[en] Folates are essential micronutrients for human health. To determine the total folate content, the extraction and quantification of seven monoglutamate folate derivatives in cereals (maize, rice, and wheat) were optimised and validated in this study. Di-enzyme treatment with α-amylase and rat conjugase was proved ideal for folate extraction from the cereal grains. The quantification method by liquid chromatography-tandem mass spectrometry was validated based on its matrix effect, linearity, sensitivity, recovery, inter-day and intra-day precision. The limits of detection and quantification of folate derivatives ranged from 0.03–0.88 and 0.1–1.0 μg/100 g among the three cereal samples. The absolute recoveries of most folate derivatives were 72–96 % for these cereal samples, with the exception of dihydrofolate, tetrahydrofolate, and folic acid (44–65 %). The inter-day and intra-day precisions were < 12 % for the three cereals. Analysis of folate content and composition in several cereal grains showed that the total folate levels were approximately 26−37 μg/100 g, with 5-methyl-tetrahydrofolate and 5-methyl-tetrahydrofolate as the dominant. MeFox, an oxidation product of 5-methyltetrahydrofolate, was detected at concentrations 20–39-fold higher than those of total folates in rice and wheat grains. This validated method is an efficient approach for folate determination in cereal crops.
Disciplines :
Chemistry
Author, co-author :
Shahid, Mehmood; Biotechnology Research Institute, Chinese Academy of Agricultural Sciences, Beijing, China
Lian, Tong ; Université de Liège - ULiège > TERRA Research Centre ; Biotechnology Research Institute, Chinese Academy of Agricultural Sciences, Beijing, China
Wan, Xing; Biotechnology Research Institute, Chinese Academy of Agricultural Sciences, Beijing, China
Jiang, Ling; Biotechnology Research Institute, Chinese Academy of Agricultural Sciences, Beijing, China
Han, Lida; Biotechnology Research Institute, Chinese Academy of Agricultural Sciences, Beijing, China
Zhang, Chunyi; Biotechnology Research Institute, Chinese Academy of Agricultural Sciences, Beijing, China
Liang, Qiuju; Biotechnology Research Institute, Chinese Academy of Agricultural Sciences, Beijing, China
Language :
English
Title :
Folate monoglutamate in cereal grains: Evaluation of extraction techniques and determination by LC-MS/MS
National Special Program for Transgenic Research Technology Innovation Program of the Chinese Academy of Agricultural Sciences Shanghai Agriculture Applied Technology Development Program Collaborative Innovation Action, Agricultural Science
Funders :
NSCF - National Natural Science Foundation of China Ministry of Science and Technology of the People's Republic of China
Funding text :
This work was supported by the National Natural Science Foundation of China ( 31970326 ), National Special Program for Transgenic Research ( 2016ZX08003-002 ), Ministry of Science and Technology of China ( 2016YFD0100503 ), National Natural Science Foundation of China ( 31870283 ), Shanghai Agriculture Applied Technology Development Program ( Z20180103 ), and Collaborative Innovation Action, Agricultural Science , and Technology Innovation Program of the Chinese Academy of Agricultural Sciences ( CAAS-XTCX2016009 ).This work was supported by the National Natural Science Foundation of China (31970326), National Special Program for Transgenic Research (2016ZX08003-002), Ministry of Science and Technology of China (2016YFD0100503), National Natural Science Foundation of China (31870283), Shanghai Agriculture Applied Technology Development Program (Z20180103), and Collaborative Innovation Action, Agricultural Science, and Technology Innovation Program of the Chinese Academy of Agricultural Sciences (CAAS-XTCX2016009).
Ashokkumar, K., Sivakumar, P., Saradhadevi, M., Identification and determination of naturally occurring folates in grains of rice (Oryza sativa L.) by UPLC-MS/MS analysis. Nat. Prod. Res. 32:14 (2018), 1733–1737.
