Center for Molecular Modeling - K. Raes

A comparative theoretical study on the solvent dependency of anthocyanin extraction profiles

kphan — Mon, 24 Jan 2022 08:43:36 +0000

K.T. Phan, E. Van den Broeck, K. Raes, K. De Clerck, V. Van Speybroeck, S. De Meester

Journal of Molecular Liquids

351

2022

Abstract

Anthocyanidins and anthocyanins are flavonoids with nutritional, antioxidative and color properties that are present in various food products and biomass, such as food waste. The large chemical diversity amongst these molecules potentially leads to different affinities or activities in food and non-food applications. In order to characterize the extraction profile, advanced analytical techniques along with optimized separation procedures are required. Alternatively, theoretical tools can be applied for predicting the solubility or binding affinity of molecules in various reaction media. In this paper, the solubility of anthocyanidins and anthocyanins was analyzed by various theoretical tools such as group contribution methods (e.g., Hansen solubility parameters and Flory-Huggins interaction parameter (χ₁₂)) and molecular modeling (e.g., static calculations based on Density Functional Theory (DFT) and COSMO-RS). It was found that COSMO-RS was able to give quantitative information on the solubility behavior within various pure solvents and it is able to describe the main intermolecular interactions between colorant and solvent, while Hansen solubility parameters were most appropriate to find the most optimal organic solvent-water mixture ratio. In general, solvents with electron-rich aromatic rings and/or containing electron donors, acting as hydrogen bond acceptors, showed the highest solubilizing power for anthocyanidins and anthocyanins.

Gold Open Access

DOI

http://dx.doi.org/10.1016/j.molliq.2022.118606

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1-s2.0-S016773222200143X-main.pdf

Non-food applications of natural dyes extracted from agro-food residues: A critical review

kphan — Tue, 13 Apr 2021 08:22:04 +0000

K.T. Phan, K. Raes, V. Van Speybroeck, M. Roosen, K. De Clerck, S. De Meester

Journal of Cleaner Production

126920

2021

Abstract

Fruit and vegetables contain molecules that have particular colors, which can potentially be an environmentally attractive substitute for their synthetic counterparts in (non )food applications. The most sustainable source for such natural colorants would be by the valorization of by-products from the fruit and vegetable industries, but qualitative and quantitative characteristics of food by-products for this purpose remain scarce. Natural dyes also show mediocre stability and affinity toward textile fibers, which questions their potential feasibility for application and level of sustainability to overcome these issues. This review describes three dye classes (i.e., anthocyanins, quinones, and carotenoids) along with their occurrence, mass, and concentration in by-products that are generated from agricultural losses as well as the fruit and vegetable processing industries. To tackle the shortcomings of natural dyes on fibers, several application techniques were collected from the literature. A discussion on techno-economic potential and environmental sustainability is included. The latter is done by including a life cycle assessment (LCA) to investigate the environmental impact of extracting anthocyanins, quinones, and carotenoids from fruit and vegetable processing by-products and their subsequent application to the dyeing process. The mapping of by-products for each natural dye class illustrates the vast availability of agro-food residues (>0.1 Mt annually in the EU-28) with a natural dye content of up to 56 kg/t DW for anthocyanins, 18 kg/t DW for quinones, and 593 kg/t DW for carotenoids. Metallic mordants are mostly favored for improving the fixation of natural dyes but entail potential environmental issues. Greener approaches, such as biomordants and enzymes, still show room for improvement, chemical modification methods might also guarantee dye fixation, though questionable in environmental sustainability. The different valorization scenarios of anthocyanins, quinones, and carotenoids from food waste, analyzed with LCA, showed the environmental competitiveness of these natural dyes, applied as a crude extract, compared to synthetic dyes. The valorization routes design shows that agricultural losses and food processing waste streams are adequate sources of natural dyes, especially to be applied in niche scale applications.

DOI

https://doi.org/10.1016/j.jclepro.2021.126920

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PhanNon-food applications of natural dyes extracted from agro-foodresidues A critical review.pdf

