Compositional Study of Phospholipids from the Dried Big Head and Opossum Shrimp, Mussel, and Sea Cucumber Using 31P NMR Spectroscopy: Content and Fatty Acid Composition of Plasmalogen.

Herein, we present a qualitative and quantitative analysis of the compositions of plasmalogens and phospholipids (PLs) in dried big head shrimp (Solenocera melantho), opossum shrimp (Neomysis awatschensis), mussel (Mytilus galloprovincialis), and sea cucumber (Apostichopus japonicus). We also analyze the fatty acid composition of the extracted lipids, phosphatidyl choline (PtdCho), and plasmalogen choline (PlsCho) from each sample. In big head shrimp, opossum shrimp, and mussel, phosphatidyl choline (PtdCho) was the most abundant PL at 1677.9, 1603, and 1661.6 mg/100 g of dried sample, respectively, whereas the most abundant PL in sea cucumber was PlsCho (206.9 mg/100 g of dried sample). In all four samples, plasmalogen ethanolamine (PlsEtn) was higher than phosphatidyl ethanolamine (PtdEtn). The content (mg/100 g of dried sample) of PlsCho was highest in mussel (379.0), and it was higher in big head shrimp (262.3) and opossum shrimp (245.6) than sea cucumber (206.9). The contents (mg/100 g of dried sample) of PlsEtn were in the order of mussel (675.4) > big head shrimp (629.5) > opossum shrimp (217.9) > sea cucumber (51.5). For analyzing the fatty acids at the sn-2 position of PlsCho, the consecutive treatment with phospholipase A1, solid phase extraction, thin-layer chromatography (TLC), and GC-FID were applied. The most abundant fatty acid was eicosapentaenoic acid (EPA, C20:5, n-3) in big head shrimp and sea cucumber, palmitoleic acid (C16:1, n-7) in opossum shrimp, and docosadienoic acid (C22:2, n-6) in mussel.

Development and Physicochemical Properties of Low Saturation Alternative Fat for Whipping Cream.

We developed an alternative whipping cream fat using shea butter but with low saturation. Enriched stearic-oleic-stearic (SOS) solid fat was obtained from shea butter via solvent fractionation. Acyl migration reactant, which mainly contains asymmetric SSO triacylglycerol (TAG), was prepared through enzymatic acyl migration to obtain the creaming quality derived from the ß'-crystal form. Through enzymatic acyl migration, we obtained a 3.4-fold higher content of saturated-saturated-unsaturated (SSU) TAG than saturated-unsaturated-saturated (SUS) TAG. The acyl migration reactant was refined to obtain refined acyl migration reactant (RAMR). An alternative fat product was prepared by blending RAMR and hydrogenated palm kernel oil (HPKO) at a ratio of 4:6 (w/w). The melting points, solid fat index (SFI), and melting curves of the alternative products were similar to those of commercial whipping cream fat. The alternative fat had a content of total unsaturated fatty acids 20% higher than that of HPKO. The atherogenic index (AI) of alternative fat was 3.61, much lower than those of whipping cream fat (14.59) and HPKO (1220.3), because of its low atherogenic fatty acid content and high total unsaturated fatty acids. The polymorphic crystal form determined by X-ray diffraction spectroscopy showed that the ß'-crystal form was predominant. Therefore, the alternative fat is comparable with whipping cream that requires creaming quality, and has a reduced saturated fat content.

Presence of Cholesterol in Non-Animal Organisms: Identification and Quantification of Cholesterol in Crude Seed Oil from Perilla frutescens and Dehydrated Pyropia tenera.

Studies have reported that cholesterol, a molecule found mainly in animals, is also present in some plants and algae. This study aimed to determine whether cholesterol exists in three dehydrated algae species, namely, Pyropia tenera, Saccharina japonica, and Undaria pinnatifida, and in one plant species, namely, Perilla frutescens (four perilla seed oil samples were analyzed). These species were chosen for investigation because they are common ingredients in East Asian cuisine. Gas chromatography-flame ionization detection (GC-FID) analysis found that cholesterol was present in P. tenera (14.6 mg/100 g) and in all four perilla seed oil samples (0.3-0.5 mg/100 g). High-performance liquid chromatography with evaporative light-scattering detection (HPLC-ELSD) also demonstrated that cholesterol was present in P. tenera (14.2 mg/100 g) and allowed the separation of cholesterol from its isomer lathosterol. However, cholesterol could not be detected by HPLC-ELSD in the perilla seed oil samples, most likely because it is only present in trace amounts. Moreover, liquid chromatography-tandem mass spectrometry (LC-MS/MS) confirmed the presence of cholesterol in both P. tenera and perilla seed oil. MRM results further suggested that lathosterol (a precursor of cholesterol) was present in P. tenera.

