Fatty Acid Profiles of Virgin Olive Oils from the Five Olive-Growing Zones of Extremadura (Spain)

In this study, 278 samples of virgin olive oil from 40 mills belonging to five olive-growing zones of Extremadura were evaluated according to their fatty acid composition. An analysis of variance of the fatty acid contents, and their principal group subtotals and ratios revealed significant differences at the 95 % confidence level between zones. Means were compared using Tukey’s HSD test (p < 0.05). A discriminant analysis, taking the zone as the grouping variable and the different fatty acids and their ratios as independent variables, explained nearly 90 % of the variance with the first two functions. The model correctly classified 88.8 % of the analysed samples into their proper olive-growing zone. Validation against an extra test set of 30 samples resulted in 90 % being correctly classified; the results of the discriminant analysis were therefore considered to be validated. A two-dimensional graphical representation of the different groups studied using the first two resulting canonical discriminant functions clearly showed the Sierra Norte of Cáceres and Vegas del Guadiana each to be clearly separated from the rest and from each other, while the other three zones—Siberia, Serena and Tierra de Barros—overlapped considerably.     

Detection of Extra Virgin Olive Oil Adulteration With Edible Oils Using Front‐Face Fluorescence and Visible Spectroscopies

Synchronous front‐face fluorescence and visible spectroscopies are utilized for the simple, rapid, and nondestructive quantification of extra virgin olive oil (EVOO) adulteration with corn, soybean, and sunflower oils. For each adulterant, 42 adulterated EVOO samples in the adulterant amount in the range 1.0–50 g/100 g were prepared. The partial‐least‐squares regression was executed for quantification. Both full (leave‐one‐out) cross‐validation and external validation were performed to evaluate the predictive ability. The plots of observed vs. predicted values exhibit high linearity. The coefficient of determination (R²) values are larger than 0.99. The root mean square errors of both cross‐validation and prediction are no more than 2%. The detection limits for the three seed oils using fluorescence and visible spectroscopies are in the range of 1.5–2.2% and 1.8–2.4%, respectively. The merit of this method is that both the front‐face fluorescence and visible spectroscopies are recorded toward neat oils, avoiding any sample pretreatment including dilution.     

Detection of Argan Oil Adulteration Using Quantitative Campesterol GC-Analysis

Detection of edible oil adulteration is of utmost important to ensure product quality and customer protection. Campesterol, a sterol found in seed oils, represents less than 0.4% of argan oil total sterol content. Quantitative analysis of campesterol by gas chromatography of argan oil and of a mixture of argan oil and readily commercially available vegetable oils, consecutively with sterol separation, was carried out. Our study clearly demonstrated that determination of the campesterol level in argan oil (or oil presented as argan oil) can be proposed as the major analysis method to assess unambiguously argan oil purity up to 98%.     

Characterization of sacha inchi (<Emphasis Type="Italic">Plukenetia volubilis</Emphasis> L.) oil by FTIR spectroscopy and <Superscript>1</Superscript>H NMR. Comparison with linseed oil

Three oil samples obtained from sacha inchi (Plukenetia volubilis L.) seeds were studied by means of FTIR and ¹H NMR. Frequency data of the most significant bands of the IR spectrum of this oil are given. These data show that sacha inchi oil has a high degree of unsaturation. The same fact is deduced from the ratio between the absorbance of the bands due to the stretching vibrations of the cis olefinic CH double bonds at 3010.5 cm⁻¹ and to the methylene symmetrical stretching vibrations at 2855.1 cm⁻¹. The proportions of monounsaturated, polyunsaturated, and saturated acyl groups were predicted from the frequency of some IR bands, and these were in satisfactory agreement with the values obtained through FAME generation and their quantification by GC. Likewise, simple observation of the ¹H NMR spectra provided a great deal of information about sacha inchi oil, with regard not only to the relative proportions of the different acyl groups but also to their nature. Thus, the presence of γ-linolenic acyl groups was discounted. Furthermore, the area of some ¹H NMR signals was used to determine the proportion of saturated and mono-, di-, and triunsaturated acyl groups, which also were in satisfactory agreement with the values obtained by classical methods. IR and ¹H NMR determinations take very little time in comparison with classical methods and do not require chemical manipulation or transformation of the sample. A comparison was also made between the compositions of sacha inchi and linseed oil. Both oils are important sources of the healthful n−3 linolenic acyl groups, and sacha inchi also contains high proportions of the n−6 linoleic acyl groups.     