A comparative study on the photophysical properties of anthocyanins and pyranoanthocyanins

kphan — Thu, 21 Jan 2021 16:40:17 +0000

K.T. Phan, S. De Meester, K. Raes, K. De Clerck, V. Van Speybroeck

Chemistry - A European Journal

27 (19), 5956-5971

2021

Abstract

Anthocyanins and pyranoanthocyanins are flavonoids that are present in various food products (e.g. fruit, vegetables, wine, etc.). The large chemical diversity amongst these molecules leads to compound specific properties such as color and stability towards external conditions. These properties are also attractive for food and non‐food applications. The photophysical experimental characterization is not easy as this generally demands advanced analytical techniques along with optimized separation procedures. Molecular modeling can provide insights into the fundamental understanding of the photophysical properties of these compounds in a uniform way for a broad set of compounds. However, the current literature is quite fragmented on this topic. Herein, a large set of 140 naturally derived anthocyanins was evaluated in a systematic way with three functionals (B3LYP, PBE0 and CAM‐B3LYP). The accuracy of these functionals was determined with experimental literature λ max,vis ‐values. Next to λ max,vis ‐values, TD‐DFT calculations also provided oscillator strengths, molar absorption coefficients and orbital energies, which define whether specific natural anthocyanin‐based compounds can be deployed in food and non‐food applications such as food additives/colorants, textile dyeing, analytical standards and dye sensitized solar cells (DSSCs).

DOI

https://doi.org/10.1002/chem.202004639

The potential of anthocyanins from blueberries as a natural dye for cotton: A combined experimental and theoretical study

kphan — Tue, 28 Jan 2020 15:30:58 +0000

K.T. Phan, E. Van den Broeck, V. Van Speybroeck, K. De Clerck, K. Raes, S. De Meester

Dyes and Pigments

176, 108180

2020

Abstract

Natural dyes might be more environmentally sustainable compared to their synthetic counterparts, however in general their performance is worse. Therefore, typically metallic mordants are applied to improve the natural dye's affinity towards substrates, but this is not a suitable technique in a ‘green story’. In this paper, we test the potential of using anthocyanins from blueberry waste for dyeing cotton with biomordants, which are selected to tailor the intermolecular interactions such as hydrogen bonds, ionic bonds and π-π interactions with the dye molecule. In the experimental part, parameters during extraction and dyeing were optimized (e.g. temperature, pH, dyeing time and concentration). The effect of the (bio)mordants was monitored by Fourier transform infrared spectroscopy, spectrophotometric measurements and standard ISO wash and light tests. It was shown that stannous chloride stands out as metallic mordant, while no biomordants show sufficient intermolecular interactions to replace this metal salt. The experimental study has been corroborated with a series of molecular modeling calculations to obtain more insight into the intermolecular interactions between dye and (bio)mordants. To this end, both static Density Functional Theory based calculations as semi-empirical and force field based molecular dynamics calculations have been performed. The results indeed confirm that, in general, too small interaction energies for the biomordants of interest with the dye molecules are found, in correspondence with experimental findings. Overall, by performing systematic experiments in combination with the interpretation of the molecular models, this study yields valuable insights into the development of green routes towards use of anthocyanins as a natural dye for cellulose-based materials.

Open Access version available at UGent repository

DOI

https://doi.org/10.1016/j.dyepig.2019.108180

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1-s2.0-S0143720819322910-main.pdf

Non-Food Applications of Anthocyanins Extracted from Agro-Food Residues: a Combined Experimental and Theoretical Study

leen — Tue, 26 Oct 2021 13:00:18 +0000

K.T. Phan

Mon, 07/06/2021

Faculty of Bioscience Engineering, Coupure links, Ghent

https://biblio.ugent.be/publication/8709612

Supervisors

Prof. dr. ir. Steven De Meester; Prof. dr. ir. Veronique Van Speybroeck; Prof. dr. ir. Katleen Raes; Prof. dr. ir. Karen De Clerck

Attachment (private)

PhDThesisKP280521Final (1)-gecomprimeerd.pdf

The valorization of natural colorants from waste streams and subsequent application on fibers

samuel — Thu, 06 Feb 2020 08:45:06 +0000

K.T. Phan, V. Van Speybroeck, K. Raes, S. De Meester

ISBN/ISSN:

Talk

Conference / event / venue

14th International conference on Renewable Resources and Biorefineries (RRB-14)

Gent, Belgium

Wednesday, 30 May, 2018 to Friday, 1 June, 2018

Exploring the potential of anthocyanins as a natural dye for non-food applications

samuel — Thu, 06 Feb 2020 08:23:20 +0000

K.T. Phan, E. Van den Broeck, V. Van Speybroeck, K. De Clerck, K. Raes, S. De Meester

ISBN/ISSN:

Talk

Conference / event / venue

23rd Green Chemistry & Engineering conference (GCE) ; 9th International conference on Green and Sustainable Chemistry (GSC)

Reston, VA, USA

Tuesday, 11 June, 2019 to Thursday, 13 June, 2019

Natural dyes from food waste; the use of molecular engineering to develop fit-for-purpose extraction pathways

wim — Tue, 02 May 2017 06:34:19 +0000

K.T. Phan

Supervisors

Prof. Dr. S. De Meester, Prof. Dr. ir. Veronique Van Speybroeck, Prof. Dr. Kathleen Raes