An Intricate Review on Nutritional and Analytical Profiling of Coconut,Flaxseed, Olive,and Sunflower Oil Blends

Vegetable oils (VOs), being our major dietary fat source, play a vital role in nourishment. Different VOs have highly contrasting fatty acid (FA) profiles and hence possess varying levels of health protectiveness. Consumption of a single VO cannot meet the recommended allowances of various FA either from saturated FA (SFA), monounsaturated FA (MUFA), polyunsaturated FA (PUFA), Ω-3 PUFAs, and medium-chain triglycerides (MCTs). Coconut oil (CO), flaxseed oil (FO), olive oil (OO), and sunflower oil (SFO) are among the top listed contrast VOs that are highly appreciated based on their rich contents of SFAs, Ω-3 PUFAs, MUFAs, and Ω-6 PUFA, respectively. Besides being protective against various disease biomarkers, these contrasting VOs are still inappropriate when consumed alone in 100% of daily fat recommendations. This review compiles the available data on blending of such contrasting VOs into single tailored blended oil (BO) with suitable FA composition to meet the recommended levels of SFA, MUFA, PUFA, MCTs, and Ω-3 to Ω-6 PUFA ratios which could ultimately serve as a cost-effective dietary intervention towards the health protectiveness and improvement of the whole population in general. The blending of any two or more VOs from CO, FO, OO, and SFO in the form of binary, ternary, or another type of blending was found to be very conclusive towards balancing FA composition; enhancing physiochemical and stability properties; and promising the therapeutic protectiveness of the resultant BOs.     

Fatty acid profile of different species of algae of the Cystoseira genus: a nutraceutical perspective

The fatty acid (FA) composition of six macroalgae from the Cystoseira genus, namely Cystoseira compressa, Cystoseira humilis, Cystoseira tamariscifolia, Cystoseira nodicaulis, Cystoseira baccata and Cystoseira barbata, was determined. Polyunsaturated fatty acids (PUFA) corresponded to 29–46% of the total FA detected. C. compressa, C. tamariscifolia and C. nodicaulis stood out for their low PUFA/saturated fatty acid, low n-6 PUFA/n-3 PUFA ratios as well as favourable unsaturation, atherogenicity and thrombogenicity indices, suggesting a high nutritional value with potential applications in the nutraceutical industry.     

Hemp Seeds of the Polish ‘Bialobrzeskie’ and ‘Henola’ Varieties (Cannabis sativa L. var. sativa) as Prospective Plant Sources for Food Production

This publication characterizes the nutritional value of the Polish hemp seeds of the ‘Bialobrzeskie’ and ‘Henola’ varieties, including the profile/content of fatty acids and amino acids. Hemp seeds were found to be rich in protein, fat, and dietary fiber. Polyunsaturated fatty acids (PUFA) dominated the unsaturated fatty acids (UFA) profile. Their average share within the total fatty acids (FA) was as high as 75%. Linoleic acid belonging to this group accounted for 55% of the total FA. Lipid profile indices (Σ n − 6/Σ n − 3, Σ PUFA/Σ SFA, the thrombogenicity index, the atherogenicity index and the hypocholesterolemic/hypercholesterolemic ratio) proved the high nutritional value of hemp oil. Considering the tyrosine + phenylalanine and histidine contents, hemp protein exhibited a great degree of similarity to egg protein, which is known and valued for its high biological value.     

Properties of Ozone-Oxidized Tapioca Starch and Its Use in Coating of Fried Peanuts

Oxidation of tapioca via ozone oxidation was carried out under different conditions in comparison with H₂O₂. The impact of ozonation on physicochemical properties of tapioca was studied and fried peanuts coated with different tapioca were characterized. Different ozone oxidation times (10, 20, and 30 min) and various pH values (5, 7, and 9) were used for tapioca modification. Tapioca oxidized by ozone for 20 min at pH 7 had higher swelling power (SP), water holding capacity (WHC), oil holding capacity (OHC), and viscosity than the native counterpart (P < 0.05). This coincided with the higher carbonyl and carboxyl contents (P < 0.05). The highest frying expansion (FE) with the lowest hardness was attained for fried peanut coated with tapioca oxidized under the aforementioned condition. Therefore, oxidation of tapioca using ozone under optimal conditions could be a potential means to improve frying expansion as well as the crispiness of the fried coated peanuts.     