Blancquaert, D., Storozhenko, S., Loizeau, K., De Steur, H., De Brouwer, V., Viaene, J., Ravanel, S., Rebeille, F., Lambert, W., Van Der Straeten, D., Folates and folic acid: from fundamental research toward sustainable health. Crit. Rev. Plant Sci. 29:1 (2010), 14–35.
Chandra-Hioe, M.V., Bucknall, M.P., Arcot, J., Evaluating folate extraction from infant milk formulae and adult nutritionals: enzymatic digestion versus enzyme-free heat treatment. Food Chem. 234 (2017), 365–371.
Dams, R., Huestis, M.A., Lambert, W.E., Murphy, C.M., Matrix effect in bio-analysis of illicit drugs with LC-MS/MS: influence of ionization type, sample preparation, and biofluid. J. Am. Soc. Mass Spectrom. 14:11 (2003), 1290–1294.
De Brouwer, V., Storozhenko, S., Van de Steene, J.C., Wille, S.M.R., Stove, C.P., Van Der Straeten, D., Lambert, W.E., Optimisation and validation of a liquid chromatography-tandem mass spectrometry method for folates in rice. J. Chromatogr. A 1215:1–2 (2008), 125–132.
De Brouwer, V., Storozhenko, S., Stove, C.P., Van Daele, J., Van Der Straeten, D., Lambert, W.E., Ultra-performance liquid chromatography-tandem mass spectrometry (UPLC-MS/MS) for the sensitive determination of folates in rice. J. Chromatogr. B 878:3–4 (2010), 509–513.
Dong, W., Cheng, Z.J., Wang, X.L., Wang, B., Zhang, H.Z., Su, N., Yamamaro, C., Lei, C.L., Wang, J., Wang, J.L., Zhang, X., Guo, X.P., Wu, F.Q., Zhai, H.Q., Wan, J.M., Determination of folate content in rice germplasm (Oryza sativa L.) using tri-enzyme extraction and microbiological assays. Int. J. Food Sci. Nutr. 62:5 (2011), 537–543.
Fazili, Z., Pfeiffer, C.M., Accounting for an isobaric interference allows correct determination of folate vitamers in serum by isotope dilution-liquid chromatography-tandem MS. J. Nutr. 143:1 (2013), 108–113.
Freisleben, A., Schieberle, P., Rychlik, M., Comparison of folate quantification in foods by high-performance liquid chromatography-fluorescence detection to that by stable isotope dilution assays using high-performance liquid chromatography-tandem mass spectrometry. Anal. Biochem. 315:2 (2003), 247–255.
Hanson, A.D., Gregory, J.F. 3rd, Folate biosynthesis, turnover, and transport in plants. Annual Rev. Plant Bio. 62 (2011), 105–125.
Hanson, A.D., Gage, D.A., Shachar-Hill, Y., Plant one-carbon metabolism and its engineering. Trends Plant Sci. 5:5 (2000), 206–213.
Hyun, T.H., Tamura, T., Trienzyme extraction in combination with microbiologic assay in food folate analysis: an updated review. Exp. Biol. Med. 230:7 (2005), 444–454.
Iniesta, M.D., Perez-Conesa, D., Garcia-Alonso, J., Ros, G., Periago, M.J., Folate content in tomato (Lycopersicon esculentum). Influence of cultivar, ripeness, year of harvest, and pasteurization and storage temperatures. J. Agric. Food Chem. 57:11 (2009), 4739–4745.
Jha, A.B., Ashokkumar, K., Diapari, M., Ambrose, S.J., Zhang, H.X., Tar'an, B., Bett, K.E., Vandenberg, A., Warkentin, T.D., Purves, R.W., Genetic diversity of folate profiles in seeds of common bean, lentil, chickpea and pea. J. Food Compos. Anal. 42 (2015), 134–140.
Matuszewski, B.K., Constanzer, M.L., Chavez-Eng, C.M., Strategies for the assessment of matrix effect in quantitative bioanalytical methods based on HPLC-MS/MS. Anal. Chem. 75:13 (2003), 3019–3030.
