phenyl protons to a virtually first order pattern. At a shift reagent to substrate molar ratio of 0.75, and a substrate concentration of 0.25M (as the free base) in CDCl3, the resonances for the cis- and trans-ortho-phenyl protons at 11.39 and 9.99 ppm, respectively, were sufficiently resolved to be of use in quantitative work. Analysis of synthetic diastereomeric mixtures of 2-phenylcyclopropylamine sulfate by the proposed method yielded results that were in close agreement with the expected values. The mean recovery (SD) of trans-diastereomer was 100.51% (0.40) (n = 6). Levels of less than 2% of cis-diastereomer were measurable in cis-trans mixtures.     

Analysis of polychlorinated biphenyls by carbon-13 nuclear magnetic resonance spectroscopy.

A technique is presented for the analysis of polychlorinated biphenyl mixtures by assigning 13C resonances to the observed peaks and matching these shifts to the shifts of known individual polychlorinated biphenyls. The technique has not proved to be as useful for heavily chlorinated mixtures.     

Identification of soil organic phosphorus by 31P nuclear magnetic resonance spectroscopy

Abstract

Soil samples from different land use systems were collected before cropping (in spring) and after harvest (in fall) for organic phosphorus (P) extractions by 0.4M sodium hydroxide (NaOH) and characterization by ³¹P nuclear magnetic resonance spectroscopy. To prevent hydrolysis of organic P compounds prior to sample concentration, NaOH was removed from the NaOH soil extracts using a G‐25 Sephadex column. The ³¹P NMR spectra in the NaOH soil extracts showed the presence of glucose‐6 phosphate (up to 64%), glycerophosphate (up to 45%), nucleoside monophosphates (up to 91%), and polynucleotides (up to 58%) as the major forms of organic P in soils. The relative concentration of nucleoside monophosphates and polynucleotides decreased in some of the soils after harvest. The ³¹P NMR spectra of the extracts also revealed the presence of phosphoenolpyruvates, a previously unreported form of soil organic P.     

Quantitative characterization of a hardwood milled wood lignin by nuclear magnetic resonance spectroscopy

The structure of Eucalyptus grandis milled wood lignin (MWL) was investigated by 2D 1H-13C HSQC, HMQC, and 1H-1H TOCSY correlation NMR techniques and by quantitative 13C NMR as well as by the permanganate oxidation degradation technique. The combination of 2D NMR and quantitative 13C NMR spectroscopy of nonacetylated and acetylated lignin preparations allowed reliable identification and calculation of the amount of different lignin structures. About 85% of side-chain moieties were estimated on the structural level. This information was substantiated by data on the quantity of various functional groups and interunit linkages as a whole. A modified method for calculation of the h:g:s ratio has been suggested and compared with previously suggested approaches. E. grandis MWL has been determined to have an h:g:s ratio of 2:36:62. The amounts of various phenolic/etherified noncondensed/condensed guaiacyl and syringyl moieties were approximately estimated. E. grandis MWL contained approximately 0.60/Ar of beta-O-4 moieties along with small amounts of other structural units such as pino/syringyresinol (0.03/Ar), phenylcoumaran (0.03/Ar), and spirodienone (0.05/Ar). The degree of condensation was estimated at approximately 21%; the main condensed structures are 4-O-5 moieties (approximately 0.09/Ar). The structure of E. grandis MWL was compared with those of other lignin preparations isolated from various hardwoods.     

Oil stability prediction by high-resolution (13)C nuclear magnetic resonance spectroscopy

(13)C NMR spectra of oil fractions obtained chromatographically from 66 vegetable oils were obtained and analyzed to evaluate the potential use of those fractions in predicting oil stabilities and to compare those results with oil stability prediction by using chemical determinations. The oils included the following: virgin olive oils from different cultivars and regions of Europe and north Africa; "lampante" olive, refined olive, refined olive pomace, low-erucic rapeseed, high-oleic sunflower, corn, grapeseed, soybean, and sunflower oils. Oils were analyzed for fatty acid and triacylglycerol composition, as well as for phenol and tocopherol contents. By using stepwise linear regression analysis (SLRA), the chemical determinations and the (13)C NMR data that better explained the oil stability determined by the Rancimat were selected. These selected variables were related to both the susceptibility of the oil to be oxidized and the content of minor components that most contributed to oil stability. Because (13)C NMR considered many more variables than those determined by chemical analysis, the predicted stabilities calculated by using NMR data were always better than those obtained by using chemical determinations. All these results suggest that (13)C NMR may be a powerful tool to predict oil stabilities when applied to chromatographically enriched oil fractions.     