Determination of benzene and total aromatics in commercial gasolines using packed column GC and NMR techniques

A simple, accurate and rapid method has been developed for the estimation of benzene and total aromatics (0.5-50% w/w) including heavier aromatics (C₈, C₉, and C₁₀) in commercial gasoline using packed column GC and NMR techniques. The benzene content can be estimated as low as 0.1% w/w. The response of a flame ionisation detector (FID) to each major aromatic group in gasoline was calculated using internal standard. The results have been compared with the NMR and standard ASTM D5580 methods. The limitations of NMR and GC techniques for the estimation of total aromatics particularly in reformulated gasoline containing oxygenates have been discussed and attempts have been made to overcome problems associated with the analysis. The results obtained by both the techniques for a number of commercial gasoline samples containing olefins or free of olefins received from different refineries processing variety of crudes using different refining technologies have shown excellent correlation. The ¹H NMR method has a wider scope, convenient and fast, and also applicable to heavier naphtha. The method can routinely be adopted for the quality control of commercial gasoline at refinery as well as marketing terminals for monitoring benzene and total aromatic content. The time consumption for single run using gas chromatographic technique is approximately 35 min.     

Miscibility and morphology of chiral semicrystalline poly‐(R)‐(3‐hydroxybutyrate)/chitosan and poly‐(R)‐(3‐hydroxybutyrate‐co‐3‐hydroxyvalerate)/chitosan blends studied with DSC, 1H T1 and T1ρ CRAMPS

The phase structure of poly‐(R)‐(3‐hydroxybutyrate) (PHB)/chitosan and poly‐(R)‐(3‐hydroxybutyrate‐co‐3‐hydroxyvalerate) (P(HB‐co‐HV))/chitosan blends were studied with ¹H CRAMPS (combined rotation and multiple pulse spectroscopy). ¹H T₁ was measured with a modified BR24 sequence that yielded an intensity decay to zero mode rather than the traditional inversion‐recovery mode. ¹H T_1ρ was measured with a 40‐kHz spin‐lock pulse inserted between the initial 90° pulse and the BR24 pulse train. The chemical shift scale is referenced to the methyl group of PHB as 1.27 ppm relative to tetramethylsilane (TMS) based on ¹H liquid NMR of PHB. Single exponential T₁ decay is observed for the β‐hydrogen of PHB or P(HB‐co‐HV) at 5.4 ppm and for the chitosan at 3.7 ppm. T₁ values of the blends are either faster than or intermediate to those of the plain polymers. The T_1ρ decay of β‐hydrogen is bi‐exponential. The slow T_1ρ decay component is interpreted as the crystalline phase of PHB or P(HB‐co‐HV). The degree of crystallinity decreases with increasing wt % of chitosan in the blend. The fast T_1ρ of β‐hydrogen and the T_1ρ of chitosan in the blends either follow the same trend as or faster than the weight‐averaged values based on the T_1ρ of the plain polymers. Together with the observation by differential scanning calorimeter (DSC) of a melting point depression and one effective glass transition temperature in the blends, the experimental evidence strongly suggests that chitosan is miscible with either PHB or P(HB‐co‐HV) at all compositions. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 1253–1258, 2002     

Discrimination of Cod Liver Oil According to Wild/Farmed and Geographical Origins by GC and <Superscript>13</Superscript>C NMR

The objective of this study was to test the possibility of using lipid profiles obtained by gas chromatography (GC) and ¹³C nuclear magnetic resonance (NMR) in authentication of cod liver oils according to wild/farmed and geographical origin. GC and ¹³C-NMR data of cod liver oil from wild and farmed fish from different locations in Norway and Scotland were obtained, and analyzed by principal component analysis (PCA) and linear discriminant analysis (LDA) to test if it was possible to differentiate oil from wild and cultured cod (Gadus morhua L.), and to further elucidate differences between fish from the different farms/catch area. Cod liver oils of wild and farmed origin were clearly separated in the PCA score plot both from GC and NMR data. From NMR data it was also possible to observe groupings based on geographical origin (farm/catch area) of the different samples. Using LDA with cross validation the wild/farmed classification rates were 97% for GC data and 100% for NMR data. In the classification of cod liver oils according to geographical origin (38 samples from six different farms/catch area), the correct classification rate was 63% for GC data and 95% for NMR data.     

