Enhancement of resistant starch content in ethyl cellulose-based oleogels cakes with the incorporation of glycerol monostearate

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Current Research in Food Science 8 (2024) 100770

Available online 15 May 2024

nc-nd/4.0/).

Enhancement of resistant starch content in ethyl cellulose-based oleogels

cakes with the incorporation of glycerol monostearate

Xiaohan Chen

, Dongming Lan

, Daoming Li

, Weifei Wang

, Yonghua Wang

Department of Food Science and Engineering, School of Food Science and Engineering, South China University of Technology, Guangzhou, 510640, China

Sericultural & Agri-Food Research Institute, Guangdong Academy of Agricultural Sciences, Key Laboratory of Functional Foods, Ministry of Agriculture and Rural

Affairs, Guangdong Key Laboratory of Agricultural Products Processing, Guangzhou, 510610, China

School of Food and Biological Engineering, Shaanxi University of Science and Technology, Xi’an, 710021, China

ARTICLE INFO

Handling editor: A.G. Marangoni

Keywords:

Diacylglycerol oil

Oleogel

Lipid-amylose complexes

Starch digestibility

ABSTRACT

The objective of this work was to completely replace margarine with peanut diacylglycerol oil/ethyl cellulose-

glycerol monostearate oleogel (DEC/GMS) oleogel, and evaluate its effect on starch digestibility of cakes. The

in vitro digestibility analysis demonstrated that the DEC/GMS-6 cake exhibited a 26.36% increase in slowly

digestible starch (SDS) and resistant starch (RS) contents, compared to cakes formulated with margarine. The

increased SDS and RS contents might mainly be due to the hydrophobic nature of OSA-wheat our, which could

promote the formation of lipid-amylose complexes with GMS and peanut diacylglycerol oil. XRD pattern sug-

gested that the presence of GMS in DEC-based oleogels facilitated the formation of lipid-amylose complexes. The

DSC analysis revealed that the addition of GMS resulted in a signicant increase in gelatinization enthalpy, rising

from 249.7 to 551.9 J/g, which indicates an improved resistance to gelatinization. The FTIR spectra indicated

that the combination of GMS could enhance the hydrogen bonding forces and short-range ordered structure in

DEC-based cakes. The rheological analysis revealed that an increase in GMS concentration resulted in enhanced

viscoelasticity of DEC-based cake compared to TEC-based cakes. The DEC-based cakes exhibited a more satis-

factory texture prole and higher overall acceptability than those of TEC-based cakes. Overall, these ndings

demonstrated that the utilization of DEC-based oleogel presented a viable alternative to commercial margarine in

the development of cakes with reduced starch digestibility.

1. Introduction

Currently, the use of oleogel as a margarine substitute is an active

area of research in the bakery industry (Roufegarinejad et al., 2023).

This is owing to the high levels of saturated and trans fatty acids found in

margarine, which have been associated with various adverse health

outcomes in humans (Aliasl Khiabani, Tabibiazar, Roufegarinejad,

Hamishehkar and Alizadeh, 2020). However, it has been discovered that

the substitution of margarine with oleogel enhanced the digestibility of

starch in bakery food (Alvarez-Ramirez et al., 2020; Barrag´

an-Martínez

et al., 2022). The increased digestibility of starch is closely associated

with the increase in and prevalence of human health conditions, such as

obesity (Li et al., 2023), diabetes (Zhang et al., 2023), and cardiovas-

cular disease (Xu et al., 2023). Therefore, the research on reducing

starch digestibility is of signicant importance for oleogel-based bakery

food.

Peanut diacylglycerol oil (PDO) based oleogel plays an important

role in reducing the digestibility of bakery products, that can improve

insulin resistance and lower blood lipid levels due to its high oleic acid

content (Lei et al., 2018; Zhi-hao, Ai-min, Rui, Hong-zhi, Hui and Qiang,

2022). Our previous research has discovered that the PDO-based oleo-

gel, which consists of ethyl cellulose (EC) and glycerol monostearate

(GMS), can potentially serve as a substitute for margarine in cake for-

mulations (Chen et al., 2023). Glycerol monostearate (GMS) was proved

to possess a tailoring capacity for the structural, rheological and tribo-

logical properties of ethylcellulose (EC)-based oleogels/oleogel emul-

sions (Garcia-Ortega et al., 2021; Rupp and Cramer, 2022; Zhang et al.,

2022). However, limited research has been conducted on the inuence

of GMS in oleogels on the starch digestibility of cakes. Many studies have

demonstrated that lipids, such as fatty acids (Cervantes-Ramirez et al.,

* Corresponding author.