Identification of amino acids in wines by one- and two-dimensional nuclear magnetic resonance spectroscopy

Amino acids are minor compounds in wines, but they have a profound influence on wine quality, and amino acids composition can be used to differentiate wines according to the vine variety, geographical origin, and year of production. The NMR signals of amino acids in NMR spectra are overlapped by the signals of other compounds present and especially by the signals of dominant compounds such as water, ethanol, and glycerol. In this work we used 1D (1)H and (13)C, 2D homonuclear COSY, TOCSY, and 2D heteronuclear HSQC and HMQC pulse sequences, also with an incorporated WET pulse sequence element that allows the simultaneous suppression of several frequencies. Complete (1)H and (13)C NMR assignments for 17 amino acids commonly present in wine and of gamma-aminobutyric acid at pH 3 have been achieved in wine sample of Sauvignon from the Coastal wine-growing region of Slovenia, vintage 1994.     

Study of the compositional changes of mango during ripening by use of nuclear magnetic resonance spectroscopy

Liquid-state NMR spectroscopy was used to follow the compositional changes in mango juice during ripening, whereas MAS and HR-MAS techniques enabled resolved (13)C and (1)H NMR spectra of mango pulps to be recorded. Spectral assignment enabled the identification of several organic acids, amino acids, and other minor components, and the compositional changes upon ripening were followed through the changes in the spectra. In pulps, sucrose was found to predominate over fructose and glucose at most ripening stages, and citric acid content decreased markedly after the initial ripening stages while alanine increased significantly. Other spectral changes reflect the complex biochemistry of mango ripening and enabled the role played by some compounds to be discussed. Some differences observed between the composition of juices and pulps are discussed. This work shows that NMR spectroscopy enables the direct characterization of intact mango pulps, thus allowing the noninvasive study of the overall biochemistry in the whole fruit.     

Metabolic profiling of potential probiotic or synbiotic cheeses by nuclear magnetic resonance (NMR) spectroscopy

To assess ripening of potential probiotic cheeses (containing either Lactobacillus casei -01 or Bifidobacterium lactis B94) or synbiotic cheeses with fructooligosaccharides (FOS) or a 50:50 mix of FOS/inulin, metabolic profiles have been obtained via classical biochemical analyses and by NMR spectroscopy. The addition of prebiotics to the cheeses resulted in lower proteolysis indices, especially in those synbiotic cheeses inoculated with B. lactis B94. Among synbiotic cheeses the combination of FOS and inulin resulted in an increase in lipolytic activity. The metabolic profiles of the cheeses analyzed by NMR spectroscopy, combined with multivariate statistics, allowed profiles to be distinguished by maturation time, added probiotic bacteria, or, in the case of B. lactis B94 cheese, added prebiotic. The NMR results are in agreement with the biochemical analyses and demonstrate the potential of NMR for the study of metabolic processes in probiotic/synbiotic food matrices.     

Characterization of commercial kava-kava herbal drug and herbal drug preparations by means of nuclear magnetic resonance spectroscopy

The efficiency of one- and two-dimensional NMR experiments in characterizing the content of the constituents of both herbal drugs and herbal drug preparations is demonstrated for kava-kava. These experiments directly detect active constituents represented by kavalactones in both a finely powdered herbal drug and a commercial extract. In addition, NMR spectroscopy can detect all other compounds present in the extract. As previously evidenced, NMR experiments can represent a generally applicable technique for rapid screening and are a complement to the classical analytical techniques such as high-performance thin-layer chromatography, high-performance liquid chromatography, capillary gas chromatography, and electrophoresis. These experiments can be considered a very simple and fast analytical method to obtain a fingerprint of the herbal drugs and their preparations, and to quantify the content of the active principles of the extract.     