Study of Ozonated Sunflower Oil Using 1H NMR and Microbiological Analysis

Prior studies have proven that ozonated vegetable oils present a high germicidal power. Ozonation of sunflower oil at different applied ozone dosage was carried out and peroxide and aldehydes indices along with antimicrobial activity were determined. The reaction products were identified using Proton Nuclear Magnetic Resonance Spectroscopy (¹H NMR). The principal signals intensity values were used for following the reaction course between ozone and sunflower oil. The reaction was following up to peroxide index values of 1202 mmol-equi/kg. The intensities of olefinic proton signals decreased with the gradual increase in ozone concentration but without disappearing completely. The Criegee ozonides obtained at 107.1 mg/g of ozone doses were approximately 3.9-fold higher than that at beginning of the reaction. The aldehyde protons were observed as a weak intensity signal in all the spectra. The signals belonging to olefinic protons from hydroperoxides appeared weak and increased with the increase in ozone doses. Signals from other oxygenated groups were assigned. The highest action spectrum of antimicrobial activity was obtained with the higher peroxide index. It was concluded that at higher applied ozone doses, the higher the antimicrobial activity potential of ozonized sunflower oil     

Sequence analysis of poly(ethylene/1,4-cyclohexanedimethylene terephthalate) copolymer using H and C NMR

The triad-level sequence analysis of poly(ethylene/1,4-cyclohexanedimethylene terephthalate) copolymer was reported in a solvent system of o-chlorophenol/deuterated chloroform mixture (50/50 v/v) at 80 °C using 600 MHz ¹H NMR. The well-resolved alcoholic CH₂ proton peak of the glycol units was observed, which made the detailed sequence analysis possible. The peaks of the cis- and trans-forms of the 1,4-cyclohexanedimethylene glycol units were split into the triad sequence in the chain and could be assigned by a comparison of the spectra with those of homopolymers and by an additional two-dimensional heteronuclear multiple bond correlation observation. The triad sequence distributions centered on 1,4-cyclohexanedimethylene glycol units were determined, which was independent of the cis- and trans-forms of the units and controlled according to Bernoullian statistics.     

Solid-state nuclear magnetic resonance (NMR): Application to precursors of ceramics—Polycarbosilane

The chemical structures of oxidation- and electron irradiation-cured polycarbosilane fibers has been studied by IR and chemical analysis, but its structure has not been identified in detail. In this work, the chemical structure and curing mechanism was examined by solid-state high-resolution NMR spectroscopy. From the analysis of NMR spectra, it is explained that (i) in oxidation curing of PCS fibers, oxygen attacks first the SiC₃H bond and forms the SiC₃O bond and, next, the SiC₄ backbone bond and forms the SiC₂O₂ units; (ii) in electron irradiation curing, the signal intensity of SiC₃H units decreases with the increase in dose, the increase in the signal being due to the formation of SiC₄ units; (iii) solid-state²⁹Si high-resolution (CP/MAS) NMR spectroscopy is a powerful tool for investigating the chemical structure and curing mechanism of PCS fibers complementing infrared and solid-state¹³C high-resolution NMR spectroscopy; and (iv)¹H CRAMPS NMR spectroscopy is very useful for investigating the chemical structure and curing mechanism of PCS fibers.     

Copolymerization of norbornene with ethylene: A high-resolution liquid NMR, DSC and solid state NMR study

In this paper, we report the monomer reactivity on the copolymerization of norbornene and ethylene. The reactivity ratios for ethylene (M₁) and norbornene (M₂) are 18.5 and 0.035, respectively. Different copolymerization conditions can produce COC with different microstructures. A ¹³C NMR shift assignment in pentad sequences in copolymers has been obtained. More isolated polynorbornene or a micro-block length can be obtained using a low Zr/Al catalyst/co-catalyst ratio and at a lower NB/ethylene feed ratio. The T_1p ^C decay curve shows two component decays in all resonance peaks. These two component decays come from different norbornene microstructures, while the block and alternative have similar T_1p ^C values.     

