New (1)h NMR procedure for the characterization of native and modified food-grade starches

A novel, fast, and straightforward procedure is presented for the characterization of starch (the largest energy component in food) and modified starches (such as octenyl succinic anhydride (OSA)-modified starches used as a dispersing agent in the food industry). The method uses (1)H NMR to measure the degree of branching and also, for modified starches, the degree of chemical substitution. The substrate is dissolved in dimethyl-d(6) sulfoxide; addition of a very low amount of deuterated trifluoroacetic acid (d(1)-TFA) to the medium gives rise to a shift to high frequency of the exchangeable protons of the starch hydroxyl groups, leading to a clear and well-defined (1)H NMR spectrum, which provides an improved way to determine the degrees of both branching and chemical substitution. Measurements of the size and molecular weight distributions by multiple-detector size exclusion chromatography show that degradation by TFA does not affect the accuracy of the method.     

Two-dimensional 1H-13C nuclear magnetic resonance (NMR)-based comprehensive analysis of roasted coffee bean extract

Coffee was characterized by proton and carbon nuclear magnetic resonance (NMR) spectroscopy. To identify the coffee components, a detailed and approximately 90% signal assignment was carried out using various two-dimensional NMR spectra and a spiking method, in which authentic compounds were added to the roasted coffee bean extract (RCBE) sample. A total of 24 coffee components, including 5 polysaccharide units, 3 stereoisomers of chlorogenic acids, and 2 stereoisomers of quinic acids, were identified with the NMR spectra of RCBE. On the basis of the signal assignment, state analyses were further launched for the metal ion-citrate complexes and caffeine-chlorogenate complexes. On the basis of the signal integration, the coffee components were successfully quantified. This NMR methodology yielded detailed information on RCBE using only a single observation and provides a systemic approach for the analysis of other complex mixtures.     

Multielement analysis of Canadian wines by inductively coupled plasma mass spectrometry (ICP-MS) and multivariate statistics

Trace element fingerprints were deciphered for wines from Canada's two major wine-producing regions, the Okanagan Valley and the Niagara Peninsula, for the purpose of examining differences in wine element composition with region of origin and identifying elements important to determining provenance. Analysis by ICP-MS allowed simultaneous determination of 34 trace elements in wine (Li, Be, Mg, Al, P, Cl, Ca, Ti, V, Mn, Fe, Co, Ni, Cu, Zn, As, Se, Br, Rb, Sr, Mo, Ag, Cd, Sb, I, Cs, Ba, La, Ce, Tl, Pb, Bi, Th, and U) at low levels of detection, and patterns in trace element concentrations were deciphered by multivariate statistical analysis. The two regions were discriminated with 100% accuracy using 10 of these elements. Differences in soil chemistry between the Niagara and Okanagan vineyards were evident, without a good correlation between soil and wine composition. The element Sr was found to be a good indicator of provenance and has been reported in fingerprinting studies of other regions.     

Metabolite profiling using (1)H NMR spectroscopy for quality assessment of green tea, Camellia sinensis (L.)

A set of 191 green teas from different countries was collected and analyzed by (1)H NMR. It was proposed to establish if the teas could be discriminated according to the country of origin or with respect to quality. Both principal component analysis (PCA) and cluster analysis were applied to the data. Some separation of Chinese and non-Chinese teas was observed. The present results did not allow allocation of samples to individual countries, but cluster analysis suggested that it might be possible with an augmented sample set. The PCA did show a separation between the Longjing type (highest quality Chinese tea) and most other Chinese teas and indicated some metabolites that could be responsible for the difference. Longjing teas showed higher levels of theanine, gallic acid, caffeine, epigallocatechin gallate, and epicatechin gallate and lower levels of epigallocatechin when compared with other teas. These compounds have been mentioned previously in connection with quality, but it was also shown that higher levels of theogallin (5-galloyl quinic acid), theobromine, 2-O-(beta-l-arabinopyranosyl)-myo-inositol and some minor sugar-containing compounds were found in Longjing teas while higher levels of fatty acids and sucrose were found in the other teas. These new markers could prove to be useful for the authentication of bulk tea.     