** Corresponding author.

E-mail address: wangweifei@gdaas.cn (W. Wang).

Contents lists available at ScienceDirect

Current Research in Food Science

journal homepage: www.sciencedirect.com/journal/current-research-in-food-science

https://doi.org/10.1016/j.crfs.2024.100770

Received 5 March 2024; Received in revised form 9 May 2024; Accepted 14 May 2024

Current Research in Food Science 8 (2024) 100770

2020), GMS (Kawai et al., 2012; Wang et al., 2023) and diacylglycerols

(Feng et al., 2024), can form complexes with amylose to create

lipid-amylose complexes. These complexes are characterized by a more

stable and compact ordered structure, which leads to reduced suscep-

tibility to enzyme decomposition and ultimately contributes to a

decrease in starch digestibility (Liu et al., 2023). Therefore, investi-

gating the relationship between lipid-amylose complexes and starch

digestibility holds signicant importance in oleogel-based bakery food.

However, investigating lipid-amylose complexes poses several chal-

lenges. For example, the tight arrangement and difcult depolymeriza-

tion of amylose, as well as the large molecular weight and steric

hindrance of diacylglycerols, moderately affect the formation of com-

plexes (Wang et al., 2021). To address these issues, one approach is the

esterication modication of wheat our using octenyl succinic anhy-

dride (OSA), which can enhance its hydrophobicity. The United States

Food and Drug Administration (FDA) has granted approval for the

maximum allowable concentration of OSA to be limited to 3% (w/w

starch basis) (Zheng et al., 2024). The OSA-wheat our helix cavity

could create a favorable environment for accommodating the hydro-

carbon chain of the lipid molecule through a series of non-covalent in-

teractions, due to its hydrophobic nature (Chen et al., 2022). The

esterication of OSA for starch modication, as discovered by Liu et al.

(2022), has been found to signicantly enhance the formation of com-

plexes between OSA-starch and linoleic acid, resulting in enhanced

resistance to digestion. Although extensive investigations have been

conducted on the formation of lipid-amylose complexes within

OSA-starch and fatty acids, there remains a lack of studies focusing on

the interaction between GMS and OSA-wheat our. Additionally, an

unexplored examination of the inuence of GMS in PDO-based oleogel

on starch digestibility in cake is needed.

The objective of this study was to assess the effects of substituting

margarine with PDO-based oleogel on the starch digestibility in cakes.

The effect of oleogels on the digestibility of cakes was investigated by

measuring the levels of rapidly digestible starch (RDS), slowly digestible

starch (SDS), and resistant starch (RS). The underlying mechanism of

oleogels on the digestibility of cakes was elucidated through compre-

hensive analysis techniques including X-ray diffraction (XRD), differ-

ential scanning calorimetry (DSC), Fourier transform infrared

spectroscopy (FTIR), and rheological analysis.

2. Materials and methods

2.1. Materials

Peanut triacylglycerol oil (PTO, 4.16% DAG, 93.55% TAG, 11.55%

C16:0, 3.86% C18:0, 40.33% C18:1 and 38.2% C18:2) and peanut

diacylglycerol oil (PDO, 81.27% DAG, 18.73% TAG, 10.95% C16:0,

3.26% C18:0, 41.09% C18:1 and 37.55% C18:2) were provided by

Guangdong Yue-shan Special Nutrition Technology Co., Ltd. (Guang-

dong, China), ethyl cellulose (EC) (viscosity 46 cP; 5% in toluene/

ethanol 80:20 (v/v); 48% ethoxy, Tg =120 ◦C), glycerol monostearate

(GMS),

-amylase and pepsin were provided by Yuanye Bio-Technology

Co., Ltd. (Shanghai, China). Margarine (69.83% saturated fatty acid)

and wheat our (carbohydrate 76.50%, protein: 8.00%, fat:1.6%) were

obtained at a local Walmart supermarket (Guangdong, China). All other

chemical reagents, which were analytically pure, were provided by

Aladdin Biochemical Technology Co., Ltd. (Shanghai, China). Distilled

water was used in all formulations.

