Fatty acid profile of Romanian’s common bean (Phaseolus vulgaris L.) lipid fractions and their complexation ability by β-cyclodextrin

Autoři: Ioan David aff001;  Manuela D. Orboi aff002;  Marius D. Simandi aff001;  Cosmina A. Chirilă aff001;  Corina I. Megyesi aff001;  Laura Rădulescu aff001;  Lavinia P. Drăghia aff003;  Alexandra T. Lukinich-Gruia aff003;  Cornelia Muntean aff004;  Daniel I. Hădărugă aff006;  Nicoleta G. Hădărugă aff001
Působiště autorů: Department of Food Science, Banat’s University of Agricultural Sciences and Veterinary Medicine “King Michael I of Romania” from Timişoara, Timişoara, Romania aff001;  Department of Economics and Company Financing, Banat’s University of Agricultural Sciences and Veterinary Medicine “King Michael I of Romania” from Timişoara, Timişoara, Romania aff002;  Centre for Gene and Cellular Therapies in the Treatment of Cancer–OncoGen, Clinical County Hospital of Timişoara, Timişoara, Romania aff003;  Department of Applied Chemistry and Engineering of Inorganic Compounds and Environment, Polytechnic University of Timişoara, Timişoara, Romania aff004;  Research Institute for Renewable Energy, Polytechnic University of Timişoara, Timișoara, Romania aff005;  Department of Applied Chemistry, Organic and Natural Compounds Engineering, Polytechnic University of Timişoara, Timişoara, Romania aff006
Vyšlo v časopise: PLoS ONE 14(11)
Kategorie: Research Article
doi: 10.1371/journal.pone.0225474


The goal of the present study was the evaluation of the fatty acid (FA) profile of lipid fraction from dry common beans (Phaseolus vulgaris L.) (CBO) harvested from North-East (NE) and South-West (SW) of Romania and to protect against thermal and oxidative degradation of the contained omega-3 and omega-6 polyunsaturated fatty acid (PUFA) glycerides by β-cyclodextrin (β-CD) nanoencapsulation, using kneading method. The most abundant FAs in the CBO samples were PUFAs, according to gas chromatography-mass spectrometry (GC-MS) analysis. Linoleic acid (methyl ester) was the main constituent, having relative concentrations of 43.4 (±1.95) % and 35.23 (±0.68) % for the lipid fractions separated from the common beans harvested from the NE and SW of Romania, respectively. Higher relative concentrations were obtained for the omega-3 α-linolenic acid methyl ester at values of 13.13 (±0.59) % and 15.72 (±0.30) % for NE and SW Romanian samples, respectively. The omega-3/omega-6 ratio consistently exceeds the lower limit value of 0.2, from where the PUFA glyceride mixture is valuable for the human health. This value was 0.32 (±0.02) for the NE samples and significantly higher for the CBO-SW samples, 0.51 (±0.01). These highly hydrophobic mixtures especially consisting of PUFA triglycerides provide β-CD complexes having higher thermal and oxidative stability. Kneading method allowed obtaining β-CD/CBO powder-like complexes with higher recovery yields of >70%. Thermal analyses of complexes revealed a lower content of hydration water (3.3–5.8% up to 110°C in thermogravimetry (TG) analysis and 154–347 J/g endothermal effect in differential scanning calorimetry (DSC) analysis) in comparison with the β-CD hydrate (12.1% and 479.5–480 J/g, respectively). These findings support the molecular inclusion process of FA moieties into the β-CD cavity. Attenuated total reflectance-Fourier transform infrared spectroscopy (ATR-FTIR) analysis reveals the formation of the β-CD/CBO inclusion complexes by restricting the vibration and bending of some bonds from the host and guest molecules. Moreover, powder X-ray diffractometry (PXRD) analysis confirm the formation of the host-guest complexes by modifying the diffractograms for β-CD/CBO complexes in comparison with the β-CD and β-CD + CBO physical mixtures. A significant reduction of the level of crystallinity from 93.3 (±5.3) % for β-CD to 60–60.9% for the corresponding β-CD/CBO complexes have been determined. The encapsulation efficiency (EE), the profile of FAs, as well as the controlled release of the encapsulated oil have also been evaluated. The EE was >40% in all cases, the highest value being obtained for β-CD/CBO-SW complex. The SFA content increased, while the unsaturated FA glycerides had lower relative concentrations in the encapsulated CBO samples. It can be emphasized that the main omega-3 FA (namely α-linolenic acid glycerides) had close concentrations in the encapsulated and raw CBOs (13.13 (±0.59) % and 14.04 (±1.54) % for non-encapsulated and encapsulated CBO-NE samples, 15.72 (±0.30) % and 12.41 (±1.95) % for the corresponding CBO-SW samples, respectively). The overall unsaturated FA content significantly decreased after complexation (from 19.03–19.16% for the raw CBOs to 17.3–17.7% for encapsulated oils in the case of MUFAs, and from 55.7–58.8% to 35.13–43.36% for PUFAs). On the other hand, the omega-3/omega-6 ratio increased by β-CD nanoencapsulation to 0.51 (±0.07) and 0.76 (0.26) for β-CD/CBO-NE and β-CD/CBO-SW complexes, respectively. As a conclusion, the lipid fractions of the Romanian common beans are good candidates for β-CD complexation and they can be protected against thermal and oxidative degradation in common beans based food products such as functional foods or food supplements using natural CDs.