Correlations of Fat Content in Human Milk with Fat Droplet Size and Phospholipid Species.

Fat globule size and phospholipid (PL) content in human milk (HM) were investigated. HM was classified into three groups depending on fat content (A < B < C). PL content (mg/100 g HM) was significantly higher in the C group (p < 0.05), indicating its positive relationship with HM fat content. When the PL content was normalized (mg/g fat), that of group A was significantly higher (p < 0.05) and fat droplet size in group C was slightly larger, suggesting that HM fat content is affected by fat droplet numbers to a larger extent than by fat droplet size. A correlation between PC and SM content in HM was observed regardless of fat content, while correlation between PE and either PC or SM increased in the order of C > B > A, hence the composition and content of PL species in HM varied according to its fat content.

Cu(OTf)2-Promoted 1,4-Addition of Alkyl Bromides to Dehydroalanine.

Zn/Cu(OTf)2-mediated addition of alkyl bromides to dehydroalanine (Dha) derivatives including dipeptides and tripeptides in good to high yields under an aqueous medium was developed. This protocol allows selective and biocompatible access to various amino acid units from Dha derivatives.

Approach Study for Mass Balance of Pesticide Residues in Distillers' Stillage along with Distillate and Absence Verification of Pesticides in Distilled Spirits from Pilot-Scale of Distillation Column.

Herein, contaminants remaining in distillate and distillers' stillage were quantitatively measured after distillation. After rice bran powder was contaminated with 10 ppm of lead (Pb) and cadmium (Cd) or 0.02-1.27 ppm of five pesticides (terbufos, fenthion, iprobenfos, flutolanil, and ethoprophos) followed by fermentation, single-stage distillation was performed. In the obtained distillate, no Pb or Cd was found, as expected. However, when the pesticides were added as contaminants, trace-0.05 ppm of some pesticides were detected in the distillate, possibly due to the high vapor pressure (e.g., that of ethoprophos) and contamination amount (e.g., that of flutolanil, terbufos, and fenthion). In contrast, none of the contaminating pesticides were observed in the distilled spirits when a fermented liquefaction contaminated with 0.04-4 ppm of six pesticides (fenthion, terbufos, ethoprophos, iprobenfos, oxadiazon, and flutolanil) was distilled using a pilot-plant scale distillation column, indicating that the pesticides hardly migrate to the distilled spirits.

Choroidal volume in branch retinal vein occlusion before and after intravitreal anti-VEGF injection.

PURPOSE: The aim of this study is to evaluate the subfoveal choroidal volume change in the patients with branch retinal vein occlusion before and after intravitreal anti-vascular endothelial growth factor injection using the enhanced depth imaging optical coherence tomography. METHODS: We measured the bilateral subfoveal choroidal volume in 15 patients (mean age, 64.47 ± 7.13 years) with unilateral branch retinal vein occlusion by using the enhanced depth imaging methods of the Spectralis optical coherence tomography system. After an injection of intravitreal bevacizumab, we measured the subfoveal choroidal volume of the eye with regressed macular edema. RESULTS: The mean subfoveal choroidal volume measured in 15 eligible eyes of 15 patients was 7.74 ± 0.70 mm, which was significantly greater than the volume of the fellow eyes (6.38 ± 0.69 mm; P = 0.001, Wilcoxon signed-rank test). The subfoveal choroidal volume of the eye with regressed macular edema was 6.56 ± 0.79 mm, which was significantly lower than the volume before the treatment (P = 0.001, Wilcoxon signed-rank test). CONCLUSION: The subfoveal choroidal volume of the branch retinal vein occlusion eyes was significantly greater than the volume of the fellow eyes and decreased significantly after an intravitreal anti-vascular endothelial growth factor treatment.

Quantitative Analysis of Nervonic and Erucic Acids in Human Milk: Comparison with Infant Formula with Different Fat Sources and Nutritional Stages.