Bioactive compounds in cod (Gadus morhua) products and suitability of 1H NMR metabolite profiling for classification of the products using multivariate data analyses

This work investigates the suitability of (1)H NMR spectroscopy to identify the fate of some bioactive compounds in seafood submitted to several processing conditions and examines the possibility of using (1)H NMR spectroscopy profiling to classify such products. Perchloric acid extracts of cod white muscle from newly killed and (i) unprocessed, (ii) boiled, and (iii) fried fillets and from (iv) frozen fillets, (v) the frozen fillets after thawing, and (vi) their drip loss and from (vii) rehydrated cod klippfish (n = 5) were analyzed by 500 MHz (1)H NMR spectroscopy. It was possible to identify taurine, betaine, anserine, creatine, and trimethylamine oxide (TMAO) in all extracts examined, and frozen fish was recognizable by the presence of dimethylamine (DMA). None of the heating procedures seemed to induce the loss of bioactive compounds from the fillet, but freezing and thawing did: the compounds were lost in what is known as drip loss. About 80% of the samples were correctly classified using a probabilistic neural network procedure having as inputs the scores of the first 20 principal components of the principal component analysis of a selected region of the NMR spectra.     

Multiple compound quality index for cold-smoked salmon (Salmo salar) developed by multivariate regression of biogenic amines and pH

Production of biogenic amines during chill storage of 12 lots of cold-smoked salmon was studied. These data allowed for a multiple compound quality index to be developed by multivariate regression (partial least square regression). The quality index was based on concentrations of cadaverine, histamine, putrescine, and tyramine and pH and showed good correlation with sensory assessments. Biogenic amines were indicators of spoilage rather than casual agents of spoilage off-flavors. Four different biogenic amine profiles were found at the time of spoilage in cold-smoked salmon. These were the results of differences in the spoilage microflora. Histamine was detected above regulatory limits but below toxic levels. Measurements of salt and dry matter for calculation of water phase salt could be substituted by rapid water activity measurements.     

Multivariate analysis of NMR and FTIR data as a potential tool for the quality control of beer

In this work, principal component analysis (PCA) is applied to the FTIR-ATR and the (1)H NMR spectra of 50 beers differing in label and type (ale, lager, alcohol-free), to identify the spectral parameters that may provide rapid information about factors affecting beer production. PCA of FTIR data resulted in the separation of beers mainly according to their alcoholic content, providing little information on components other than ethanol contributing to the variability within the samples. PCA of (1)H NMR spectra, performed on the region where major beer components resonate (3.0-6.0 ppm), resulted in the separation of samples into four groups: two groups characterized by the predominance of dextrins, one group of alcohol-free beers characterized by the predominance of maltose, and one group where glucose was found to predominate. By performing PCA on aliphatic and aromatic regions, the contribution of minor components was highlighted. In particular, most ales, lagers, and alcohol-free samples could be distinguished based on their aromatic composition, thus reflecting the high sensitivity of the low-field NMR region toward different types of beer fermentation.     

GC-FID- and acyl carbon number-based determination of characteristic groupings of complex triglyceride (Benefat S and other) mixtures

Techniques for the gas and liquid chromatographic separation of complex mixtures of triglycerides have evolved over the past two decades, as reviewed in detail by Huang et al. (J. Agric. Food Chem. 1995, 43, 1834-1844; J. Agric. Food Chem. 1997, 45, 1770-1778). A novel method for the quantitative partitioning of complex mixtures of triglycerides into functionally related groups is developed and applied to a low-calorie triglyceride mixture [namely, Benefat S or Salatrim plus mid-chain (C(6,8,10,12)) fatty acids]. The method is based on a nonlinear calibration of retention times (RTs) of a suite of standard triglycerides on their acyl carbon numbers [(ACNs), the sum of all the acyl carbon atoms in a given triglyceride] to estimate all of the intermediate ACNs (from 6 to 66). With the calibrated ACN scale and identifications of some components of a complex mixture's composition, ACN-based partitions were established and a Benefat S-triglyceride chromatogram was partitioned into seven functionally related groups. This method is provisional in the sense that it would typically be employed when the identifications of many components of a complex, homologous series were unknown, yet functionally related groups needed to be quantified. This method has proven to be particularly useful in the intercalibration of research laboratories with production facility laboratories during complex ( approximately 50-90 compounds) and large-scale ( approximately 20 ton) syntheses because of the high reproducibility of the ACN-based partitioning of complex chromatograms. This carbon number and statistically based method can be generally applicable to other complex mixtures of organic compounds and is readily adaptable to laboratory intercalibration efforts.     