Simultaneous Structural Identification of Natural Products in Fractions of Crude Extract of the Rare Endangered Plant Anoectochilus roxburghii Using H NMR/RRLC-MS Parallel Dynamic Spectroscopy

Nuclear magnetic resonance/liquid chromatography-mass spectroscopy parallel dynamic spectroscopy (NMR/LC-MS PDS) is a method aimed at the simultaneous structural identification of natural products in complex mixtures. In this study, the method is illustrated with respect to (1)H NMR and rapid resolution liquid chromatography-mass spectroscopy (RRLC-MS) data, acquired from the crude extract of Anoectochilus roxburghii, which was separated into a series of fractions with the concentration of constituent dynamic variation using reversed-phase preparative chromatography. Through fraction ranges and intensity changing profiles in (1)H NMR/RRLC-MS PDS spectrum, (1)H NMR and the extracted ion chromatogram (XIC) signals deriving from the same individual constituent, were correlated due to the signal amplitude co-variation resulting from the concentration variation of constituents in a series of incompletely separated fractions. 1H NMR/RRLC-MS PDS was then successfully used to identify three types of natural products, including eight flavonoids, four organic acids and p-hydroxybenzaldehyde, five of which have not previously been reported in Anoectochilus roxburghii. In addition, two groups of co-eluted compounds were successfully identified. The results prove that this approach should be of benefit in the unequivocal structural determination of a variety of classes of compounds from extremely complex mixtures, such as herbs and biological samples, which will lead to improved efficiency in the identification of new potential lead compounds.     

NMR investigation of the miscibility of new antiplasticizers in densely cross-linked epoxy-amine resins

The behaviour of antiplasticized epoxy-amine networks was investigated by variable-temperature determinations of ¹H NMR free induction decays. Up to 50 °C, all antiplasticized resins exhibited a solid-like behaviour. At higher temperatures, resins containing the less polar additives were shown to be phase-separated, in contrast to systems containing polar additives. The temperature dependence of the phase composition of the resins, as detected by NMR, supports the conclusions previously deduced from the dynamic mechanical analysis (DMA) study: non- or slightly-polar antiplasticizer molecules are sharply phase-separated in highly cross-linked epoxy-amine networks cured extensively. The resulting morphology mainly consists in nano-scale aggregates of additives entrapped within the polymer matrix.     

Quantification of soybean oil ethanolysis with <Superscript>1</Superscript>H NMR

In this study, proton NMR spectroscopy (200 MHz) was used for quantifying the content of ethyl esters in known mixtures of soybean oil and ethyl soyate (biodiesel). For this purpose, the peak areas of ester ethoxy and glycerol methylenic peaks in the region of 4.05–4.40 ppm were measured and a calibration plot of the respective peak areas vs. the known composition of the oil/ethyl ester mixtures was used. The transesterification values determined in this way were compared with viscosity and total glycerol determinations and a good correlation was obtained. Therefore, for routine analysis, the conversion (in %) of oil to ethyl esters was determined. The methodology presented in this work proved to be quicker and simpler than others reported in the literature, such as GC and/or HPLC.     

Quality control of gasoline by H NMR: Aromatics, olefinics, paraffinics, and oxygenated and benzene contents

A simple and fast ¹H NMR method, without any pretreatment, was developed for quality control of gasoline. It is based on the average group molecular weight approach and relative-content concept involving aromatics, olefinics and paraffinics, including also ethanol and benzene contents. The ethanol content was evaluated for Brazilian samples, but the method can be easily adapted to any oxygenated compound (ex. MTBE), and to gasoline from other countries. Twenty two laboratory prepared gasoline samples (gasoline from Brazilian refineries plus hydrocarbon solvents) and thirty four real (i.e., Brazilian gas stations) gasoline samples were tested. The routine quality control carried out through the usual physicochemical analyses reached a level of confidence of 75% and 73% in detecting non conformity in laboratory and real gasoline samples, respectively. The NMR method was very superior reaching 100% and 97% of confidence, respectively. It was better suited for laboratories with high sample throughput since measurement time is short and only one NMR experiment is needed per sample.     