SKIN PERMEATION ENHANCEMENT BY FATTY ACIDS

The present study elucidates the skin permeation enhancement effects of a number of fatty acids, i.e. straight-chain saturated (SFA), monounsaturated (MUFA) and polyunsaturated acids (PUFA). The effects were studied using human stratum corneum (SC) and p-aminobenzoic acid (PABA) as a model permeant. The fatty acids in propylene glycol (FA/PG) were applied according to a pre-treatment/co-treatment protocol. SFA with 6 to 12 carbons exhibit a parabolic correlation between enhancement effect and chain-length, with a maximum at nonanoic-decanoic acids (with 9 and 10 carbons). All cis-6-, 9-, 11- or 13-octadecenoic acids (MUFA) enhance the permeation of PABA to the same extent. PUFA — linoleic (LA), α-linolenic (ALA) and arachidonic acids — enhance PABA permeation stronger than MUFA but additional double bonds do not further increase the degree of enhancement. The enhancement effects of fatty acids on the PABA penetration through SC are structure-dependent, associated with the existence of a balance between the permeability of pure fatty acids across SC and the interaction of the acids to skin lipids. Based on this and other studies, a set of mechanisms of action is proposed for fatty acids.     

Study of the Seasonal Variations of the Fatty Acid Profiles of Selected Macroalgae

Due to the high consumption of fat-rich processed foods, efforts are being done to reduce their saturated fat (SFA) contents and replace it with polyunsaturated fatty acids (PUFA), creating a necessity to find alternative PUFA sources. Macroalgae, being a promising natural source of healthy food, may be such an alternative. The fatty acid (FA) profile of Fucus spiralis, Bifurcaria bifurcata, Ulva lactuca, and Saccorhiza polyschides were determined through direct transesterification and their seasonal variation was studied. F. spiralis showed the highest FA content overall, B. bifurcata presented the higher PUFA amounts, and U. lactuca and S. polyschides the higher SFA. The production of FA was shown to be influenced by the seasons. Spring and summer seemed to induce the FA production in F. spiralis and B. bifurcata while in U. lactuca the same was verified in winter. U. lactuca presented a ω6/ω3 ratio between 0.59 and 1.38 while B. bifurcata presented a ratio around 1.31. The study on the seasonal variations of the macroalgal FA profile can be helpful to understand the best season to yield FA of interest, such as ALA, EPA, and DHA. It may also provide valuable information on the best culturing conditions for the production of desired FAs.     

Marine macroalgae analyzed by mass spectrometry are rich sources of polyunsaturated fatty acids

Algae from cold water (Canada) and warm water (China) were analyzed for their total lipid content, and for their fatty acid (FA) composition and content. The major findings are that FA from Canadian algae are generally richer in polyunsaturated FA (PUFA), with a higher n-3/n-6 FA ratio, and a higher degree of total unsaturation. The 18 C, 4 double bonds FA (18 : 4 stearidonic acid, morotic acid as synonym) was detected in greater amounts in cold water samples. The high levels of total PUFA, and especially of n-3 FA in Canadian algae, suggests their possible utilizations for nutritional purposes.     

Electronic spectra of α,β-unsaturated carbonyl compounds—II : An evaluation of increments characteristic of structural features of β-oxy-α,β-unsaturated ketones

By comparing UV spectra of β-alkoxy-α,β-unsaturated ketones of established steric structure, spectral constants characteristic of the cis/trans configuration change and s-cis/s-trans and O-s-cis/O-s-trans conformation changes have been evaluated. These are: Δλ^cis_trans = 0, Δλ^s-cis_s-trans = 8 nm and Δλ^O-s-trans_O-s-cis = 6 nm. A comparison of cis-s-cis enol ethers with the parent enols yielded the increment for the intramolecular (“chelating”) H-bond, Δγ_chel = 24 nm. The methanol-induced bathochromic shift has been found to depend strongly on s-cis/s-trans isomerism. The substituent increments have been shown to be dependent on the degree of substitution in the reference molecule. The results obtained have been summarized in a set of spectral increments complementing the basic system of Woodward and the Fiesers.     

