Solid-state (13)C CP MAS NMR spectroscopy of mushrooms gives directly the ratio between proteins and polysaccharides

The solid-state (13)C CP MAS NMR technique has the potential of monitoring the chemical composition in the solid state of an intact food sample. This property has been utilized to study mushrooms of different species (Pleurotus ostreatus, Pleurotus eryngii, Pleurotus pulmunarius, and Lentinula edodes), already characterized by chemical analyses for protein and dietary fiber components. Solid-state (13)C CP MAS NMR spectroscopy reveals a large difference in the ratio between the glucidic and the proteic resonances probably depending on the mushroom species. An accurate inspection by model compounds and suitable mixtures of proteins and saccharides gives a methodology to interpret these experimental data. A good correlation (R(2) = 0.93; R(2) = 0.81) has been obtained by comparing the NMR data with the results of the chemical analyses. The results suggest the possibility to perform a taxonomic study and/or a nutritional study on the basis of the ratio between protein and polysaccharide levels determined by NMR or chemical methodologies.     

Characterization of lycopene nanoparticles combining solid-state and suspended-state NMR spectroscopy

The core-shell structure of lycopene micronizates can be verified by employing a combination of solid-state and suspended-state NMR spectroscopy. The type of molecular aggregation of carotenoid nanoparticles can be clearly determined from their characteristic fingerprint pattern in the solid-state NMR spectra.     

Effect of solutes and matrix structure on water mobility in glycerol-agar-water gel systems: a nuclear magnetic resonance approach

Nuclear magnetic resonance spectroscopy (NMR) has been widely used to determine water molecular mobility in food systems. This study aimed to examine the effects of matrix structure and solutes on the dynamics of water molecules in model mixed systems, glycerol-agar-water gels, using low- and high-resolution NMR. Simple models to explain water relaxation rates and self-diffusion coefficients in mixed systems were developed using the experimental values obtained for the individual binary systems (glycerol-water solutions and agar-water gels). The spin-lattice relaxation of mixed systems was influenced by interactions of both glycerol and agar with water, while the spin-spin relaxation of mixed systems was dominated by the interaction of agar with water. Water diffusion was influenced by not only molecular interactions between all components but also the gel matrix structure. These models are able to differentiate the effect of solutes from that of matrix structure on water molecular dynamics.     

Influence of ingredients on the self-diffusion of aroma compounds in a model fruit preparation: an nuclear magnetic resonance-diffusion-ordered spectroscopy investigation

Diffusion-ordered spectroscopy (DOSY)-pulsed field gradient (PGF) nuclear magnetic resonance (NMR) spectroscopy was used to measure self-diffusion coefficients of aroma molecules in model fruit preparations. The impact of the sucrose content on aroma diffusion was specifically investigated, and the relationship with viscosity, water activity, and dry matter parameters was evidenced. DOSY-PGF NMR spectroscopy was found to be a relevant and accurate technique to follow self-diffusion of aroma compounds at low concentrations in a complex food matrix and to obtain information on diffusion of the sucrose and of the water molecules. We showed that aroma self-diffusion was strongly decreased in fruit preparation because of the high sucrose content, which induces the formation of a network through hydrogen bonds with water. Self-diffusion coefficients were determined for aroma molecules of different natures, and values are related to the physicochemical properties of the molecule.     

基于固态13C核磁共振波谱研究植物残体分解和转化机制的进展

植物残体在土壤中的分解和转化影响了其养分归还和有机质形成过程。由于缺乏高分辨率的分析方法,对不同气候、植被和土壤类型条件下植物残体在分解过程中化学结构组成的演变特征和机制仍不清楚。核磁共振波谱技术在解析自然有机物化学组成方面具有独特的优势,本文综述了基于固态~(13)C核磁共振波谱(solid-state ~(13)C-NMR spectroscopy)技术评价植物残体的基质质量、解析植物残体的分解速率及其官能团组成的变化特征、揭示土壤腐殖质特性等方面的主要进展。未来针对植物残体分解和有机质形成机制的研究,应该结合稳定性同位素质谱和扫描电镜分析方法,综合分析植物残体中的有机化合物组成和物理结构;从多时空尺度揭示不同类型植物残体中有机碳官能团的降解路径;结合高通量测序和基因芯片分析方法,深入研究土壤微生物群落与植物残体化学结构的协同演变机制,提出不同气候–土壤–植被类型区促进土壤有机质形成的调控措施。     

Identification of 4,5-didemethyl-4-O-alpha-D-glucopyranosylsimmondsin and pinitol alpha-D-galactosides in jojoba seed meal (Simmondsia chinensis)

