journal article·2025-05-25Open access

DART-HRMS for the Rapid Assessment of Bioactive Compounds in Ultrasound-Processed Rapeseed Meal By-Product

Anna Lante, Andrea Massaro, Carmela Zacometti, Dasha Mihaylova, Vesela Chalova, Albert Krastanov, Hristo Kalaydzhiev, Miluska Cisneros, Greta Morbin, Giorgia Riuzzi, Severino Segato, Alessandra Tata

Applied Sciences· Volume 15· Issue 11

Abstract

In line with the recommended European policy for a zero-waste crop supply chain, a lab-pilot optimisation process to valorise the by-products of industrially produced rapeseed meal (RM) was performed. Three batches of RM were first processed into ethanol-wash solutes (EWS) and then optimised (OEWS) by an ultrasound-assisted (UA) treatment. After direct analysis in real time–high resolution mass spectrometry (DART-HRMS) analysis, data were processed applying a partial least square–discriminant analysis (PLS-DA), which retrieved the 15 most discriminative ions able to characterise the biochemical changes during the ethanol-washing and UA optimisation process. The metabolomic fingerprinting of EWS and OEWS generated an accurate and well-defined 3D spatial clusterisation based on a restricted pool of informative bioactive compounds. A significantly higher relative abundance of sinapic, azelaic, and vernolic acids and a lower incidence of the oleic and palmitic fatty acids were detected in OEWS. DART-HRMS generated a vast amount of biochemical information in one single run, also demonstrating that its association with an untargeted multivariate statistical approach would be a valuable tool for revealing specific functional biomarkers. This would eventually enhance the circular and effective use of rapeseed residuals coming from this plant’s oilseed industry.
Source: crossref · Quality: baseline

Research context

OpenAlex topics: Metabolomics and Mass Spectrometry Studies · Meat and Animal Product Quality · Advanced Chemical Sensor Technologies

SciVX discovery tags are terminology-based. OpenAlex topics are source-provided classifications.

Affiliations

Department of Agronomy, Food, Natural Resources, Animals, and Environment-DAFNAE, Padova University, Viale dell’Università, 16, 35020 Legnaro, Italy

Experimental Chemistry Laboratory, Istituto Zooprofilattico Sperimentale delle Venezie, Viale Fiume, 78, 36100 Vicenza, Italy

Department of Microbiology and Biotechnology, University of Food Technologies, 26 Maritza Blvd., 4002 Plovdiv, Bulgaria

Department of Biochemistry and Nutrition, University of Food Technologies, 26 Maritza Blvd., 4002 Plovdiv, Bulgaria

Department of Analytical Chemistry and Physical Chemistry, University of Food Technologies, 26 Maritza Blvd., 4002 Plovdiv, Bulgaria

Department of Animal Medicine, Production and Health, Padova University, Viale dell’Università, 16, 35020 Legnaro, Italy

Funding

Interconnected Nord-Est Innovation Ecosystem (iNEST) from the European Union Next GenerationEU · Bulgarian National Science Fund

References (49)

