Supercritical fluid chromatography with post-column addition of supporting electrolyte solution for electrochemical determination of tocopherol and tocotrienol isomers

Kazuhiro Yamamoto, Takuma Nishimura, Koichi Machida, Akira Kotani, Hideki Hakamata

J Sep Sci . 2022 Mar 5. doi: 10.1002/jssc.202100923. Online ahead of print.

Abstract

A supercritical fluid chromatography with electrochemical detection system was developed for the simultaneous determination of tocopherol and tocotrienol isomers. The supercritical fluid chromatography with electrochemical detection system was connected with an additional pump to create a flow path to add a supporting electrolyte solution. The supporting electrolyte solution was mixed with a mobile phase in a post-column fashion, enabling the independent control of the separation and detection. After optimization of the measurement conditions, vitamin E isomers and an internal standard substance (2,2,5,7,8-pentamethyl-6-hydroxychroman) were separated within 30 min using a mixture of supercritical carbon dioxide and methanol (99:1, v/v) as a mobile phase and a cyanopropyl column (4.6 mm inner diameter × 250 mm length, 5 μm). For the electrochemical detection, methanol containing 1.0 mol/L ammonium acetate was used as a supporting electrolyte solution, and the applied potential was set at +0.8 V. This analytical method showed good linearity (5-100 μg/mL) and repeatability (less than 2.5% relative standard deviation, n = 6) and was applicable to the determination of tocopherol and tocotrienol isomers in nutrition supplements.

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Vitamin E in foodstuff: Nutritional, analytical, and food technology aspects

Farah Zaaboul, YuanFa Liu

Compr Rev Food Sci Food Saf . 2022 Feb 18. doi: 10.1111/1541-4337.12924. Online ahead of print.

Abstract

Vitamin E is a group of isoprenoid chromanols with different biological activities. It comprises eight oil-soluble compounds: four tocopherols, namely, α-, β-, γ-, and δ-tocopherols; and four tocotrienols, namely, α-, β-, γ, and δ-tocotrienols. Vitamin E isomers are well-known for their antioxidant activity, gene-regulation effects, and anti-inflammatory and nephroprotective properties. Considering that vitamin E is exclusively synthesized by photosynthetic organisms, animals can only acquire it through their diet. Plant-based food is the primary source of vitamin E; hence, oils, nuts, fruits, and vegetables with high contents of vitamin E are mostly consumed after processing, including industrial processes and home-cooking, which involve vitamin E profile and content alteration during their preparation. Accordingly, it is essential to identify the vitamin E content and profile in foodstuff to match daily intake requirements. This review summarizes recent advances in vitamin E chemistry, metabolism and metabolites, current knowledge on their contents and profiles in raw and processed plant foods, and finally, their modern developments in analytical methods.

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Secretory Production of Tocotrienols in Saccharomyces cerevisiae

Xue Jiao 1, Bin Shen 1, Min Li 1, Lidan Ye 1 2, Hongwei Yu 1

ACS Synth Biol . 2022 Jan 31. doi: 10.1021/acssynbio.1c00484. Online ahead of print.

Abstract

Tocotrienols as important components of vitamin E have attracted increasing attention, with recent progress made in their heterologous biosynthesis, but all as intracellular products. Aiming to further improve the tocotrienol production capacity of engineered yeast and to advance toward industrial fermentation of tocotrienols, we first optimized the synthetic pathway to enhance the tocotrienol yield and then attempted to realize their secretory production by exploring biphasic extractive fermentation conditions and screening for endogenous transporters. Finally, a Saccharomyces cerevisiae strain with tocotrienol yield of 25.57 mg/g dry cell weight was generated, and the tocotrienol titer reached 82.68 mg/L in shake-flask cultures, with 73.66% of the product secreted into the organic phase. For the first time, we have reported that the vitamin E components could be harvested as extracellular products of microbial cell factories, which could largely simplify the downstream process and could be of significance for fermentative production of these products.

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Transport of Vitamin E from Ethanol/Water Solution into Contact Lenses and Impact on Drug Transport

Zhen Liu, Meredith Overton, Anuj Chauhan

J Ocul Pharmacol Ther . 2022 Jan 19. doi: 10.1089/jop.2021.0094. Online ahead of print.