This study aims to quantitatively analyze nervonic (C24:1 n-9) and erucic (C22:1 n-9) acids in human milk (HM) collected from Korean mothers, along with the infant formulas (IFs) with different fat sources and nutritional stages. The content of nervonic and erucic acids in HM from Korean mothers were 2.13 and 2.81 mg/100 g, accounting for 0.06 and 0.08% of the total fatty acids (FAs), respectively. These acids in IFs based on fat from plant-oil formula were higher than those in IFs based on cow milk formula. The composition of erucic acid in IFs based on cow milk formula and plant-oil formula increased with the nutritional stages, while nervonic acid only increased in IFs based on the plant-oil formula.

Intranasal delivery of the cytoplasmic domain of CTLA-4 using a novel protein transduction domain prevents allergic inflammation.

CTLA-4 is a negative regulator of T-cell activation, and its inhibitory effects can be accomplished either by competition with CD28 or by transmitting negative signals through its intracellular domain. To utilize the cytoplasmic domain of CTLA-4 to suppress allergic inflammation, we fused it to a novel protein-transduction domain in the human transcriptional factor Hph-1. Transduction efficiency was verified in vitro and in vivo after ocular, intranasal and intradermal administration. After transduction into T cells, the Hph-1-ctCTLA-4 fusion protein inhibited the production of interleukin (IL)-2, and downregulated CD69 and CD25. Intranasal administration of Hph-1-ctCTLA-4 resulted in markedly reduced infiltration of inflammatory cells, secretion of T helper type 2 (T(H)2) cytokines, serum IgE levels and airway hyper-responsiveness in a mouse model of allergic airway inflammation. These results indicated that Hph-1-ctCTLA-4 constitutes an effective immunosuppressive protein drug for potential use in the treatment of allergic asthma, via nasal administration.

Migration Degree of Selected Mycotoxins in the Distillation Process and Their Determination in Distilled Spirits from Pilot-Scale Continuous Distillation.

Mycotoxins (ochratoxin A (20 ppb), aflatoxin B1 (40 ppb), deoxynivalenol (4 ppm), and zearalenone (800 ppb)) were intentionally added to rice bran raw materials. After fermentation, their contents were determined in the distillate and distillery stillage obtained using single-stage and continuous pilot plant-scale columns. After single-stage distillation, aflatoxin B1, deoxynivalenol, and zearalenone were not detected in the distillate, indicating that even if a certain amount (four times the maximum residue limit (MRL)) was present in the raw material, it would not remain in the distillate after fermentation and distillation. Most mycotoxins remained in the distillery stillage, and their residual rates ranged from 54.0-96.2%. For ochratoxin A, 0.19 ppb was found in the distillate and this migration occurred in three consecutive distillations (0.11-0.22 ppb). Ochratoxin A and aflatoxin B1 were not detected in the distillate (alcohol content 93.9% and 95.4%, respectively) obtained from the contaminated fermented liquid (approximately three times the MRL based on the raw material) using the pilot-plant scale continuous distillation column. Therefore, the migration of mycotoxins is difficult when the distilled spirit is produced using a continuous distillation column, even if the raw material is contaminated with certain amounts of the investigated mycotoxins.

Oxidation stability of oil-in-water emulsion prepared from perilla seed oil and soy sauce with high salt concentration using OSA-starch.

The O/W emulsions were prepared using perilla seed oil (PSO) dispersed in soy sauce (PSE) and in distilled water (PWE), respectively. Octenyl succinic anhydride-modified starch (OSA starch, 3 wt%) showed the most efficient emulsifying ability and its stabilities of emulsion and oxidation in PSE and PWE were studied at different storage periods (0, 4, and 8 weeks) and temperatures (4, 25, and 40 °C). Negligible change in droplet diameter of PSE was observed without coalescence or flocculation during storing for 8 weeks at 4 °C. The stabilizing ability of OSA-starch despite the high ionic strength of soy sauce is attributed to the starch backbone, which promotes steric repulsions between droplets. A lower oxidation degree was observed for PSE prepared than PWE and PSO under all storage conditions. Thus, the O/W emulsion prepared from PSO and soy sauce can be applied to the production of ω-3 fatty acid-enriched Asian-style emulsified products.

Lipase-catalyzed preparation of deacidified Buah Merah (Pandanus conoideus) oil.