The isolation and identification of two pinitol alpha-D-galactosides from jojoba meal are described. The products were isolated by a combination of preparative HPLC on silica gel and TLC on amino silica gel and were identified by MS, NMR spectroscopy, and chemical derivatization as 5-O-(alpha-D-galactopyranosyl)-3-O-methyl-D-chiro-inositol or 5-alpha-D-galactopyranosyl-D-pinitol and 2-O-(alpha-D-galactopyranosyl)-3-O-methyl-D-chiro-inositol or 2-alpha-D-galactopyranosyl-D-pinitol. The same preparative HPLC method on silica gel allowed a new simmondsin derivative to be isolated and identified as 4,5-didemethyl-4-O-alpha-D-glucopyranosylsimmondsin mainly by NMR spectroscopy and high-resolution mass spectrometry.     

C and N NMR spectroscopy as a tool in soil organic matter studies

Nuclear magnetic resonance (NMR) is a valuable tool for the characterization of soil organic matter and humification processes in soils. This review highlights soil organic matter studies based mainly on solid-state ¹³C and ¹⁵N NMR spectroscopy and some emerging applications, that may provide significant progress in our knowledge on soil organic matter. A major advantage of Nmr spectroscopy is that it can be used as a non-invasive method for solid soil samples or soil fractions. Although resolution is limited, one can obtain an overview on the organic matter structures present in the soil sample. Application of ¹³C and ¹⁵N NMR to soils has, for a long time, been confined to the study of bulk soils or humic extracts for structural characterization. The transformations of soil organic C and N are now being investigated after addition of ¹³C- and ¹⁵N-labelled parent materials to the soil and following their evolution in different C and N pools. With labelling techniques it is also possible to study the interaction of organic pollutants with soil organic matter. Contamination of a soil with man-made additives, such as soot or brown coal dust, can also be detected in soils or individual soil fractions.     

Single-sided and semisingle-sided NMR sensors for highly diffusive samples: application to bottled beverages

Single-sided NMR sensors such as the NMR-MOUSE have been very successfully implemented for quality control applications in the rubber and polymer industries. More recently, single-sided NMR was also applied in characterization of the fat components in foods. Both industrial polymers and the fat components in food exhibit relatively low self-diffusion coefficients on the order of 5x10(-11) m2/s or lower. The application of conventional single-sided NMR to highly mobile, watery phases in foods and beverages is hampered by the strong magnetic field gradient present in standard single-sided NMR devices. In this contribution, we present both a single-sided NMR sensor with a reduced magnetic field gradient and another ("semisingle-sided") sensor design with an open sample bay using a single-sided RF coil. The latter design allows much better sensitivity without sacrificing the necessary open access needed for measurements on entire food packages such as bottles. As a first application, the sensors were used for determining the oxygen content in bottles with superoxygenated table water.     

Speciation of aluminum in soil environments

Although aluminum (Al) is abundant in soil environments, it is not an essential element and it is toxic to most organisms. Since the toxicity of Al depends on their chemical forms, the importance of Al speciation has been recognized worldwide. Difficulties in Al speciation are caused by the complex coordination chemistry of Al for the hydrolysis and formation of polynuclear species with a variable degree of solubility in aqueous solution. Nondestructive analyses, such as nuclear magnetic resonance (NMR) spectroscopy, could supply primarily im-portant information on the chemical forms of Al and may enable to evaluate the results ob-tained by other methodologies. In the present report, NMR spectral characteristics of environmentally important Al-containing components, such as hydoxyaluminum ions, Alinorganic complexes, Al-organic complexes, and primary and secondary minerals, are summarized for the nuclei of ²⁷Al and ²⁹Si determined by solution NMR and solid-state magic angle spinning (MAS) NMR. Applications of NMR techniques to soil science, including speciation of phytotoxic Al in soil environments and whole soil NMR studies, are described.     

Characterization of Compost Leachate Fractions Using NMR Spectroscopy

A distilled water leachate was prepared from a hardwood-leaf compost. The ¹³C NMR (nuclear magnetic resonance) spectra of organic acids isolates from this leachate provided support for the hypothesis that the composition of the dissolved organic carbon (DOC) in the leachate is very similar to that in natural soil pore waters. The leachate DOC was adsorbed by a model mineral surface, and the organic coating on the surface was characterized by solid-state ¹³C NMR spectroscopy.     