Determination of nuclear magnetic resonance T2 cutoff in remoulded loess by the freezing point

Proton nuclear magnetic resonance (NMR) is widely applied to characterize the microscopic properties of hydrogen-containing porous media. The transverse relaxation time cutoff (T_2c) value is the crucial parameter for the quantitative analysis of NMR data. Currently, there is no universal method for the determination of the T_2c in clayey soils. This study aimed to develop a laboratory method for determining the T_2c of remoulded loess by the freezing point of loosely bound water. Malan loess, a kind of typical clayey silt, was used as test material. Based on the soil freezing characteristic, NMR measurements were performed on remoulded loess with different macro-parameter controls during the cooling process to obtain the T₂ spectrum at each target temperature. By analysing the variation of unfrozen water content with temperature reduction, the freezing point of loosely bound water and the T_2c value within the freezing-point range was determined. The freezing point of loosely bound water in remoulded loess is about −3 to −5°C and that of firmly bound water is less than −5°C. Accordingly, the T_2c value of remoulded loess is determined to be 1.5–1.8 ms. The assessment of heating and cooling process and different methods for determining the T_2c shows that the laboratory method by the freezing point is effective and reliable, and the T_2c determined by statistical methods is worthy of further study and improvement. The saturated permeability of remoulded loess is evaluated according to the determined T_2c, and two NMR-based permeability equations can well reflect pore water distribution in remoulded loess, but to a certain extent, both equations ignore soil microstructure, pore connectivity and chemical effects of pore solution. The laboratory method by the freezing point and the determined T_2c value of remoulded loess fill the gap of NMR measurement in loess analysis and are of great significance for low-plastic clays and clay types.     

High-resolution nuclear magnetic resonance spectroscopy and multivariate analysis for the characterization of beer

Beer contains a very complex mixture of nutrients, which in this work are identified to some extent by high-field high-resolution nuclear magnetic resonance (NMR) one- and two-dimensional methods. The (1)H NMR spectrum of beer shows a predominance of strongly overlapped peaks arising from several carbohydrates. Minor components are clearly observed both in the aliphatic and in the aromatic regions of the spectrum. With the aid of two-dimensional methods, spectral assignment was carried out, enabling the identification of approximately 30 compounds and identifying about the same number of spin systems for further assignment. The variability of the spectral profile of beers differing in type and label was studied by principal component analysis (PCA), and it was found that, although some distinction is achieved on the basis of the aliphatic and sugar compositions, clearer separation between ales and lagers is obtained by PCA of the aromatic profiles alone. The potential of this technique as a rapid and informative quality control tool is discussed.     

Indirect determination of micrograms of sulfate by barium absorption spectroscopy

Abstract

The indirect procedure for sulfate determination by Ba absorption spectroscopy was modified so that low concentrations of SO₄ in small volumes of solutions could be determined rapidly and precisely. Major modifications consisted of seeding the sample with BaSO₄, precipitating in ethanol solutions to lower BaSO₄ solubility, and determining Ba in a N₂O‐acetylene flame using the absorption mode.

The results showed: complete SO₄ precipitation as BaSO₄ after 15 min of shaking, little or no effect from solution Al on SO₄ determination, quantitative recovery of SO₄ from 0.01 M Ca(H₂PO₄)₂ soil extracts, and greater precision of SO₄ measurement with indirect method than with turbidimetric method.     

Identification of the production chain of Asiago d'Allevo cheese by nuclear magnetic resonance spectroscopy and principal component analysis

In the present work, a rapid and simple NMR method to discriminate Asiago d'Allevo cheese samples from different production chains is described. A fast and reproducible extraction of the organic fraction was employed. By applying chemometric analysis to NMR data, it is possible to differentiate PDO Asiago cheese produced in alpine farms from that produced in lowland and mountain industrialized factories. PCA of both (1)H and (13)C NMR spectra showed a good separation of alpine farm products from the other ones, whereas the lowland and mountain industrialized cheeses are undistinguishable. The samples were differentiated on the basis of a higher content of unsaturated fatty acids, principally oleic, linoleic, linolenic, and conjugated linoleic acids for the alpine farm cheeses and a higher content of saturated fatty acids for the industrialized products. Conjugated linoleic acid and 1-pentene are also discriminating components.     