Caffeine and resistance of coffee to the berry borer Hypothenemus hampei (Coleoptera: Scolytidae)

The role of caffeine as a chemical defense of coffee against the berry borer Hypothenemus hampei was investigated. No positive correlation was observed between resistance and caffeine content in experiments in which seeds from several coffee species presenting genetic variability for the alkaloid were exposed to adult insects. The same was observed in an experiment with coffee seeds that had their caffeine content doubled by imbibition with caffeine aqueous solutions. Other experiments showed that the attractiveness to insects was not related to the caffeine content of mature fruits. These results indicate that H. hampei has evolved an adaptation to handle the toxic effects of caffeine.     

Water distribution in brine salted cod (Gadus morhua) and salmon (Salmo salar): a low-field 1H NMR study

Low-field (LF) (1)H NMR T 2 relaxation measurements were used to study changes in water distribution in lean (Atlantic cod) and fatty (Atlantic salmon) fish during salting in 15% NaCl and 25% NaCl brines. The NMR data were treated by PCA, continuous distribution analysis, and biexponential fitting and compared with physicochemical data. Two main water pools were observed in unsalted fish, T 21, with relaxation times in the range 20-100 ms, and T 22, with relaxation times in the range 100-300 ms. Pronounced changes in T 2 relaxation data were observed during salting, revealing changes in the water properties. Salting in 15% brine lead to a shift toward longer relaxation times, reflecting increased water mobility, whereas, salting in saturated brines had the opposite effect. Water mobility changes were observed earlier in the salting process for cod compared to salmon. Good linear correlations ( F 相似文献   

1H NMR metabolite fingerprint and pattern recognition of mullet (Mugil cephalus) bottarga

Nuclear magnetic resonance (NMR) spectroscopy combined with multivariate data analysis (MVA) was used to investigate the molecular components of the aqueous extract of samples of bottarga, that is, salted and dried mullet (Mugil cephalus) roe, manufactured in Sardinia (Italy) from mullets of known and unknown geographical provenience. Principal component analysis (PCA) applied to the processed (1)H NMR spectra indicated that samples tend to cluster according to their geographical origin and also on the basis of storage and manufacturing procedures. The most important metabolites that characterized grouping of samples are the free amino acids methionine (Met), glutamate (Glu), histidine (His), phenylalanine (Phe), tyrosine (Tyr), and isoleucine (Ile); trimethylamine (TMA) and dimethylamine (DMA), both biomarkers of degradation; nucleotides and derivatives; choline (Cho) and phosphorylcholine (P-cho); and lactate (Lac).     

Volatile composition of coffee berries at different stages of ripeness and their possible attraction to the coffee berry borer Hypothenemus hampei (Coleoptera: Curculionidae)

The analysis of volatile emissions of coffee berries in different physiological states of ripeness was performed using dynamic headspace and gas chromatography/mass spectrometry analysis for Coffea arabica, var. Colombia. The composition of the volatiles emitted by coffee berries is dominated by very high levels of alcohols, mainly ethanol, in all stages of ripeness in comparison with other compounds. Overripe coffee berries have high volatile emissions and show a composition dominated mainly by esters followed by alcohols, ketones, and aldehydes. The lowest level compounds were monoterpenes. 2-Methyl furan was detected in various ripening stages; this compound has not been previously reported as a coffee berry volatile. The presence of ethanol and other alcohols in the volatile composition might explain the effectiveness of using traps with mixed alcohols for detection and capture of coffee berry borers.     

Application of cryoprobe 1H nuclear magnetic resonance spectroscopy and multivariate analysis for the verification of corsican honey

Proton nuclear magnetic resonance spectroscopy ((1)H NMR) and multivariate analysis techniques have been used to classify honey into two groups by geographical origin. Honey from Corsica (Miel de Corse) was used as an example of a protected designation of origin product. Mathematical models were constructed to determine the feasibility of distinguishing between honey from Corsica and that from other geographical locations in Europe, using (1)H NMR spectroscopy. Honey from 10 different regions within five countries was analyzed. (1)H NMR spectra were used as input variables for projection to latent structures (PLS) followed by linear discriminant analysis (LDA) and genetic programming (GP). Models were generated using three methods, PLS-LDA, two-stage GP, and a combination of PLS and GP (PLS-GP). The PLS-GP model used variables selected by PLS for subsequent GP calculations. All models were generated using Venetian blind cross-validation. Overall classification rates for the discrimination of Corsican and non-Corsican honey of 75.8, 94.5, and 96.2% were determined using PLS-LDA, two-stage GP, and PLS-GP, respectively. The variables utilized by PLS-GP were related to their (1)H NMR chemical shifts, and this led to the identification of trigonelline in honey for the first time.     