Soil organic matter transformations induced by Hieracium pilosella L. in tussock grassland of New Zealand

 To study the effect of Hieracium pilosella L. invasion on the transformations of soil organic matter of New Zealand tussock grassland soils (Ustochrepts), plant material and soils underneath Hieracium, the surrounding halo, and the adjacent herbfield (depleted tussock grassland) were examined for their chemical composition. An attempt was made to reveal possible changes in chemical composition of the soil organic matter induced by H. pilosella invasion. Small differences were detected by solid-state ¹³C nuclear magnetic resonance (NMR) spectroscopy in the composition of the plant and soil materials from these zones. Most of the differences in soil organic matter occurred due to differences in the amount and quality of plant-residue inputs. Comparable amounts of phenolic C were detected in the solid-state ¹³C NMR spectra of H. pilosella and herbfield vegetation, while alkaline CuO oxidation yielded considerable lower lignin oxidation products for H. pilosella. A slightly higher proportion of these compounds in H. pilosella soil revealed an accumulation and a low degradation rate of lignin compounds under H. pilosella. The HCl hydrolysis and solid-state ¹⁵N NMR spectroscopy showed similar chemical compositions of the N fractions of the three different soils. The absence of ¹⁵N NMR signal intensity assignable to aniline derivatives or aromatic heterocyclic N indicates that the condensation of phenolic compounds with N groups plays a minor role in N sequestration in these soils. Received: 6 September 1999     

腐熟鸡粪和农业废弃物堆肥中的芳香结构抑制了水芹种子和哈茨木霉的生长

To better understand the role of organic matter （OM） prepared from chicken manure and agriculture residues compost on the growth of plants （Lepidium sativum L.） and antagonistic fungi （Trichoderma harzianum）, we analyzed the structure and composition of extracted OM using fluorescence excitation-emission matrix （EEM） spectroscopy and solid-state 13C cross-polarization magic-angle- spinning nuclear magnetic resonance （13C CPMAS NMR） spectroscopy. The results showed that the EEM contours of water-extracted OM （WEOM） and alkali-extracted OM （AEOM） were similar. Furthermore, solid-state 13C CPMAS NMR spectroscopy demonstrated that water extraction could not proportionally pull out aromatic moieties （112-145 ppm） from compost, but the alkali method in proportion extracted both carbohydrates （65 85 ppm） and aromatic moieties. The results suggest that AEOM may better reflect the bulk OM composition of compost, and one should be cautious when applying WEOM as an alternative indicator of total compost OM. Further investigations demonstrated that, compared to carbohydrates, aromatic moieties played a predominant role in growth suppression of Lepidium sativum L. seeds and Trichoderma harzianum.     

High-resolution NMR and diffusion-ordered spectroscopy of port wine

The use of high-resolution NMR and high-resolution diffusion-ordered spectroscopy (DOSY) for the characterization of selected Port wine samples of different ages with the aim of identifying changes in composition is described. Conventional 1D and 2D NMR methods enabled the identification of about 35 compounds, including minor components such as some medium-chain alcohols, amino acids, and organic acids. High-resolution (HR) DOSY extended sample characterization, increasing the number of compounds identified and NMR assignments made, by providing information on the relative molecular sizes of the metabolites present. Port wines of different ages were found to differ mainly in their content of (a) organic acids and some amino acids, (b) an unidentified possible disaccharide, and (c) large aromatic species. The relative amount of these last high Mw aromatics is seen to decrease significantly in the oldest wine, as expected from the known formation and precipitation of anthocyanin-based polymers during red wine aging.     

Differences between lignin in unprocessed wood, milled wood, mutant wood, and extracted lignin detected by 13C solid-state NMR

Solid-state 13C nuclear magnetic resonance (NMR) spectroscopy was applied to intact and isolated loblolly pine wood samples to identify potential structural changes induced by tree age, milling, lignin extraction, or naturally occurring mutations. Special attention was paid to ketone and aldehyde as well as nonpolar alkyl groups, which could be observed at low concentrations (<2 in 1000 C) using improved spinning-sideband suppression with gated decoupling. Carbonyl structures were present in intact wood, and there are more keto groups than aldehydes. Their concentrations increased from juvenile to mature wood and with milling time, whereas extraction did not alter the C=O fraction. Significant amounts of aldehyde and dihydroconiferyl alcohol residues were present in coniferyl aldehyde dehydrogenase-deficient wood, confirming solution-state NMR spectra of the corresponding lignin. These results demonstrate the utility of solid-state NMR as an assay for changes in the lignin structure of genetically modified plants.     