Show source-provided references
1. Rapeseed proteins for technical applications: Processing, isolation, modification and functional properties—A review10.1016/j.indcrop.2020.112986 ↗
2. Determination of vanillin compounds in oilseed using solid-phase extraction with ultra-performance liquid chromatography–mass spectrometry10.1016/j.jfca.2024.106388 ↗
3. Marudova, M., Viraneva, A., Antova, G., Nikolova, K., Petkova, Z., and Teneva, O. (2025). Physico-Chemical Characterization of Sesame/Rapeseed Oil Mixtures. Appl. Sci., 15.10.3390/app15020704 ↗
4. Wongsirichot, P., Gonzalez-Miquel, M., and Winterburn, J. (2022). Recent advances in rapeseed meal as alternative feedstock for industrial biotechnology. Biochem. Eng. J., 180.10.1016/j.bej.2022.108373 ↗
5. Dygas, D., Liszkowska, W., Steglinska, A., Sulyok, M., Kregiel, D., and Berlowska, J. (2023). Rapeseed Meal Waste Biomass as a Single-Cell Protein Substrate for Nutritionally-Enhanced Feed Components. Processes, 11.10.20944/preprints202305.0279.v1 ↗
6. Multescu, M., Marinas, I.C., Susman, I.E., and Belc, N. (2022). Byproducts (flour, meals, and groats) from the vegetable oil industry as as potential source of antioxidants. Foods, 11.10.3390/foods11030253 ↗
7. Petraru, A., and Amariei, S. (2024). Rapeseed—An Important Oleaginous Plant in the Oil Industry and the Resulting Meal a Valuable Source of Bioactive Compounds. Plants, 13.10.3390/plants13213085 ↗
8. Di Lena, G., Del Pulgar, J.S., Lucarini, M., Durazzo, A., Ondrejíčková, P., Oancea, F., Frincu, R.M., Aguzzi, A., Nicoli, S.F., and Casini, I. (2021). Valorization potentials of rapeseed meal in a biorefinery perspective: Focus on nutritional and bioactive components. Molecules, 26.10.3390/molecules26226787 ↗
9. Effects of oilseed supplements on milk production and quality in dairy cows fed a hay-based diet10.4081/ijas.2007.395 ↗
10. Lestingi, A. (2024). Alternative and sustainable protein sources in pig diet: A review. Animals, 14.10.3390/ani14020310 ↗
11. Canola Seed Meal as a Potential Source of Natural Antioxidant
12. Increasing levels of rapeseed expeller meal in diets for pigs: Effects on protein and energy metabolism10.1017/S1751731118000988 ↗
13. Kaempferol 3-O-(2‴-O- Sinapoyl-β-sophoroside) Causes the Undesired Bitter Taste of Canola/Rapeseed Protein Isolates10.1021/acs.jafc.8b06260 ↗
14. Manikandan, A., Muthusamy, S., Wang, E.S., Ivarson, E., Manickam, S., Sivakami, R., Narayanan, M.B., Zhu, L.-H., Rajasekaran, R., and Kanagarajan, S. (2024). Breeding and biotechnology approaches to enhance the nutritional quality of rapeseed byproducts for sustainable alternative protein sources—A critical review. Front. Plant Sci., 15.10.3389/fpls.2024.1468675 ↗
15. Antioxidant capacity of rapeseed extracts obtained by conventional and ultrasound-assisted extraction10.1007/s11746-014-2557-4 ↗
16. Micronutrient content of cold-pressed, hot-pressed, solvent extracted and RBD canola oil: Implications for nutrition and quality10.1002/ejlt.201300288 ↗
17. Hussain, S., Rehman, A.U., Obied, H.K., Luckett, D.J., and Blanchard, C.L. (2022). Extraction, Chemical Characterization, In Vitro Antioxidant, and Antidiabetic Activity of Canola (Brassica napus L.) Meal. Separations, 9.10.3390/separations9020038 ↗
18. Sesame defatted flour: Antioxidant response and improvement in carbohydrate metabolism in high-fructose/high-saturated fatty acids diet-fed mice10.1007/s13197-024-06049-2 ↗
19. Yang, G., Zhu, L., Wang, Y., Yu, Y., Liu, X., Xia, J., Yang, Y., Wang, H., and Feng, B. (2025). Antihypertensive effect of sinapine extracted from rapeseed meal in 2K1C hypertensive rats. Sci. Rep., 15.10.1038/s41598-025-88926-0 ↗
20. Valorization of Rapeseed Meal: Influence of Ethanol Antinutrients Removal on Protein Extractability, Amino Acid Composition and Fractional Profile10.1007/s12649-018-00553-1 ↗
21. Improvement in enzymolysis efficiency and bioavailability of rapeseed meal protein concentrate by sequential dual frequency ultrasound pretreatment10.1016/j.procbio.2021.01.012 ↗
22. Recent Advances in the Extraction of Phenolic Compounds from Food Wastes by Emerging Technologies10.1007/s11947-024-03365-5 ↗
23. A comprehensive review on different classes of polyphenolic compounds present in edible oils10.1016/j.foodres.2021.110312 ↗
24. Analytical techniques for the chemical analysis of plant biomass and biomass products10.1039/C4AY00388H ↗