激光共聚焦显微拉曼快速测定食用调和油脂肪酸

目的:采用激光共聚焦显微拉曼光谱技术快速测定食用调和油饱和脂肪酸(Saturated fatty acids,SFA)、单不饱和脂肪酸(Monounsaturated fatty acids,MUFA)和多不饱和脂肪酸(Polyunsaturated fatty acids,PUFA)含量及比例。方法:通过导数预处理净化拉曼光谱信息,采用偏最小二乘法建立优化后的SFA、MUFA、PUFA的拉曼定量预测模型,为计算脂肪酸比例提供准确的数据基础。结果:SFA、MUFA和PUFA定量分析模型的决定系数R2均大于0.99,相对分析误差RPD均大于3,表明模型具有较高的稳定性和良好的预测能力。结论:激光拉曼光谱法结合化学计量学方法可以快速、准确地测定食用调和油SFA、MUFA、PUFA含量及比例,为快速检测食用调和油品质提供切实可行的检测手段。     

Chemometric Analysis of Fatty Acid Composition of Raw Chicken,Beef, and Pork Meat with Plant Extract Addition during Refrigerated Storage

During the shelf-life, meat undergoes a number of processes that negatively affect the quality of the product, including fatty acid composition. The application of various plant extracts in meat could affect the changes of fatty acids during storage. Thus, the aim of this study was to investigate the effect of various spice and herb extracts on fatty acid composition in raw pork, beef, and chicken meat when stored at 4 °C for 13 days. Based on multivariate statistical analysis, two datasets were extracted from each type of meat. One dataset included samples with allspice, bay leaf, black seed, cardamom, caraway, clove, and nutmeg with the high share of total MUFA (monounsaturated fatty acids) in chicken and pork meat and high MUFA and PUFA (polyunsaturated fatty acids) contribution in beef meat after storage. The second dataset included basil, garlic, onion, oregano, rosemary, and thyme with high PUFA share in chicken and pork meat and high SFA (saturated fatty acids) contribution in beef meat. From the regression analysis, a significant effect of time on fatty acid composition in meat was reported. Generally, the rates of fatty acid changes were dependent on the plant extract incorporated into the meat. The most visible effect of plant extracts was obtained in chicken meat. In chicken meat with plant extracts, the rates of SFA and PUFA changes with time were slower compared to the control sample. In summary, the fatty acid composition of intramuscular fat varied during storage, and the addition of plant extracts significantly affected the rate of these changes, which was dependent on the meat matrix.     

A complete evaluation of thermal and oxidative stability of chia oil

Chia (Salvia hispanica L.) seed oil is the richest natural source of α-linolenic acid, an n ? 3 polyunsaturated fatty acid (ω-3 PUFA), contributing to its use as functional and nutraceutical food in large part of Latin America. However, a food with such fatty acid composition could be highly susceptible to lipid oxidation. Thus, the present study was conducted to determine the thermal and oxidative stability of chia oil by various methods. Rancimat method was used to evaluate the effect of synthetic and natural antioxidants in the oxidative stability. Pressurized differential scanning calorimetry (PDSC), Schaal test and ¹H NMR spectroscopy were used to assess the thermal stability. The effect of frying temperature and/or heating time on fatty acid composition was assessed by ¹H NMR. The results show that tert-butylhydroquinone (TBHQ) and a mixture of TBHQ and rosemary extract were effective in increasing the oxidative stability of chia oil. Concerning the storage conditions, PDSC, Schaal test and ¹H NMR data showed that chia oil is stable at 60 °C; hence, there is no need for special storage conditions. PDSC and ¹H NMR results indicate that chia oil cannot be used in cooking and frying, because at high temperatures severe degradation of the unsaturated groups and loss of the nutritional properties of the oil occur.     

Investigation of folic acid stability in fortified instant noodles by use of capillary electrophoresis and reversed-phase high performance liquid chromatography