Synthesis of dimer and oligomers from (R)-methyl hydnocarpate

We report synthesis and characterization of dimer and oligomer acids from chaulmoogra oil. (R)-Methyl hydnocarpate (methyl ester of the major fatty acid component of chaulmoogra oil) was brominated to give threo-2,3-dibromocyclopentane-1-methyl undecanoate. Formation of two diastereoisomers, viz., threo-2(R),3(R)-dibromocyclopentane-1(R)-methyl undecanoate and threo-2(S),3(S)-dibromocyclopentane-(R)-1-methyl undecanoate, was observed. Dehydrobromination of bromo derivatives using alcoholic KOH gave a cyclopentadiene derivative as intermediate, which underwent Diels-Alder reaction to give dimer and oligomer fatty acids. The products were characterized by ultraviolet, direct exposure probe-mass spectroscopy, ¹H nuclear magnetic resonance (NMR), and ¹³C NMR spectroscopic techniques.     

Determination of Methemoglobin in Hemoglobin Submicron Particles Using NMR Relaxometry

Methemoglobin (MetHb) is a hemoglobin (Hb) derivative with the heme iron in ferric state (Fe³⁺), unable to deliver oxygen. Quantification of methemoglobin is a very important diagnostic parameter in hypoxia. Recently, novel hemoglobin microparticles (Hb-MP) with a narrow size distribution around 700 nm, consisting of cross-linked Hb were proposed as artificial oxygen carriers. The cross-linking of Hb by glutaraldehyde (GA) generates a certain amount of MetHb. Due to the strong light scattering, quantitative determination of MetHb in Hb-MP suspensions by common spectrophotometry is not possible. Here, we demonstrate that ¹H₂O NMR relaxometry is a perfect tool for direct measurement of total Hb and MetHb concentrations in Hb-MP samples. The longitudinal relaxation rate 1/T₁ shows a linear increase with increasing MetHb concentration, whereas the transverse relaxation rate 1/T₂ linearly increases with the total Hb concentration. In both linear regressions the determination coefficient (R²) is higher than 0.99. The method does not require time-consuming pretreatment or digestion of the particles and is not impaired by light scattering. Therefore, it can be established as the method of choice for the quality control of Hb-MP and similar hemoglobin-based oxygen carriers in the future.     

Effect of time on the hydration and temperature-induced phase separation in aqueous polymer solutions. H NMR study

Dehydration during temperature-induced phase separation in D₂O solutions of poly(vinyl methyl ether) (PVME), poly(N-isopropylmethacrylamide) (PIPMAm) and poly(N-isopropylacrylamide) (PIPAAm) was followed from time dependences of NMR spin-spin relaxation times T₂ of HDO. Both the time characterizing the exclusion of the water from mesoglobules (manifested by the increase in T₂ values) and the induction period which precedes the increase in T₂ values, increased in the order PVME < PIPMAm < PIPAAm. For D₂O solutions of PIPMAm/PVME (or PIPMAm/PIPAAm) mixtures a direct connection between the state of the mesoglobules (hydrated or dehydrated) formed by the component with lower LCST (PVME, PIPAAm) and the temperatures of the phase transition of the PIPMAm component was established by NMR spectroscopy.     

Identification, FT-IR, NMR (H and C) and GC/MS studies of fatty acid methyl esters in biodiesel from rocket seed oil

Biodiesel was synthesized from rocket seed oil by base-catalyzed transesterification with methanol. The synthesis of biodiesel was confirmed by FT-IR and NMR (¹H and ¹³C) spectroscopy. Various fuel properties of the synthesized biodiesel were determined using ASTM methods and discussed accordingly. A total of eleven fatty acid methyl esters (FAMEs) were identified in rocket seed oil biodiesel (RSOB) by the retention time and the fragmentation pattern data of GC/MS analysis. The identified FAMEs were, methyl 9-hexadecenoate (C16:1), 14-methyl pentadecanoate (C16:0), methyl 9,12-octadecadienoate (C18:2), methyl 9-octadecenoate (C18:1), methyl octadecanoate (C18:0), methyl 11-eicosenoate (C20:1), methyl eicosanoate (C20:0), methyl 13-docosenoate (C22:1), methyl docosanoate (C22:0), methyl 15-tetracosenoate (24:1) and methyl tetracosanoate (C24:0). The percentage conversion of triglycerides to corresponding methyl esters determined by ¹H NMR was 88.49%.