Pathways for the hydrolysis of phorate: product studies by (31)P NMR and GC-MS

A new intramolecular mechanism is proposed for the hydrolysis of phorate. (31)P NMR was used to study the formation of P-containing products of phorate hydrolysis in situ. When hydrolysis was followed by (31)P NMR, a dominant P-containing product was found and was identified to be diethyl dithiophosphate using methylation and GC-MS. Combining the data from phorate hydrolysis at three different temperatures, thermodynamic parameters were calculated. The contributions of various possible pathways to phorate hydrolysis are discussed.     

1-MCP和壳聚糖处理保持红枣贮藏品质及其机理研究

以新疆灰枣为试材,研究纸片型1-甲基环丙烯(1-methylcyclopropene,1-MCP)与壳聚糖(chitosan,COS)处理在(0±1)℃条件下对灰枣品质及相关酶活性的影响。结果表明:至贮藏90 d时,与对照(CK)相比,1-MCP+COS的腐烂率、失质量率分别降低53.4%、51.2%,可溶性固形物(total soluble solid, TSS)含量高出18.6%。抗氧化酶系统中的超氧化物歧化酶(superoxide dismutase, SOD)峰值水平提高58.2%,过氧化氢酶(catalase, CAT)峰值高出34.8%;贮藏结束时过氧化物酶(peroxidase, POD)活性是CK的1.98倍,抗坏血酸过氧化物酶(ascorbate peroxidase, APX)活性高出51.7%,差异显著(P0.05)。1-MCP、COS及1-MCP+COS处理均可不同程度地降低果实腐烂率、失质量率,保持较高的果实硬度和TSS含量,推迟呼吸高峰和乙烯释放速率高峰的到来并抑制丙二醛(malondialdehyde,MDA)的积累,抑制脂氧合酶(lipoxygenase, LOX)和多酚氧化酶(polyphenol oxidase, PPO)活性,显著提高抗氧化酶系统活性。其中1.50μL/L纸片型1-MCP与1%COS复合处理对保持果实贮藏品质、延缓果实衰老、延长货架期最有利。     

1-MCP和壳聚糖处理保持红枣贮藏品质及其机理研究

以新疆灰枣为试材,研究纸片型1-甲基环丙烯（1-methylcyclopropene,1-MCP）与壳聚糖（chitosan,COS）处理在（0±1）℃条件下对灰枣品质及相关酶活性的影响。结果表明：至贮藏90 d时,与对照（CK）相比,1-MCP＋COS的腐烂率、失质量率分别降低53.4%、51.2%,可溶性固形物（total soluble solid, TSS）含量高出18.6%。抗氧化酶系统中的超氧化物歧化酶（superoxide dismutase, SOD）峰值水平提高58.2%,过氧化氢酶（catalase, CAT）峰值高出34.8%;贮藏结束时过氧化物酶（peroxidase, POD）活性是CK的1.98倍,抗坏血酸过氧化物酶（ascorbate peroxidase, APX）活性高出51.7%,差异显著（P＜0.05）。1-MCP、COS及1-MCP+COS处理均可不同程度地降低果实腐烂率、失质量率,保持较高的果实硬度和TSS含量,推迟呼吸高峰和乙烯释放速率高峰的到来并抑制丙二醛（malondialdehyde, MDA）的积累,抑制脂氧合酶（lipoxygenase, LOX）和多酚氧化酶（polyphenol oxidase, PPO）活性,显著提高抗氧化酶系统活性。其中1.50 μL/L纸片型1-MCP与1% COS复合处理对保持果实贮藏品质、延缓果实衰老、延长货架期最有利。     

Characterization of lignin structures and lignin-carbohydrate complex (LCC) linkages by quantitative 13C and 2D HSQC NMR spectroscopy