A single enzyme treatment with alpha-amylase, prior to the quantification of added folic acid (FA) in fortified instant fried Asian noodles with analysis performed by capillary zone electrophoresis (CZE) and reversed-phase high performance liquid chromatography (RP-HPLC) with UV detection, is described. The method was validated and optimized for capillary electrophoresis (CE) with separation achieved using a 8 mM phosphate-12 mM borate run buffer with 5% MeOH at pH 9.5. FA was well separated from matrix components with nicotinic acid (NA) employed as an internal standard. In a comparative study, separation of FA was performed using HPLC with a mobile phase consisting of 27% MeOH (v/v) in aqueous potassium phosphate buffer (3.5 mM KH(2)PO(4) and 3.2 mM K(2)HPO(4)), pH 8.5, and containing 5 mM tetrabutylammonium dihydrogen phosphate as an ion-pairing agent. For both methods, excellent results were obtained for various analytical parameters including linearity, accuracy and precision. The limit of detection was calculated to be 2.2 mg/L for CE without sample stacking and 0.10 mg/L with high performance liquid chromatography (HPLC). Sample extraction involved homogenization and enzymatic extraction with alpha-amylase. Results indicated that FA was stable during four main stages of instant fried noodle manufacturing (dough crumbs, cut sheets, steaming and frying).     

Determination of fatty acid compositions and cholesterol levels of some freshwater fish living in Porsuk Dam,Turkey

We determined the oil content, fatty acid composition, and cholesterol content of common carp (Cyprinus carpio), crucian carp (Carassius carassius), chub (Leusiscus cephalus), and tench (Tinca tinca) by GLC. The saturated fatty acids (SFA), monounsaturated fatty acids (MUFA), and polyunsaturated fatty acids (PUFA) levels were found to be 36.49%, 31.92%, 31.59% in common carp; 32.92%, 32.21%, and 34.87% in crucian carp; 36.19%, 32.91%, and 30.90% in chub; and 32.86%, 30.77%, and 36.37% in tench, respectively. The cholesterol (mg/100 g oil) levels of common carp, crucian carp, chub, and tench were determined by GLC methods as 119 ± 2.64 mg, 170.37 ± 2.36 mg, 94.68 ± 3.13 mg, and 179.84 ± 6.75 mg, respectively. Thus, the cholesterol contents of the analyzed freshwater fish species were low but their PUFA contents and nutritional values were high. Published in Khimiya Prirodnykh Soedinenii, No. 1, pp. 15–17, January–February, 2009.     

Conformational analysis,barriers to internal rotation,vibrational assignment and ab initio calculations of chloroacetone

The infrared (3500-20 cm⁻¹) and Raman (3200-10 cm⁻¹) spectra have been recorded for gaseous and solid chloroacetone (1-chloro-2-propanone), CH₂ClC(O)CH₃. Additionally, the Raman spectrum of the liquid has been recorded and qualitative depolarization values have been obtained. These data have been interpreted on the basis that the molecule exists predominantly in a gauche conformation having a “near cis” structure of C₁ symmetry (dih ClCCO=142°C) in the vapor but for the liquid a second conformer having a trans structure (chlorine atom oriented trans to the methyl group) with C_s point group symmetry is present. From a study of the Raman spectrum of the liquid at variable temperatures, the trans conformation has been determined to be more stable than the gauche form by 1042±203 cm⁻¹ (2.98±0.6 kcal mol⁻¹ and is the only conformer present in the spectrum of the annealed solid. From ab initio calculations at the 3-21G* and 6-31G* basis set levels optimized geometries for both the gauche and trans conformers have been obtained and the potential surfaces governing internal rotation of the symmetric and asymmetric rotors have been obtained. The observed vibrational frequencies and assignments to the fundamental vibrations for both the gauche and trans conformers are compared to those calculated with the 3-21G* basis set. The results are discussed and compared with the corresponding quantities obtained for some similar molecules.     

Conformational analysis,barriers to internal rotation,ab initio calculations and vibrational assignment of fluoroacetone