Klíčová slova:

Esters – Fatty acids – Gas chromatography-mass spectrometry – Lipids – Oils – Vibration – Glycerides – Hydrates


1. Belitz H-D, Grosch W, Schieberle P, Food chemistry. Springer-Verlag: Berlin Heidelberg, 2009.

2. Gepts P, Beans: Origins and Development. In Encyclopedia of global archaeology, Springer: New York 2014.

3. Jones AL, Phaseolus bean: Post-harvest Operations. Food and Agriculture Organization of the United Nations: 1999.

4. Pathania A, Sharma SK, Sharma PN, Common Bean. In Broadening the genetic base of grain legumes, Singh M. et al. (eds.), Ed. Springer India: 2014.

5. Luna-Vital DA, Mojica L, González de Mejía E, Mendoza S, Loarca-Piña G. Biological potential of protein hydrolysates and peptides from common bean (Phaseolus vulgaris L.): A review. Food Research International. 2015;76:39–50. doi: 10.1016/j.foodres.2014.11.024

6. Celmeli T, Sari H, Canci H, Sari D, Adak A, Eker T, et al. The nutritional content of common bean (Phaseolus vulgaris L.) landraces in comparison to modern varieties. Agronomy. 2018;8:Art. 166. doi: 10.3390/agronomy8090166

7. Pirman T, Stibilj V. An influence of cooking on fatty acid composition in three varieties of common beans and in lentil. European Journal of Lipid Science and Technology. 2003;217:498–503. doi: 10.1007/s00217-003-0784-2

8. Stefanov K, Popova I, Nikolova-Damyanova B, Kimenov G, Popov S. Lipid and sterol changes in Phaseolus vulgaris caused by lead ions. Phytochemistry. 1992;31:3745–3748. doi: 10.1016/S0031-9422(00)97520-4

9. Yoshida H, Tomiyama Y, Kita S, Mizushina Y. Lipid classes, fatty acid composition and triacylglycerol molecular species of kidney beans (Phaseolus vulgaris L.). European Journal of Lipid Science and Technology. 2005;107:307–315. doi: 10.1002/ejlt.200401078

10. Yoshida H, Tomiyama Y, Mizushina Y. Characterization in the fatty acid distributions of triacylglycerols and phospholipids in kidney beans (Phaseolus vulgaris L.). Journal of Food Lipids. 2005;12:169–180. doi: 10.1111/j.1745-4522.2005.00016.x

11. Augustin MA, Sanguansri L. Use of encapsulation to inhibit oxidation of lipid ingredients in foods. In Oxidation in foods and beverages and antioxidant applications, Volume 2: Management in different industry sectors, Elias EDR, McClements DJ (eds.), Woodhead Publishing Limited: Cambridge, England: 2010;2:479–495.

12. Khare AR, Vasisht N. Nanoencapsulation in the food industry: Technology of the future. In Microencapsulation in the food industry. A practical implementation guide, Gaonkar AG, Vasisht N, Khare AR, Sobel R (eds.), Elsevier Inc.: Amsterdam: 2014;151–155.

