Oleic acid and whey protein reduced the digestion of oxidized and/or hydroxypropyl starches by changing their properties and microstructure

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LWT - Food Science and Technology 204 (2024) 116424

Available online 1 July 2024

nc-nd/4.0/).

Oleic acid and whey protein reduced the digestion of oxidized and/or

hydroxypropyl starches by changing their properties and microstructure

Jing Sun

, Shuang-yi Zheng

, Hai-long Zhang

, Run-jiao Zhang

, Shen-sheng Xiao

Xue-dong Wang

***

, Jing Du

Key Laboratory for Deep Processing of Major Grain and Oil, Ministry of Education, Wuhan Polytechnic University, Wuhan, 430023, China

Hubei Key Laboratory for Processing and Transformation of Agricultural Products, Wuhan Polytechnic University, Wuhan, 430023, China

College of Food Science and Engineering, Wuhan Polytechnic University, Wuhan, 430023, China

ARTICLE INFO

Keywords:

Modied starches

Starch digestibility

Starch-based complexes

Physical properties

ABSTRACT

Fatty acids and protein play a crucial role in reducing starch digestion. To investigate the effect of oleic acid (OA)

and whey protein (WP) on the digestion of oxidized and/or hydroxypropyl starches and its mechanism, the

changes on digestion, properties and microstructure of starch before and after complexation with OA and WP

were analyzed using rapid viscosity analyzer (RVA), rheometer, scanning electron microscope (SEM), Fourier

transformation infrared spectroscopy (FT-IR) and X-ray diffractometer (XRD). Results showed that starches with

OA and WP showed cooling peaks in RVA curve due to starch-OA-WP complexes formation. Additionally, OA and

WP had synergistic effects on the increase of storage modulus (G

′

), the decrease of gel pore size and digestion of

starches. OA and WP had a greater effect on digestion of oxidized hydroxypropyl starch (OHPS) than that of

hydroxypropyl starch (HPS) and oxidized starch (OS). Specically, resistant starch content in HPS, OS and OHPS

was increased by 82.41%, 58.67% and 279.18%, respectively, due to OA and WP incorporation. This was

attributed to the decrease of solubility and increase of order degree of OHPS caused by OA and WP. Therefore,

the appropriate hydrophilic and lipophilic properties of OHPS was helpful to complex with OA and WP.

1. Introduction

With the growing concern of rapid digestion of starch, physical and

chemical means have been reported to reduce starch digestibility (Li Y

et al., 2018), and one of a simple methods is the complexation of starch

and non-starch components. Lipids and proteins are important compo-

nents of starch-based foods, which often interact with starch and affect

the processing properties and quality of food (Zheng M et al., 2018). For

example, starch could interact with lipids/fatty acids to form

starch-lipids/fatty acids complexes with V-type structure (Kang X et al.,

2022), which decreased the solubility, swelling power and the di-

gestibility of starch (Niu et al., 2019; Oyeyinka, Singh, and Venter,

2017). Additionally, proteins and fatty acids could interact with starches

to form starch-fatty acid-protein complexes (Lin et al., 2020), which had

lower digestibility and gel strength (Wang S et al., 2020; Zheng M et al.,

2018) and higher gelatinization viscosity, relative crystallinity than the

homologous starch-fatty acids complexes (Wang S, Zheng M, Yu J, Wang

S&Copeland L, 2017). Because of its role in limiting starch digestion, the

complexation of starch, fatty acids and protein has promising applica-

tions (Raigond and Ezekiel, 2015).

The determinants inuencing the complexation of starch with fatty

acids and proteins were the features of starch, fatty acids and protein

and complexation conditions, among which the characteristics of starch

were one of the key factors (Chao C et al., 2018, Wang S, Wang S, Liu L,

Wang S&Copeland L, 2017). Generally, amylose formed

starch-lipid-protein complexes was more easily than amylopectin

because the extremely branched structure of amylopectin restricted the

formation of the essential mono-helical glucan conformation (Wang

et al., 2016). Wang et al. (2023) found that after complexation with

monoglycerides and β-lactoglobulin, octenyl succinic anhydride

(OSA)-modied starch had greater anti-digestibility than unmodied

starch because it was more conducive to

* Corresponding author. College of Food Science and Engineering, Wuhan Polytechnic University, Wuhan, 430023, China.

** Corresponding author. Key Laboratory for Deep Processing of Major Grain and Oil, Ministry of Education, Wuhan Polytechnic University, Wuhan, 430023, China.

*** Corresponding author. Key Laboratory for Deep Processing of Major Grain and Oil, Ministry of Education, Wuhan Polytechnic University, Wuhan, 430023,

China.

E-mail addresses: zhanghailong@whpu.edu.cn (H.-l. Zhang), xuedongwuhan@163.com (X.-d. Wang), dj890520@126.com (J. Du).