Solid-state 15N NMR studies of tobacco leaves

Nitrogen-containing compounds are one important class of constituents in tobacco because of various pharmacological and biological properties. Three types of tobacco leaves (burley, bright, and oriental) were studied using solid-state (15)N NMR cross polarization with magic-angle spinning, dipolar dephasing and five pi replicated magic angle turning (FIREMAT) experiments. The results show that burley tobacco leaves contain significantly more pyridinic nitrogen than that of bright or oriental tobacco leaves. The principal values of (15)N chemical shift tensors of nitrogen functional groups were obtained from the FIREMAT data. Possible assignments of solid-state (15)N NMR resonances were made using nitrogen chemical shift tensors in some model compounds or isotropic chemical shift values from liquid NMR results. To the best of our knowledge, this is the first solid-state (15)N NMR study of tobacco plant material.     

Microwave‐Assisted Rapid Modification of Zein by Octenyl Succinic Anhydride

Corn is one of the most important food and industrial crops in the United States. Zein constitutes about half of the endosperm proteins in corn. Potential applications of zein include use in fibers, adhesives, inks, cosmetics, textiles, and chewing gum. Recently, attempts have been made to utilize zein for food coatings and biodegradable materials. The new applications of zein require it to be resistant to water. Thus, we are interested in new routes for chemical modification of zein (Biswas et al, unpublished). 2‐Octenyl succinic anhydride (OSA) is extensively used in modifying food starches. Our objective was to take advantage of OSA hydophobicity, flexibility, and compatibility with nonpolar groups and incorporate OSA onto zein. This OSA‐modified zein would possess the best of both OSA and zein. A zein solution in dimethyl formamide (DMF) was reacted with various levels of OSA to give modified zein. In a microwave reactor, the reactions proceeded tremendously fast and they were over in 5 min. The anhydride group of OSA reacted with the hydroxyl/amine group of zein to form ester/amide of zein. The reaction of OSA‐modified zein was confirmed by proton nuclear magnetic resonance (NMR) and IR spectroscopy. The preliminary evaluation showed that zein and OSA‐modified zein had comparable mechanical properties.     

New bioactive biomaterials based on quaternized chitosan

Chitosan was chemically modified to produce quaternary ammonium salts in order to improve its antimicrobial activity and physicochemical properties. Quaternization of N-alkyl chitosan derivatives was carried out using alkyl iodide to elaborate water-soluble cationic polyelectrolytes ( N, N, N-trimethylchitosan, TMC). TMC was characterized by (1)H NMR spectroscopy; the quaternization degree was determined from (1)H NMR spectra and by titration of iodide ion. The antibacterial activity of hydroxypropylcellulose (HPC) films or coatings associated with chitosan or TMC as biocide was evaluated against the growth of Listeria monocytogenes and Salmonella typhimurium. The HPC-chitosan and HPC-TMC coatings exhibited a total inhibition on solid medium of both bacterial strains. Experiments conducted in liquid medium showed that the inhibitory activity against the growth of Listeria innocua was improved after chemical modification. Moreover, physicochemical properties of films were evaluated to determine their potential for food applications. The addition of the antibacterial agents showed a significant impact on the moisture barrier and mechanical properties of HPC films.     

New analogues of (E)-β-farnesene with insecticidal activity and binding affinity to aphid odorant-binding proteins

(E)-β-farnesene is a strong and efficient alarm pheromone in most aphid species. However, applications in agriculture are prevented by its relatively high volatility, its susceptibility to oxidation and its complex and expensive synthesis. To develop novel compounds for aphid control, we have designed and synthesized analogues of (E)-β-farnesene, containing a pyrazole moiety present in several insecticides. Their structures have been confirmed by 1H NMR, elemental analysis, high-resolution mass spectroscopy and IR. Binding activities to three odorant-binding proteins (OBPs) of the pea aphid Acythosiphon pisum have been evaluated and correlated with their structures with reference to (E)-β-farnesene. Several derivatives were shown both to bind to A. pisum OBPs with a specificity similar to that of (E)-β-farnesene and to have aphicidal activity comparable to that of thiacloprid, a commercial insecticide. The compounds synthesized in this work represent new potential agents for aphid population control and provide guidelines to design analogues of (E)-β-farnesene endowed with both insecticidal and repellent activity for aphids.     

Relationship between the glass transition of soy protein and molecular structure

The change in molecular structure of the soy protein samples as a result of the microbial transglutaminase treatment was studied using solid-state (13)C NMR spectroscopy and circular dichroism (CD), and the relation to the glass transition temperature (T(g)) was examined. From NMR measurements, the structure of the local region of the C(alpha) methine was observed to change, and the region had relatively high mobility. From CD measurements, the structural change seemed to be caused by the change in the secondary structure (disintegration of the beta-structure). By comparison with the T(g) of another protein, the state of the secondary structure of a protein was suggested to be a key in determining its T(g).     

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.