To characterize the lignin structures and lignin-carbohydrate complex (LCC) linkages, milled wood lignin (MWL) and mild acidolysis lignin (MAL) with a high content of associated carbohydrates were sequentially isolated from ball-milled poplar wood. Quantification of their structural features has been achieved by using a combination of quantitative (13)C and 2D HSQC NMR techniques. The results showed that acetylated 4-O-methylgluconoxylan is the main carbohydrate associated with lignins, and acetyl groups frequently acylate the C2 and C3 positions. MWL and MAL exhibited similar structural features. The main substructures were β-O-4' aryl ether, resinol, and phenylcoumaran, and their abundances per 100 Ar units changed from 41.5 to 43.3, from 14.6 to 12.7, and from 3.7 to 4.0, respectively. The S/G ratios were estimated to be 1.57 and 1.62 for MWL and MAL, respectively. Phenyl glycoside and benzyl ether LCC linkages were clearly quantified, whereas the amount of γ-ester LCC linkages was ambiguous for quantification.     

Application of (31)P NMR spectroscopy in food analysis. 1. Quantitative determination of the mono- and diglyceride composition of olive oils

This paper introduces a facile method to determine the amount of mono- and diglycerides in virgin olive oils. This method is based on the phosphorylation of the free hydroxyls of the mono- and diglycerides with 2-chloro-4,4,5,5-tetramethyldioxaphospholane and the integration of the appropriate peaks in the (31)P NMR spectrum. Quantitative (31)P NMR spectroscopy can be extended to the quantification of other constituents of olive oils bearing functional groups with labile protons.     

Comparison of analytical methodologies based on 1h and 31p NMR spectroscopy with conventional methods of analysis for the determination of some olive oil constituents

The present study was designed to assess the agreement between analytical methodologies based on 1H and 31P NMR spectroscopy and conventional analytical methods (titration, gas chromatography, and high performance liquid chromatography) for measuring certain minor and major constituents (free acidity, fatty acids, iodine value, and phenolic compounds) of olive oil. The standard deviations of the NMR method were comparable to those of the conventional methods, except perhaps those of the total hydroxytyrosol and total tyrosol. Linear regression analyses showed strong correlations between NMR and conventional methods for free acidity, total hydroxytyrosol, total tyrosol, total diacylglycerols, (+)-pinoresinol, (+)-1-acetoxypinoresinol, and apigenin; good correlations for linoleic acid, free hydroxytyrosol, and free tyrosol; and weak correlations for oleic acid, linolenic acid, saturated fatty acids, and luteolin. Furthermore, a method comparison study was conducted and the agreement between NMR and conventional methods was evaluated by using the Bland and Altman statistical analysis. The distribution of the data points in the bias plot showed that 96.4% and 100% of the measurements of free acidity and iodine value, respectively, were within the limits of agreement of the two methods. For the remaining constituents of olive oil, the percentage of measurements, located within the limits of agreement, ranged from 94% to 98.5%.     

Quantification of kavalactones and determination of kava (Piper methysticum) chemotypes using near-infrared reflectance spectroscopy for quality control in vanuatu

Kava ( Piper methysticum Forst f., Piperaceae) has anxiolytic properties and the ability to promote a state of relaxation without the loss of mental alertness. The rapid growth of the nutraceutical market between 1998 and 2000 has been stopped by a ban in Europe and Australia because of some suspicion of liver toxicity. It is now important to develop a fast, cheap, and reliable quality test to control kava exports. The aim of this study is to develop a calibration of the near-infrared reflectance spectroscopy (NIRS) using partial least-squares (PLS) regression. Two hundred thirty-six samples of kava roots, stumps, and basal stems were collected from the Vanuatu Agricultural Research and Technical Centre germplasm collection and from four villages. These samples, representing 45 different varieties, were analyzed using NIRS to record their absorption spectra between 400 and 2500 nm. A set of 101 selected samples was analyzed for their kavalactone content using HPLC. The results were used for PLS calibration of the NIRS. The NIRS prediction of the kavalactone content and the dry matter were in agreement with the HPLC results. There were good correlations between these two series of results, and coefficients ( R (2)) were all close to 1. The measurements were reproducible and had repeatability on par with the HPLC method. The NIRS system has been calibrated for the six major kavalactone content measurements, and it is suggested that this method could be used for quality control in Vanuatu.