Contents lists available at ScienceDirect

LWT

journal homepage: www.elsevier.com/locate/lwt

https://doi.org/10.1016/j.lwt.2024.116424

Received 22 December 2023; Received in revised form 25 May 2024; Accepted 30 June 2024

LWT 204 (2024) 116424

starch-monoglycerides-β-lactoglobulin complexes than unmodied

starch due to its high emulsifying property. Therefore, modied starches

with specic groups could inuence the interaction between starch,

fatty acid and protein, thereby exhibiting different properties and

structure.

It is believed that fatty acid is the bridge between starch and protein,

and its hydrophobic hydrocarbon chains enter into the helical cavity of

amylose and bind with amylose, while its polar carboxyl groups bind

with the charged groups of proteins by electrostatic interaction (Wang S

et al., 2020). Additionally, one of the main driving forces for the for-

mation and structural stability of amylose-fatty acid-protein complexes

was hydrogen bonds between amylose and protein (Wang J et al., 2023).

Based on the above theoretical knowledge of starch-lipid-protein com-

plexes formation, we hypothesized that hydroxypropyl starch (OHPS)

with high content of hydroxyl groups and carboxyl groups might be

helpful to anti-digestive starch-fatty acid-protein complexes formation

than hydroxypropyl starch (HPS) with hydroxyl groups and oxidized

starch (OS) carboxyl groups. Therefore, oleic acid (OA) and whey pro-

tein (WP) might have greater effect on the digestion of OHPS than that of

HPS and OS due to the formation of starch-fatty acid-protein complexes

with compacted and ordered structure. However, there is still limited

understanding of how OA and WP inuence the digestion of OHPS, HPS

and OS and the underlying mechanism. To verify this hypothesis, the

effect of OA and WP on the digestion of OHPS, HPS and OS and the

underlying mechanism were studied using X-ray diffraction (XRD),

Fourier transformation infrared spectroscopy (FT-IR), and other

comprehensive analysis methods. This study was of great signicance

for an in-depth exploration of the effect of fatty acid and protein on

physical properties and structure of modied starch and the rational

design of starch-based foods and precise regulation of starch

digestibility.

2. Materials and methods

2.1. Materials

Corn starch (CS) with the purity of 98% and whey protein (WP) with

the purity of 80% were purchased from Shanghai Yuanye Biotechnology

Co. Ltd (Shanghai, China). Oxidized starch (OS) with the purity of 99%

and oxidized hydroxypropyl starch (OHPS) with the purity of 98% were

provided by Shanghai Golden Bottle Ingredients Co (Shanghai, China).

Hydroxypropyl starch (HPS) with the purity of 98% was obtained from

Youbaojia Food Co., Ltd (Zhengzhou, China). Amyloglucosidase with an

enzyme activity of 100,000 U/mL was supplied by Aladdin Industries

(Shanghai, China). Amylase with an enzyme activity of 14 U/mg was

purchased from Sigma-Aldrich Co. LLC (Santa Clara, USA). Oleic acid

(OA) and other chemical reagents including sodium acetate, sodium

carbonate, potassium iodide and iodine were of analytical grade and

purchased from Sinopharm Chemical Reagent Co. Ltd (Shanghai,

China).

2.2. Starch-based complexes preparation

Starch (2.0 g), starch-OA (2.0 g of starch and 0.1 g of OA), starch-OA-

WP (2.0 g of starch, 0.2 g of WP and 0.1 g of OA) and proper distilled

water (total weight of 28 g) were placed into a test canister of a rapid

viscosity analyzer (RVA) (RVA-Super 4, Perten, Sweden). The determi-

nation parameters were based on a previous study (Du J et al., 2023) as

follows (shown in Fig. 1): the mixture was maintained for 1 min at 50 ◦C,

then raised at 14 ◦C/min to 95 ◦C and maintained at this temperature for

2.5 min, then decreased to 50 ◦C also at 14 ◦C/min and maintained for

3.06 min at 50 ◦C. The above procedure was run at 960 rpm for the rst

10 s and at 160 rpm for the rest time. The curves of starch-base com-

plexes obtained during the preparation process were used for RVA

analysis. The prepared starch gels were freeze-dried in a lyophilizer

(LGJ-10, Foring, China) at -60 ◦C (cold trap temperature) under vacuum

at 10 Pa for 72 h. The freeze-dried samples were stored in a desiccator at

25 ◦C for subsequent experiments.

2.3. Rheological properties analysis

Starch gels were prepared using a RVA (RVA-Super 4, Perten, Swe-

den) as explained in method 2.2. Rheological properties analysis was

conducted using a Multifunctional Rotational Rheometer (HR-1, TA,

USA) with a at plate (40 mm diameter) and the gap of 1 mm based on

the reported of Kang et al. (2021). Frequency sweep was performed

within the frequency range from 0.1 to 10 Hz at 25 ◦C with a strain of

1%, which was obtained by the experiment of strain sweep.

Fig. 1. Schematic diagram of sample preparation.

HPS, hydroxypropyl starch; OS, oxidized starch; OHPS, oxidized hydroxypropyl starch; OA, oleic acid; WP, whey protein.

J. Sun et al.

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