Abstract

Purpose: Contact lens-based drug delivery has many advantages over eye drops including higher bioavailability and sustained release. Commercial contact lenses release drug rapidly necessitating integration of control-release mechanisms into the lenses such as incorporation of vitamin E diffusion barriers. In prior publications, vitamin E barriers are loaded by placing the lenses in vitamin E-ethanol solution, followed by the ethanol extraction. In this article, we investigate feasibility of manufacturing vitamin E barriers by soaking contact lenses in vitamin E dissolved in ethanol-water solutions to minimize swelling. Methods: Contact lenses are soaked in solutions of vitamin E dissolved in ethanol-water mixtures. The dynamics of vitamin E transport into the measured and fitted to diffusion equation to determine diffusivity and partition coefficient. Vitamin E loaded lenses are imaged and transport of hydrophilic drug timolol is measured. Results: The partition coefficient of vitamin E increases more than 5 and 10-fold when the water content in the loading solution reaches 15% and 25% (v/v), respectively. The solubility of vitamin E in the solutions decreases as water fraction increases but the increase in partition coefficient allows for loading > 20% vitamin E in the lens. The barriers manufactured by this approach are effective at sustaining release of glaucoma drug timolol. Conclusions: Vitamin E barriers can be incorporated into contact lenses by soaking in solutions of vitamin E in water and ethanol. Vitamin E barriers extended hydrophilic drug release and the reduced swelling is beneficial in minimizing the possibility of lens damage during loading of vitamin E.

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Scrubbed Palm Fatty Acid Distillate as Vitamin E Concentrate

Amnart Soontornchatchawate, Supachai Chintanalert, Prakob Kitchaiya, Apinan Namkanisorn

J Oleo Sci . 2021 Dec 8. doi: 10.5650/jos.ess21169. Online ahead of print.

Abstract

Vitamin E (VitE) production from crude palm oil (CPO) has been extensively studied and industrially conducted. VitE in CPO is in the range of 600 to 1,000 ppm, and is usually produced from one of the main by-products of edible palm oil production, namely palm fatty acid distillate (PFAD). PFAD contains 4,000 to 5,500 ppm of VitE, and is produced from deodorization process of palm oil purification. This paper presents an innovative process of VitE concentrate production from CPO. A scrubber was designed and installed between the deodorizer and conventional PFAD scrubber. The main objective of this new scrubber was a recovery of glycerides from PFAD. This new scrubber is operated at 150 to 160℃. The scrubbed oil is named as Scrubbed Palm Fatty Acid Distillate (S-PFAD). This simple and efficient modified process can retrieve glycerides as S-PFAD at 0.3% recovery and it enhances VitE concentration in S-PFAD to the range of 28,000 to 32,000 ppm, which is the highest concentration of VitE that has ever been produced in the palm oil production. Fatty acids and glycerides in S-PFAD were esterified and transesterified to methyl esters. The methyl esters were evaporated from S-PFAD, and S-PFAD residue oil contained 24.7% VitE.

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Formulation and evaluation of a α-linolenic acid and vitamin E succinate microemulsion with low surfactant content and free of co-surfactant for use as a nutritional supplement

Dan Ye, Liyan Shen, Ying Sun, Di Zhang, Xiao Tan, Panpan Jing, Min Zhang, Qingping Tian

Food Chem . 2021 Dec 1;364:130433. doi: 10.1016/j.foodchem.2021.130433. Epub 2021 Jun 23.

Abstract

Herein, we have designed an alcohol-free and low-surfactant microemulsion to safely and effectively supply α-linolenic acid (ALA) and vitamin E (VE). Ternary phase diagrams show that the use of medium- or short-chain alcohols as the co-surfactant (CoS) was unfavorable for the formation of the ALA microemulsion due to the competitive hydrogen bonding effect and vitamin E succinate (VES) significantly increased the ALA microemulsion region by improving the hydrophilicity of the oil phase. The optimal microemulsion formulation (Mav) was 6.86% ALA, 1.14% VES, 12% surfactant and 80% water, with uniformly dispersed spherical particles with diameters of ~ 25.41 nm and viscosity of 35.17 mPa·s. The Mav was stable to high temperature, ionic strength and pH, and exhibited good physical and anti-oxidation stability. The Mav facilitated the release and hydrolysis of VES, indicating that the CoS-free microemulsion with low surfactant content is promising for the safe and effective supply of ALA and VE.

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Developing functional markers for vitamin E biosynthesis in oil palm

Yajing Dou, Wei Xia, Annaliese S Mason, Dongyi Huang, Xiwei Sun, Haikuo Fan, Yong Xiao

PLoS One . 2021 Nov 19;16(11):e0259684. doi: 10.1371/journal.pone.0259684. eCollection 2021.

Abstract

Vitamin E is essential for human health and plays positive roles in anti-oxidation. Previously, we detected large variation in vitamin E content among 161 oil palm accessions. In this study, twenty oil palm accessions with distinct variation in vitamin E contents (171.30 to 1 258.50 ppm) were selected for genetic variation analysis and developing functional markers associated with vitamin E contents. Thirty-seven homologous genes in oil palm belonging to vitamin E biosynthesis pathway were identified via BLASTP analysis, the lengths of which ranged from 426 to 25 717 bp (average 7 089 bp). Multiplex PCR sequencing for the 37 genes found 1 703 SNPs and 85 indels among the 20 oil palm accessions, with 226 SNPs locating in the coding regions. Clustering analysis for these polymorphic loci showed that the 20 oil palm accessions could be divided into five groups. Among these groups, group I included eight oil palm accessions whose vitamin E content (mean value: 893.50 ppm) was far higher than other groups (mean value 256.29 to 532.94 ppm). Correlation analysis between the markers and vitamin E traits showed that 134 SNP and 7 indel markers were significantly (p < 0.05) related with total vitamin E content. Among these functional markers, the indel EgTMT-1-24 was highly correlated with variation in vitamin E content, especially tocotrienol content. Our study identified a number of candidate function associated markers and provided clues for further research into molecular breeding for high vitamin E content oil palm.