Buah Merah oil (BMO) is unrefined edible oil containing a high level of free fatty acids (FFA; ∼30% w/w). This study was aimed at preparing deacidified BMO from BMO via lipase-catalyzed esterification of FFA in BMO with added glycerol, using Duolite A568-immobilized Eversa Transform 2.0 (Thermomyces lanuginosus lipase) as biocatalyst. BMO containing 2.4% w/w FFA and 94.6% w/w triacylglycerol was obtained under optimal reaction conditions (temperature, 70°C; FFA-to-glycerol molar ratio, 3:1; enzyme loading based on the protein quantity, 3.75 mg/g BMO, and reaction time, 48 h). No significant difference was found in the contents of ß-carotene, tocopherols, and phytosterols between raw and deacidified BMO. The induction period of oxidation was significantly longer in deacidified BMO (16.37 h) than in raw BMO (0.03 h). These results suggest that deacidified BMO could be enzymatically prepared without the loss of health-beneficial minor components while enhancing the oxidative stability. PRACTICAL APPLICATION: Although BMO has recently received much attention for its potential biological activities, the commercial use of BMO as a healthy oil has been limited due to its high FFA content. Unlike conventional alkali and steam refining, enzymatic deacidification of BMO employed in this study might help the commercialization of BMO, because this procedure enables the improvement of oil yield and the retaining of health-beneficial minor components.

Copper-catalyzed azide-alkyne cycloaddition reaction in water using cyclodextrin as a phase transfer catalyst.

1,4-Disubstituted-1,2,3-triazoles were obtained in excellent yields from azides and terminal alkynes in H(2)O in the presence of catalytic amount of ß-cyclodextrin as a phase transfer catalyst. Also, a one-pot CuAAC reaction was carried out successfully, affording 1,4-disubstituted-1,2,3-triazoles in good to high yields starting from an alkyl bromide, sodium azide, and terminal alkyne.

Effect of Fermentation on Cyanide and Ethyl Carbamate Contents in Cassava Flour and Evaluation of Their Mass Balance during Lab-Scale Continuous Distillation.

When cassava is used for the production of distilled spirits through fermentation and distillation, toxic hydrogen cyanide (HCN) is released from linamarin and carcinogenic ethyl carbamate is produced. Herein, cyanide and ethyl carbamate contents were monitored during the fermentation and lab-scale continuous distillation processes. Thereafter, mass balance and the influence of copper chips were evaluated. Results showed that 81.5% of cyanide was removed after fermentation. Use of copper chips completely prevented the migration of cyanide into the distilled spirits, while 88.3% of cyanide migrated from the fermented liquid in the absence of copper chips. Formation of ethyl carbamate was significantly promoted during distillation. Most of the produced ethyl carbamate (73.2%) was transferred into the distilled spirits in the absence of copper chips, only 9.6% of the ethyl carbamate was transferred when copper chips were used. Thus, copper chips effectively prevented the migration of cyanide and ethyl carbamate into the distilled spirts during continuous distillation.

Enrichment of pinolenic acid at the sn-2 position of triacylglycerol molecules through lipase-catalyzed reaction.

Reports have shown that Delta-5 polyunsaturated fatty acids (-5 PUFA) are enriched at sn-1,3 positions of triacylglycerols (TAG) in pine (Pinus koraiensis) nut oil (Pn). As a major Delta-5 PUFA, pinolenic acid (Pi) is about 14.2% in the oil, while the percentage of Pi at the sn-1 and/or sn-3 positions in TAG was found more than 20%. In this current study, the enhancement of Pi at the sn-2 position has been achieved by acyl migration during the lipase-catalyzed inter-esterification between Pn and palm stearin (Ps). After reaction, the proportion of Pi increased at sn-2 positional fatty acid even is similar to that in total fatty acid; for example, in the inter-esterified product of 50:50 (Pn:Ps), the same amount of Pi (7.1%) present was detected both at the sn-2 and sn-1,3 positions. However, the reduction of phytosterols and tocopherols are observed in the inter-esterified products.

Production of trans-free margarine stock by enzymatic interesterification of rice bran oil, palm stearin and coconut oil.

BACKGROUND: Trans-free interesterified fat was produced for possible usage as a spreadable margarine stock. Rice bran oil, palm stearin and coconut oil were used as substrates for lipase-catalyzed reaction. RESULTS: After interesterification, 137-150 g kg(-1) medium-chain fatty acid was incorporated into the triacylglycerol (TAG) of the interesterified fats. Solid fat contents at 25 degrees C were 15.5-34.2%, and slip melting point ranged from 27.5 to 34.3 degrees C. POP and PPP (beta-tending TAG) in palm stearin decreased after interesterification. X-ray diffraction analysis demonstrated that the interesterified fats contained mostly beta' polymorphic forms, which is a desirable property for margarines. CONCLUSIONS: The interesterified fats showed desirable physical properties and suitable crystal form (beta' polymorph) for possible use as a spreadable margarine stock. Therefore, our result suggested that the interesterified fat without trans fatty acid could be used as an alternative to partially hydrogenated fat.