The infrared (3500-20 cm⁻¹) and Raman (3200-10 cm⁻¹) spectra have been recorded for gaseous and solid fluoroacetone (1-fluoro-2-propanone), CH₂FC(O)CH₃. Additionally, the Raman spectrum of the liquid has been recorded and qualitative depolarization values have been obtained. These data have been interpreted on the basis that the molecule exists predominantly in the cis (fluorine atom oriented cis to the methyl group) conformation in the vapor but for the liquid a second conformer having a trans orientation (fluorine atom oriented trans to the methyl group) is present. From a study of the Raman spectrum of the liquid at variable temperatures the trans conformation has been determined to be more stable than the cis form by 416 ± 54 cm⁻¹ (1.19 ± 0.15 kcal mol⁻¹) and is the only conformation present in the spectrum of the annealed solid. The asymmetric torsional fundamental for the more stable cis conformer has been observed in the far infrared spectrum of the gas at 69.6 cm⁻¹ with six accompanying hot band transitions proceeding to lower frequency. The corresponding mode for the high energy trans conformer is extensively overlapped but is distinguishable at ∼65 cm⁻¹. From these data the asymmetric torsional potential function governing internal rotation about the CC bond has been determined and the potential coefficients are: V₁ = 675 ± 2, V₂ = 991 ± 5, V₃ = 74 ± 1 and V₄ = 54 ± 2 cm⁻¹. The cis to trans and trans to cis barriers are 1332 ± 5 and 731 ± 5 cm⁻¹, respectively, with an enthalpy difference of 601 ± 8 cm⁻¹ (1.72 ± 0.02 kcal mol⁻¹). From ab initio calculations at the 3-21G and 6-31G* basis set levels optimized geometries for both the cis and trans conformers have been obtained and the potential surface governing internal rotation of the asymmetric top determined. The observed vibrational frequencies with their assignments for both the cis and trans conformers are compared to those from the ab initio calculations. All of these results are compared to the corresponding quantities for some similar molecules.     

Simple Methodology for the Quantitative Analysis of Fatty Acids in Human Red Blood Cells

In the last years, there has been an increasing interest in evaluating possible relations between fatty acid (FA) patterns and the risk for chronic diseases. Due to the long life span (120 days) of red blood cells (RBCs), their FA profile reflects a longer term dietary intake and was recently suggested to be used as an appropriate biomarker to investigate correlations between FA metabolism and diseases. Therefore, the aim of this work was to develop and validate a simple and fast methodology for the quantification of a broad range of FAs in RBCs using gas chromatography with flame ionization detector, as a more common and affordable equipment suitable for biomedical and nutritional studies including a large number of samples. For this purpose, different sample preparation protocols were tested and compared, including a classic two-step method (Folch method) with modifications and different one-step methods, in which lipid extraction and derivatization were performed simultaneously. For the one-step methods, different methylation periods and the inclusion of a saponification reaction were evaluated. Differences in absolute FA concentrations were observed among the tested methods, in particular for some metabolically relevant FAs such as trans elaidic acid and eicosapentaenoic acid. The one-step method with saponification and 60 min of methylation time was selected since it allowed the identification of a higher number of FAs, and was further submitted to in-house validation. The proposed methodology provides a simple, fast and accurate tool to quantitatively analyse FAs in human RBCs, useful for clinical and nutritional studies.     

Evaluation of poly(L-lactic acid) (PLLA) rapid indicator film on deterioration degree of Refined,Bleached and Deodorised Malaysian Tenera palm olein oil (RBDPO) during long-term repetitive deep-fat frying

Palm olein oil is widely used as a medium for deep-frying purposes in the domestic and commercial sectors. However, repetitive usage beyond the recommended cycle leads to significant deterioration and spoilage of the oil. Therefore, this research investigated the effect of long-term repetitive deep-fat frying on the physicochemical properties of Refined, Bleached and Deodorised Malaysian Tenera Palm Olein oil (RBDPO) as well as the suitability of poly(L-lactic acid) (PLLA) film as a potential rapid indicator to determine the spoilage level of recycled palm olein oil. The study was carried out using three different RBDPO conditions; RBDPO without potatoes (RBDPO-1), RBDPO with potatoes (RBDPO-2), and RBDPO with Afdhal Oil (AO, an oil additive chemical) and potatoes (RBDPO-3). The deep-frying process was performed for 15 mins at 180 ± 5 °C for 15 cycles. Based on the results, the oil temperature fluctuation during the frying process was insignificant for every cycle (p > 0.05). After 15 frying cycles, all oil samples demonstrated a considerably altered and deteriorated composition, both physically and chemically. The comparison between the 1st and 15th frying cycles showed a significant difference (p < 0.05) in the decrease of moisture content and contact angle. Furthermore, the redness colour and viscosity for RBDPO-1, RBDPO-2 and RBDPO-3 increased significantly. The RBDPO-2 recorded the highest value for moisture content, contact angle, colour and viscosity after 15 frying cycles with 30.40 ± 0.2%, 26.01 ± 0.02°, 10.77 ± 0.15 Lovibond, and 133.5 ± 0.2 cP, respectively. However, the density value was insignificant (p > 0.05) between the 1st and 15th frying cycles for all types of oil. Besides, the peroxides value (PV) was steadily increased within the safety limit of Food Act (1983) (Laws of Malaysia: Act 281), with the aldehyde (CO) functional group was detected in all oil samples throughout the 15 frying cycles. Hence, the high correlation between the contact angle and all parameters except density showed that contact angle analysis using PLLA film was a suitable technique for rapid oil spoilage indicator model.     