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Lipophilic Vitamin E Diffusion through Bicontinuous Microemulsions

Dai Kato, Johtaro Yamamoto, Yoshio Suzuki, Tomoyuki Kamata, Hinako Hashimoto, Masashi Kunitake

Anal Chem . 2021 Oct 13. doi: 10.1021/acs.analchem.1c03174. Online ahead of print.

Abstract

We studied the diffusion properties of lipophilic vitamin E (VE) through bicontinuous microemulsions (BME) using both electrochemical and fluorescence correlation spectroscopy (FCS) measurements. We investigated the effect of different composition ratios of micro-water and micro-oil phases in BMEs (W/OBME). When we employed the BME with a lower W/OBME value of 40/60 (oil-rich BME) as an electrolyte solution, we obtained a larger current response from VE at a fluorinated nanocarbon film electrode. Further voltammetric studies revealed that a higher VE diffusion coefficient was observed in the oil-rich BME. The FCS results also exhibited faster diffusion through the oil-rich BME, which played a significant role in accelerating the VE diffusion probably due to the widening of the micro-oil phase pathway in the BME. Moreover, the effect of increasing the VE diffusion was pronounced at the interface between the electrode surface and the BME solution. These results indicate that controlling the conditions of the BME as the measurement electrolyte is very effective for achieving superior electrochemical measurements in a BME.

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Pressurized liquid extraction to obtain chia seeds oils extracts enriched in tocochromanols. Nanoemulsions approaches to preserve the antioxidant potential

Lucía Castro-Vázquez, Virginia Rodríguez-Robledo, María Plaza-Oliver, Manuel J Santander-Ortega, M Victoria Lozano, Joaquín González, Noemí Villaseca, Pilar Marcos, M Mar Arroyo-Jiménez

J Food Sci Technol . 2021 Oct;58(10):4034-4044. doi: 10.1007/s13197-020-04866-9. Epub 2021 Jan 5.

Abstract

The objective of this study was to use accelerated-solvent-extraction to achieve antioxidant extracts from chia seeds oils, enriched in tocopherols and tocotrienols, namely tocochromanols. Nanotechnology applications have been also incorporated to develop an innovative formulation of chia seeds oil nanoemulsion that preserve its antioxidant potential after conditions of oxidative stress. Chia seeds oils proved to be a valuable source of tocochromanols, from 568.84 to 855.98 μg g-1, depending on the geographical provenance. Quantitative data obtained by LC-DAD-ESI-MS/MS showed outstanding levels of γ-Tocopherol, over 83%, followed far behind by Tocopherols-(α, β, δ) and Tocotrienols-(α, β, δ, γ)-tocotrienols. The characteristic tocochromanols fingerprint of chia seeds oils was positively correlated with the FRAP and DPPH antioxidant activity of the extracts (between 18.81 and 138.48 mg Trolox/g). Formulation of the Chia seeds oils as nanoemulsions did not compromised the antioxidant properties of fresh extracts. Interestingly, nanoemulsions retained about the 80% of the initial antioxidant capacity after UV-induced stress, where the non-emulsified oils displayed a remarkable reduction (50-60%) on its antioxidant capacity under the same conditions. These antioxidant chia seeds formulations can constitute a promising strategy to vectorizing vitamin E isomers, in order to be used for food fortification, natural additives and to increase the self-life of food products during packing.

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Interactions between α-tocopherol and γ-oryzanol in oil-in-water emulsions

Ruru Liu, Ying Xu, Ming Chang, Ruijie Liu, Xingguo Wang

Food Chem . 2021 Sep 15;356:129648. doi: 10.1016/j.foodchem.2021.129648. Epub 2021 Mar 22.

Abstract

The interaction between antioxidants is affected by many factors, such as concentration, ratio and system. In this study, different concentrations of α-tocopherol and γ-oryzanol showed antagonistic effect in the oil-in-water emulsion, and the distribution of α-tocopherol increased in aqueous phase after combined with γ-oryzanol. The concentration could affect the degree of antagonism. According to fluorescence quenching, cyclic voltammetry measurements and the oxidative decomposition of antioxidants during storage, the inhibitory effect of γ-oryzanol on the regeneration of α-tocopherol was proposed to be responsible for the antagonism. This work can provide suggestions for studying the mechanism of antioxidant interaction in emulsion system.

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