13. Nickerson M, Yan C, Cloutier S, Zhang W. Protection and masking of omega-3 and -6 oils via microencapsulation. In Microencapsulation in the food industry. A practical implementation guide, Gaonkar AG, Vasisht N, Khare AR, Sobel R (eds.), Elsevier Inc.: Amsterdam: 2014;485–500.

14. Kurkov SV, Loftsson T. Cyclodextrins. International Journal of Pharmaceutics. 2013;453:167–180. doi: 10.1016/j.ijpharm.2012.06.055 22771733

15. Mortensen A, Aguilar F, Crebelli R, Di Domenico A, Dusemund B, Frutos MJ, et al. Re-evaluation of β-cyclodextrin (E 459) as a food additive. EFSA Journal. 2016;14:4628. doi: 10.2903/j.efsa.2016.4628

16. Crini G. Review: A History of Cyclodextrins. Chemical Reviews. 2014;114:10940–10975. doi: 10.1021/cr500081p 25247843

17. Szente L, Fenyvesi É. Cyclodextrin-lipid complexes: cavity size matters. Structural Chemistry. 2017;28:479–492. doi: 10.1007/s11224-016-0884-9

18. Zhang J, Ma PX. Cyclodextrin-based supramolecular systems for drug delivery: Recent progress and future perspective. Advanced Drug Delivery Reviews. 2013;65:1215–1233. doi: 10.1016/j.addr.2013.05.001 23673149

19. Kfoury M, Auezova L, Greige-Gerges H, Fourmentin S. Promising applications of cyclodextrins in food: Improvement of essential oils retention, controlled release and antiradical activity. Carbohydrate Polymers. 2015;131:264–272. doi: 10.1016/j.carbpol.2015.06.014 26256184

20. Durante M, Lenucci MS, Marrese PP, Rizzi V, De Caroli M, Piro G, et al. α-Cyclodextrin encapsulation of supercritical CO2 extracted oleoresins from different plant matrices: A stability study. Food Chemistry. 2016;199:684–693. doi: 10.1016/j.foodchem.2015.12.073 26776025

21. Hădărugă DI, Birău (Mitroi) CL, Gruia AT, Păunescu V, Bandur GN, Hădărugă NG. Moisture evaluation of β-cyclodextrin/fish oils complexes by thermal analyses: A data review on common barbel (Barbus barbus L.), Pontic shad (Alosa immaculata Bennett), European wels catfish (Silurus glanis L.), and common bleak (Alburnus alburnus L.) living in Danube river. Food Chemistry. 2017;236:49–58. doi: 10.1016/j.foodchem.2017.03.093 28624089

22. Hădărugă DI, Ünlüsayin M, Gruia AT, Birău (Mitroi) C, Rusu G, Hădărugă NG. Thermal and oxidative stability of Atlantic salmon oil (Salmo salar L.) and complexation with β-cyclodextrin. Beilstein Journal of Organic Chemistry. 2016;12:179–191. doi: 10.3762/bjoc.12.20 26977177

23. Trichard L, Chaminade P, Grossiord J-L, Le Bas G, Huang N, Durand D, et al. Beads made of alpha-cyclodextrin and vegetable oils: oil composition and physicochemical properties influence bead feasibility and properties. Journal of Drug Delivery Science and Technology. 2011;21:189–194. doi: 10.1016/S1773-2247(11)50021-8

24. Ünlüsayin M, Hădărugă NG, Rusu G, Gruia AT, Păunescu V, Hădărugă DI. Nano-encapsulation competitiveness of omega-3 fatty acids and correlations of thermal analysis and Karl Fischer water titration for European anchovy (Engraulis encrasicolus L.) oil/beta-cyclodextrin complexes. LWT—Food Science and Technology. 2016;68:135–144. doi: 10.1016/j.lwt.2015.12.017

25. Chew SC, Tan CP, Nyam KL. Microencapsulation of refined kenaf (Hibiscus cannabinus L.) seed oil by spray drying using β-cyclodextrin/gum arabic/sodium caseinate. Journal of Food Engineering. 2018; 237:78–85. doi: 10.1016/j.jfoodeng.2018.05.016