25. Determination of Aminophosphonate Herbicides in Glutamate Loaded Spice Mix by LC-IDMS and Method Extension to Other Food Matrices10.1007/s12161-022-02248-9 ↗
26. Developing a new screening method for the detection of antibiotic residues in muscle tissues in using liquid chromatography and high resolution mass spectrometry with a LC-LTQ-Orbitrap instrument10.1080/19440049.2011.605772 ↗
27. Ambient mass spectrometry for food science and industry10.1016/j.trac.2018.07.017 ↗
28. Recent advances in the application of direct analysis in real time-mass spectrometry (DART-MS) in food analysis10.1016/j.foodres.2024.114488 ↗
29. Novel DART-MS approach for rapid and environmentally friendly determination of the geographical origin of hazelnuts (Corylus avellana L.)10.1016/j.foodchem.2024.142265 ↗
30. DART-HRMS reveals metabolic changes of whey through microparticulation and fermentations10.1016/j.afres.2024.100443 ↗
31. Lippolis, V., De Angelis, E., Fiorino, G.M., Di Gioia, A., Arlorio, M., Logrieco, A.F., and Monaci, L. (2020). Geographical Origin Discrimination of Monofloral Honeys by Direct Analysis in Real Time Ionization-High Resolution Mass Spectrometry (DART-HRMS). Foods, 9.10.3390/foods9091205 ↗
32. Rapid screening and quantification of residual pesticides and illegal adulterants in red wine by direct analysis in real time mass spectrometry10.1016/j.chroma.2016.09.073 ↗
33. Chemical analysis and classification of black pepper (Piper nigrum L.) based on their country of origin using mass spectrometric methods and chemometrics10.1016/j.foodres.2020.109877 ↗
34. Ambient Ionization Mass Spectrometry: Recent Developments and Applications10.1021/acs.analchem.9b00807 ↗
35. Phytochemical Profile and Bioactivity of Industrial Rapeseed Meal Ethanol-Wash Solutes10.1007/s12649-021-01373-6 ↗
36. Ultrasound-assisted extraction of antioxidant bioactive compounds from wastes of rapeseed industry and their application in delaying rapeseed oil oxidation10.1016/j.eti.2023.103081 ↗
37. Ionization Mechanism of Positive-Ion Nitrogen Direct Analysis in Real Time10.1007/s13361-017-1885-7 ↗
38. Tata, A., Massaro, A., Riuzzi, G., Lanza, I., Bragolusi, M., Negro, A., Novelli, E., Piro, R., Gottardo, F., and Segato, S. (2022). Ambient mass spectrometry for rapid authentication of milk from Alpine or lowland forage. Sci. Rep., 12.10.1038/s41598-022-11178-9 ↗
39. Zacometti, C., Lante, A., Cisneros, M., Massaro, A., Mihaylova, D., Chalova, V., Krastanov, A., Kalaydzhiev, H., Riuzzi, G., and Tata, A. (2024). Rapid assessment of metabolomic fingerprinting of recycled sunflower by-products via DART-HRMS. Molecules, 29.10.3390/molecules29174092 ↗
40. Lanzhou lily as nutraceuticals: Identification of active metabolites via the UHPLC-Q-exactive orbitrap mass spectrometer10.1016/j.microc.2025.113626 ↗
41. Zhang, Y., Chen, S., Yuan, M., Xu, Y., and Xu, H. (2022). Gout and Diet: A Comprehensive Review of Mechanisms and Management. Nutrients, 14.10.3390/nu14173525 ↗
42. Definition of hyperuricemia and gouty conditions10.1097/BOR.0000000000000028 ↗
43. Sinapinic and protocatechuic acids found in rapeseed: Isolation, characterisation and potential benefits for human health as functional food ingredients
44. Processing of rapeseed oil: Effects on sinapic acid derivative content and oxidative stability10.1007/s00217-003-0721-4 ↗
45. Cairone, F., Allevi, D., Cesa, S., Fabrizi, G., Goggiamani, A., Masci, D., and Iazzetti, A. (2023). Valorisation of Side Stream Products through Green Approaches: The Rapeseed Meal Case. Foods, 12.10.3390/foods12173286 ↗
46. Sinapic acid ameliorate cadmium-induced nephrotoxicity: In vivo possible involvement of oxidative stress, apoptosis, and inflammation via NF-κB downregulation10.1016/j.etap.2017.02.014 ↗
47. Antioxidant, cholesterol lowering activity, and analysis of Caesalpinia bonducella seeds extract10.3897/pharmacia.70.e96817 ↗
48. Brenna, E., Colombo, D., Di Lecce, G., Gatti, F.G., Ghezzi, M.C., Tentori, F., Tessaro, D., and Viola, M. (2020). Conversion of oleic acid into azelaic and pelargonic acid by a chemo-enzymatic route. Molecules, 25.10.3390/molecules25081882 ↗
49. Todea, A., Deganutti, C., Spennato, M., Asaro, F., Zingone, G., Milizia, T., and Gardossi, L. (2021). Azelaic Acid: A Bio-Based Building Block for Biodegradable Polymers. Polyners, 13.10.3390/polym13234091 ↗