Gas chromatographic analysis of infant formulas for total fatty acids, including trans fatty acids

Twelve powdered and 13 liquid infant formulas were analyzed by using an extension of AOAC Official Method 996.01 for fat analysis in cereal products. Samples were hydrolyzed with 8 N HCl and extracted with ethyl and petroleum ethers. Fatty acid methyl esters were prepared by refluxing the mixed ether extracts with methanolic sodium hydroxide in the presence of 14% boron trifluoride in methanol. The extracts were analyzed by gas chromatography. In powdered formulas, saturated fatty acid (SFA) content (mean +/- SD; n = 12) was 41.05 +/- 3.94%, monounsaturated fatty acid (MUFA) content was 36.97 +/- 3.38%, polyunsaturated fatty acid (PUFA) content was 20.07 +/- 3.08%, and total trans fatty acid content was 1.30 +/- 1.27%. In liquid formulas, SFA content (mean +/- SD; n = 13) was 42.29 +/- 2.98%, MUFA content was 36.05 +/- 2.47%, PUFA content was 20.65 +/- 2.40%, and total trans fatty acid content was 0.88 +/- 0.54%. Total fat content in powdered formulas ranged from 4.4 to 5.5 g/100 kcal and linoleic acid content ranged from 868 to 1166 mg/100 kcal. In liquid formulas, total fat content ranged from 4.1 to 5.1 g/100 kcal and linoleic acid content ranged from 820 to 1100 mg/100 kcal. There were no significant differences between powdered and liquid infant formulas in concentrations of total fat, SFA, MUFA, PUFA, or trans fatty acids.     

Occurrence of oleic and 18:1 methyl-branched acyl chains in lipids of Rhodobacter sphaeroides 2.4.1

The fatty acids (FAs) composition of lipids extracted from Rhodobacter sphaeroides 2.4.1 was investigated by gas chromatography–mass spectrometry (GC–MS) analysis of the corresponding FA methyl esters (FAMEs), obtained through trans-esterification of the original lipid species. A GC stationary phase based on a highly polar ionic liquid (IL) was selected, aimed to enhance the separation of isomeric FAMEs with particular emphasis on positional and geometrical isomers of monounsaturated 16:1 and 18:1 fatty acyl chains. The occurrence of 18:1 cis-Δ⁹ (oleic) acid, a positional isomer of the well-known and most predominant 18:1 cis-Δ¹¹ (cis-vaccenic) acid, has been demonstrated here for the first time. Furthermore a methyl branched 18:1 FA was also identified and its structure tentatively assigned as 11-methyl-Δ¹²-octadecenoic acid (most likely as trans isomer). The unprecedented observation about 18:1 cis-Δ⁹ FA occurrence in R. sphaeroides 2.4.1 is, even indirectly, supported by a biosynthetic pathway postulated with the aid of the Kyoto Encyclopedia of Genes and Genomes (KEGG) database. The concurrent presence of 16:1 cis-Δ⁷ and 18:1 cis-Δ⁹ FAs suggested the existence of parallel and/or complementary processes to those invoked for the formation of most common 16:1 cis-Δ⁹ and 18:1 cis-Δ¹¹ FAs. A further route was hypothesized for the trans FAs biosynthesis in wild-type cells of R. sphaeroides.     

Vibrational spectra and rotational isomerism of methyl methylsilyl sulphide

Infrared and Raman spectra of methyl methylsilyl sulphide are measured for the liquid and solid states. The fundamental vibrations are assigned and the normal vibrations calculated for two possible rotational isomers about the Si-S bond. Two different solid spectra are obtained, one corresponding to the trans form and the other to the gauche form; the liquid spectrum shows the presence of both forms. The gauche form is more stable than the trans form in the liquid state by 80 ± 50 cal mol^?1. The crystallization process indicates that the freezing and melting points of the trans form are slightly higher than those of the gauche form.