26. Choi M-J, Ruktanonchai U, Min S-G, Chun J-Y, Soottitantawat A. Physical characteristics of fish oil encapsulated by β-cyclodextrin using an aggregation method or polycaprolactone using an emulsion-diffusion method. Food Chemistry. 2010;119:1694–1703. doi: 10.1016/j.foodchem.2009.09.052

27. Roisnel T, Rodríguez-Carvajal J. WinPLOTR: a Windows tool for powder diffraction patterns analysis. Materials Science Forum. Proceedings of the European Powder Diffraction Conference (EPDIC7). 2001;378–381:118–123.

28. Rodríguez-Carvajal J, Roisnel T. FullProf.98 and WinPLOTR: A new Windows 95/NT applications for diffraction. Commission for Powder Diffraction. International Union of Crystallography. Newsletter No 20 (May-August) Summer 1998.

29. Rubio-Rodríguez N, Beltrán S, Jaime I, de Diego SM, Sanz MT, Carballido JR. Production of omega-3 polyunsaturated fatty acid concentrates: A review. Innovative Food Science and Emerging Technologies. 2010;11:1–12. doi: 10.1016/j.ifset.2009.10.006

30. de Souza Siqueira Quintans J, Menezes PP, Santos MRV, Bonjardim LR, Almeida JRGS, Gelain DP, et al. Improvement of p-cymene antinociceptive and anti-inflammatory effects by inclusion in β-cyclodextrin. Phytomedicine. 2013;20:436–440. doi: 10.1016/j.phymed.2012.12.009 23357360

31. Lima PSS, Lucchese AM, Araújo-Filho HG, Menezes PP, Araújo AAS, Quintans-Júnior LJ, et al. Inclusion of terpenes in cyclodextrins: Preparation, characterization and pharmacological approaches. Carbohydrate Polymers. 2016;151:965–987. doi: 10.1016/j.carbpol.2016.06.040 27474645

32. Menezes PP, Serafini MR, Quintans-Júnior LJ, Silva GF, Oliveira JF, Carvalho FMS, Souza JCC, Matos JR, Alves PB, Matos IL, Hădărugă DI, Araújo AAS. Inclusion complex of (-)-linalool and β-cyclodextrin. Journal of Thermal Analysis and Calorimetry. 2014;115:2429–2437. doi: 10.1007/s10973-013-3367-x

33. Menezes PP, Serafini MR, Santana BV, Nunes RS, Quintans LJ Jr, Silva GF, et al. Solid-state β-cyclodextrin complexes containing geraniol. Thermochimica Acta. 2012;548:45–50. doi: 10.1016/j.tca.2012.08.023

34. Hădărugă NG, Bandur GN, Hădărugă DI, Ch. 4. Thermal Analyses of Cyclodextrin Complexes. In Cyclodextrin Fundamentals, Reactivity and Analysis, Fourmentin S, Crini G, Lichtfouse E (eds.). Springer International Publishing AG, Springer Nature: Singapore, 2018;155–221. doi: 10.1007/978-3-319-76159-6_4

35. Hădărugă NG, Bandur GN, David I, Hădărugă DI. A review on thermal analyses of cyclodextrins and cyclodextrin complexes. Environmental Chemistry Letters. 2019;17:349–373. doi: 10.1007/s10311-018-0806-8

36. Hădărugă NG, Szakal RN, Chirilă CA, Lukinich-Gruia AT, Păunescu V, Muntean C, Rusu G, Bujancă G, Hădărugă DI. Complexation of Danube common nase (Chondrostoma nasus L.) oil by β-cyclodextrin and 2-hydroxypropyl-β-cyclodextrin. Food Chemistry. 2020; 303:art. 125419. doi: 10.1016/j.foodchem.2019.125419 31470276

37. Nunes C, Mahendrasingam A, Suryanarayanan R. Quantification of crystallinity in substantially amorphous materials by synchrotron X-ray powder diffractometry. Pharmaceutical Research. 2005;22:1942–1953. doi: 10.1007/s11095-005-7626-9 16132342

Článek vyšel v časopise


2019 Číslo 11