Analysis of plant complex matrices by use of nuclear magnetic resonance spectroscopy: St. John's wort extract

The efficiency of two-dimensional homonuclear (1)H--(1)H correlated spectroscopy and two-dimensional reverse heteronuclear shift correlation spectroscopy (i.e., heteronuclear multiple quantum correlation) in characterizing and evaluating the relative content of herbal extract constituents is demonstrated. These experiments are able to fully assign the proton and carbon resonances of all three classes of constituents present in dried commercial extract of St. John's wort, that is, flavonols, phloroglucinols, and naphthodianthrones, with particular regard to the very unstable phloroglucinols. In addition, shikimic and chlorogenic acids, sucrose, lipids, polyphenols, and traces of solvents of the extractive process (methanol) were also identified. These experiments can be considered to be a very simple and fast analytical method for determining the quality and stability of the titled commercial extract. They represent a generally applicable technique for a rapid screening and a specific measurement of other commercial phytochemicals or, in selected cases, an alternative to the classical analytical techniques such as high-performance thin-layer chromatography, high-performance liquid chromatography, capillary gas chromatography, and electrophoresis.     

Determination of the composition of gentamicin sulfates by 1H and 13C nuclear magnetic spectroscopy

The British Pharmacopoeia test controlling the composition of gentamicin sulfate is based on CW 60 MHz magnetic resonance spectroscopy. Application of this method to FT 90 MHz spectra was evaluated. Results clearly show the limitations of this technique and point out the need for more reliable assay methods. Thus a 13C nuclear magnetic resonance (NMR) procedure for quantitative analysis of gentamicin sulfate was developed. Ratios of 4 gentamicin components (C1, C2, C1a, and C2a) were obtained from peak height measurements of selected resonance signals in spectra recorded under steady-state conditions. Relative response factors were determined from spectra of a reference mixture or, alternatively, from spectra of the individual pure components. Results obtained by the 13C NMR method were in agreement with those obtained by liquid chromatography using pre-column derivatization.     

Determination of low concentrations of sulfate by nephelometry

Abstract

Several methods for the direct determination of sulfate (SO₄) in aqueous extracts are available but most are not sensitive to low concentrations as may be found in natural waters, soil solutions, or for determining solubilities of sulfur (S) containing minerals. Nephelometry and turbidimetry analyses were undertaken to generate standard curves (0–10 ppm SO₄) in three separate matrices, water (H₂O), lithium chloride (LiCl), and calcium chloride (CaCl₂). For each standard solution of each matrix, nephelometry proved itself to be a superior analytical tool, particularly at SO₄ concentrations less than 4 ppm.     

Determination of refractory organic matter in marine sediments by chemical oxidation, analytical pyrolysis and solid-state 13C nuclear magnetic resonance spectroscopy

Seeking to quantify the amount of refractory organic matter (ROM), which includes black carbon‐like material (BC), in marine sediments, we have applied a two‐step procedure that consists of a chemical oxidation with sodium chlorite of the demineralized sediments followed by integration of the aromatic C region in the remaining residues by solid‐state ¹³C nuclear magnetic resonance (NMR) spectroscopy. The efficacy for lignin removal was tested by analytical pyrolysis in the presence of tetramethyl ammonium hydroxide (TMAH). Riverine, estuarine and offshore marine sediment samples were collected from the southwest Atlantic coast of Spain, a site of geological and environmental interest. Measured contents of BC‐like material ranged between 3.0 and 45.7% of the total organic carbon. Greater relative BC contents were found in riverine sediments close to urban areas, which show an elevated input of anthropogenic organic material. The contents of BC‐like material in offshore marine sediments (5.5–6.1%) were similar to those previously reported for these kinds of samples. However, NMR and pyrolysis‐GC/MS of the isolated ROM reveals that abundant refractory aliphatic organic material remains in most of the marine samples after chlorite oxidation. We suggest that this pool of aliphatic carbon may play an important role as a stable carbon pool within the global C cycle.