Abstract

In this paper, we investigate the potential of zwitterions like amino acids as alternative (bulking) sugar replacers. Commonly, polyols or oligosaccharides are taken as sugar placers, but they are perceived as less attractive due to laxative problems. The choice of amino acids as alternative sugar replacers is inspired by their presence in Natural Deep Eutectic Solvents (NADES) and compatible solutes, next to carbohydrates. In these compounds, hydrogen bonding plays an essential role similar to sugar (replacers) in food. Because of the novelty of the topic, we first discuss at length NADES as a potential source of alternative plasticizers/sugar replacers. Subsequently, we perform a detailed analysis of their thermodynamic properties, to investigate whether amino acids and related zwitterions indeed have the appropriate properties for sugar replacement.Our analysis shows that several zwitterions indeed have proper thermodynamic properties, which can make them good plasticizers and humectants. However, the use of several zwitterions can be restricted by their poor solubility, except for L-proline. Solubility problems can be circumvented by their use in mixtures of several sugar replacers, which enhances their solubility. The poor solubility makes it also difficult to characterize the glass transition temperatures of the pure solute Tg,g. Consequently, we have estimated them via extrapolation of the viscosity curves, which is shown to scale with Tg∕T. We have taken Tg of the plasticizer solution as a measure of the hydrogen bond density, nOH,eff.That measure is shown to explain the melting behaviour of biopolymers like egg white and starch in glycine and L-proline solutions, similar to sugar (replacers). However, our measurements of the biopolymer melting show indications of phase separation at high moisture contents for both amino acid solutions as for carbohydrate solutions. Overall, the amino acids and other compatible zwitterions have very similar thermodynamic behaviour as sugars and their carbohydrate-based replacers. In proper combinations with alternative plasticizers, the zwitterionic compatible solutes can well be used in sugar replacement strategies for foods.

Highlights

  • In bakery products sugars provide a wide variety of functionalities, next to providing sweetness (Davis, 1995; Pareyt et al, 2009; Wilderjans, Luyts, Brijs, & Delcour, 2013; van der Sman & Renzetti, 2019)

  • Like ternary systems comprising two carbohydrates, we describe the thermodynamics of amino acid/carbohydrate/water systems using Flory–Huggins theory (Van der Sman, 2017)

  • Marsh et al (2017) extend beyond the solubility range of glycine and L-alanine. This is achieved via the use of small aerosol droplets, with radii in the range of 4-30 μm, where crystallization is inhibited, but droplet curvature effects on water activity are negligible. This means a considerable extension of the data range for fitting the Flory–Huggins theory to the moisture sorption of glycine and L-alanine, which adds to the accuracy of the fitted interaction parameter χ

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Summary

Introduction

In bakery products sugars provide a wide variety of functionalities, next to providing sweetness (Davis, 1995; Pareyt et al, 2009; Wilderjans, Luyts, Brijs, & Delcour, 2013; van der Sman & Renzetti, 2019). The functionality of sugar and its replacers in bakery and confectionery products can largely be characterized by their behaviour as (1) plasticizer and (2) humectant (Wilderjans et al, 2013; van der Sman & Renzetti, 2019). For the remainder of this paper, we investigate this behaviour of the sweet amino acids, glycine, L-alanine, and L-proline, and in combination with other plasticizers like sugars. For their behaviour as plasticizer and humectant, we are interested in (a) the water activity, (b) the solubility, (c) the glass transition temperature, and (d) their influence on the melting of biopolymers. We conclude with a critical comparison of the Flory–Huggins theory with UNIFAC and PCSAFT, indicating its limitations and advantages for describing food systems with predominantly hydrophilic ingredients

Thermodynamic properties of sweet amino acids
Flory–Huggins theory for ternary mixtures
Glass transition
Hydrogen bonding and viscosity
Hydrogen bonding and biopolymer melting
Thermodynamic characterization
Viscosity
Effects on biopolymer melting
Critical discussion on Flory–Huggins theory
Conclusions
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