Rader, J.I., Schneeman, B.O., Prevalence of neural tube defects, folate status, and folate fortification of enriched cereal-grain products in the United States. Pediatrics 117:4 (2006), 1394–1399.
Riaz, B., Liang, Q.J., Wan, X., Wang, K., Zhang, C.Y., Ye, X.G., Folate content analysis of wheat cultivars developed in the North China Plain. Food Chem. 289 (2019), 377–383.
Ringling, C., Rychlik, M., Origins of the difference between food folate analysis results obtained by LC-MS/MS and microbiological assays. Anal. Bioanal. Chem. 409:7 (2017), 1815–1825.
Ringling, C., Rychlik, M., Simulation of food folate digestion and bioavailability of an oxidation product of 5-methyltetrahydrofolate. Nutrients, 9(9), 2017.
Rychlik, M., Revised folate content of foods determined by stable isotope dilution assays. J. Food Compos. Anal. 17:3–4 (2004), 475–483.
Scott, J., Rebeille, F., Fletcher, J., Folic acid and folates: the feasibility for nutritional enhancement in plant foods. J. Sci. Food Agric. 80:7 (2000), 795–824.
Shohag, M.J.I., Yang, Q.Y., Wei, Y.Y., Zhang, J., Khan, F.Z., Rychlik, M., He, Z.L., Yang, X.E., A rapid method for sensitive profiling of folates from plant leaf by ultra-performance liquid chromatography coupled to tandem quadrupole mass spectrometer. J. Chromatogr. B 1040 (2017), 169–179.
Smith, D.E.C., Kok, R.M., Teerlink, T., Jakobs, C., Smulders, Y.M., Quantitative determination of erythrocyte folate vitamer distribution by liquid chromatography-tandem mass spectrometry. Clin. Chem. Lab. Med. 44:4 (2006), 450–459.
Strobbe, S., Van Der Straeten, D., Folate biofortification in food crops. Curr. Opin. Biotechnol. 44 (2017), 202–211.
Tyagi, K., Upadhyaya, P., Sarma, S., Tamboli, V., Sreelakshmi, Y., Sharma, R., High performance liquid chromatography coupled to mass spectrometry for profiling and quantitative analysis of folate monoglutamates in tomato. Food Chem. 179 (2015), 76–84.
Upadhyaya, P., Tyagi, K., Sarma, S., Tamboli, V., Sreelakshmi, Y., Sharma, R., Natural variation in folate levels among tomato (Solanum lycopersicum) accessions. Food Chem. 217 (2017), 610–619.
Wan, X., Han, L.D., Yang, M., Zhang, H.Y., Zhang, C.Y., Hu, P., Simultaneous extraction and determination of mono-/polyglutamyl folates using high-performance liquid chromatography-tandem mass spectrometry and its applications in starchy crops. Anal. Bioanal. Chem. 411:13 (2019), 2891–2904.
Wang, C., Riedl, K.M., Schwartz, S.J., A liquid chromatography-tandem mass spectrometric method for quantitative determination of native 5-methyltetrahydrofolate and its polyglutamyl derivatives in raw vegetables. J. Chromatogr. B 878:29 (2010), 2949–2958.
Zhang, G.F., Storozhenko, S., Van Der Straeten, D., Lambert, W.E., Investigation of the extraction behavior of the main monoglutamate folates from spinach by liquid chromatography-electrospray ionization tandem mass spectrometry. J. Chromatogr. A 1078:1–2 (2005), 59–66.
Zhang, H.X., Jha, A.B., Warkentin, T.D., Vandenberg, A., Purves, R.W., Folate stability and method optimization for folate extraction from seeds of pulse crops using LC-SRM MS. J. Food Compos. Anal. 71 (2018), 44–55.
Zhang, H.X., Jha, A.B., De Silva, D., Purves, R.W., Warkentin, T.D., Vandenberg, A., Improved folate monoglutamate extraction and application to folate quantification from wild lentil seeds by ultra-performance liquid chromatography-selective reaction monitoring mass spectrometry. J. Chromatogr. B 1121 (2019), 39–47.