Determination of acetaldehyde, methanol and fusel oils in distilled liquors and sakès by headspace gas chromatography.

In this study, a headspace gas chromatography (HS-GC) method was carried out to determine the contents of acetaldehyde, methanol and fusel oils in distilled liquors and sakès from different countries. A DB-Wax column was adopted in HS-GC, which showed good linearity, high precision and accuracy and low LOQ and LOD on all the compounds. Results showed that distilled liquors contained higher levels of acetaldehyde with the values of 12.88-35.53 mg/L than sakès (0.83-29.13 mg/L). Methanol was only detected in a few distilled liquors with small amounts. Amyl alcohols, including isoamyl alcohol (2-methyl-1-butanol) and active amyl alcohol (3-methyl-1-butanol), isobutanol (2-methyl-1-propanol) and 1-propanol were the main fusel oils among the distilled liquors and sakès analyzed. Amyl alcohols contents were 2 to 4 times higher in Korean distilled liquors (203.01-428.66 mg/L) than that in Chinese distilled liquors (28.52-42.77 mg/L) and all the sakès (61.90-166.59 mg/L).

Evaluation of Oxidation Parameters of Caffeic Acid Phenethyl Ester Comparing with Caffeic Acid, Ascorbyl Palmitate, and α-Tocopherol on the Thermal Oxidation Model.

In this study, the antioxidative capacity of caffeic acid (CA), ascorbyl palmitate (AP), α-tocopherol (α-TO), and caffeic acid phenethyl ester (CAPE) was evaluated under the thermal oxidation model, in which 200 ppm of each compound was added to soybean oil, followed by thermal oxidation at 180°C for 32 h. Change of viscosity, acid value (AV), conjugated dienoic acid value (CDAV), p-anisidine value (p-AV), total polar materials (TPM), and the ratio of C18:2 to C16:0 (LA/PA) were evaluated during the reaction. All antioxidants showed significantly lower viscosity, TPM, and p-AV, and higher LA/PA, than the control (without antioxidant, CON), indicating that thermal oxidation was delayed. Among them, CAPE showed significantly lower viscosity, TPM, and p-AV, and higher LA/PA, than the other antioxidants (p < 0.05). In the correlation between the oxidation parameters measured from CON and CAPE, the correlation coefficient between p-AV and viscosity was rather low at r = 0.7603 (in CON) and r = 0.7338 (in CAPE), respectively.

Evaluation model for cocoa butter equivalents based on fatty acid compositions and triacylglycerol patterns.

An effective evaluation model was established to digitize the quality of cocoa butter equivalents (CBEs) based on determinations of total and sn-2 fatty acid compositions and triacylglycerol (TAG) profiles and the "deducting score" principle. Similarity scores for selected fats and oils calculated from the model revealed differences between them and parallel cocoa butter compositions. For CBE1 and CBE2, total similarity scores were 90.6 and 90.0, whereas those of mango (76.3), dhupa (84.1), sal fat (84.7), kokum (78.3), palm mid fractions (PMF, 77.9), shea butter (64.0), illipe butter (89.7) and Pentadesma butyracea butter (67.2), respectively. Similarity scores were found to agree with physical properties, including polymorphism, crystal morphology, crystallization or melting behaviors, and solid fat content. The present study provides an accurate means of assessing CBE quality and hopefully will contribute to the development of commercial CBEs.

Physicochemical characteristics of fat blend from hydrogenated coconut oil and acyl migrated palm mid-fraction.

Palm mid-fraction (PMF), which has a high content of symmetric POP, was converted to asymmetric PPO (APMF) via acyl migration. After solvent fractionation, the liquid phase of acyl migrated PMF (APMF-L) was obtained and blended with hydrogenated coconut oil (HCO, 50:50, w/w) to produce a fat blend (namely, an alternative fat blend) which had reduced saturated fatty acid content while having similar melting behavior to HCO. In an alternative fat blend, the major fatty acids were lauric (27.94), palmitic (26.93) and oleic (15.75 mol%) acid. The solid fat index was quite similar to that of HCO, especially at 28-44 °C. Nevertheless, an alternative fat blend had lower saturated fatty acid content, by 18%, compared to HCO. The content of highly atherogenic myristic acid was reduced by approximately 40%. The alternative fat blend in this study could be used as a raw material for non-dairy cream with low saturated fat content.