2.2. Preparation of OSA-wheat our

The OSA-wheat our preparation was conducted according to the

method of Liu et al. (2022) with some modications. Wheat our was

dispersed in distilled water (35% w/w) under continuous stirring for

approximately 10 min. Subsequently, octenyl succinic anhydride (7% of

wheat our, dry weight) was added dropwise after achieving even

dispersion. The entire reaction was maintained at a pH of 8.5 and a

temperature of 35 ◦C. To terminate the reaction, the pH of the slurry was

adjusted to 6.5 by adding dilute HCl. The mixture underwent centrifu-

gation (5000×g, 10 min), followed by 3 washes with distilled water and

3 washes with 95% ethanol. The resulting precipitate was dried in an

oven at 45 ◦C for 24 h and stored in a dryer for further analysis. The

designated names for the resulting precipitate was OSA-wheat our.

2.3. Preparation of oleogel

The oleogel was prepared following the method of Adili (2020) with

some modications. Different contents of EC and GMS powders

(EC-GMS: 6 wt%-0 wt%; 4 wt%-2 wt%; 2 wt%-4 wt%; 0 wt%-6 wt%)

were added to peanut triacylglycerol oil or peanut diacylglycerol oil,

followed by heating at a constant stirring rate of 120 ◦C for 2 h. Sub-

sequently, the oleogels were refrigerated at 4 ◦C for 24 h before being

transferred to a temperature of 20 ◦C for analysis (Rodri-

guez-Hernandez, 2021). Depending on the concentration of EC and

GMS, the oleogels were designated as TEC, TEC/GMS-2, TEC/GMS-4,

TEC/GMS-6, DEC, DEC/GMS-2, DEC/GMS-4 and DEC/GMS-6.

2.4. Preparation of cakes

The cake was prepared following the method described by Adili

(2020) with certain modications. The foaming protein was vigorously

mixed with 300 g of egg albumen and 100 g of sugar. For cake prepa-

ration, a mixture of margarine (3 g), OSA-satrch (5 g), water (5 g) and

foaming protein (20 g) was used. In the formulated cakes, margarine was

substituted with TEC-based and DEC-based oleogels. Subsequently, the

cake batter was baked at 180 ◦C for 20 min in a convection oven (Midea

Kitchen Appliance Manufacturing, Foshan, China) (Adili, 2020). Based

on the type of oleogels employed, the cakes were designated as

Margarine cake, TEC cake, TEC/GMS-2 cake, TEC/GMS-4 cake,

TEC/GMS-6 cake, DEC cake, DEC/GMS-2 cake, DEC/GMS-4 cake and

DEC/GMS-6. The rest of Margarine, TEC-based and DEC-based cake

batters were used for determination of rheological propertie. The cakes

for each formulation were prepared thrice, with three samples per batch

for subsequent measurements.

2.5. Peroxide value (PV)

The peroxide value (PV) of oils was determined according to Siva-

kanthan et al. (2024) with some modications. Briey, 2 ±0.05 g of

oleogels was weighed into a 250 mL Erlenmeyer ask, and 30 mL of

chloroform:acetic acid (2:3, v/v) was added and mixed well to dissolve

the sample. Then, 1 mL of saturated KI solution was added, stoppered,

and left to stand for 3 min in the dark with occasional shaking. Then,

100 mL of distilled water was added and titrated with 0.01 mol/L so-

dium thiosulfate using the starch in dicator. A blank determination also

was conducted in parallel. The results was calculated by the following

equation (1):

PV(mmol /kg) = (V−V0) × 1000c

2M (1)

where V and V

was the volume of sodium thiosulfate solution consumed

of the test solution and the reagent blank, c was the concentration of

sodium thiosulfateand, M was the weight of the sample.

2.6. The 2-thiobarbituric acid (TBA)

The 2-thiobarbituric acid (TBA) value was determined according to

the method of Zhao et al. (2023). Briey, the samples containing 200 mg

of oleogels were dissolved in n-butanol and xed to 25 mL. An amount of

5 mL of this solution was then mixed with 5 mL of 0.2% TBA reagent and

incubated in a water bath at 95 ◦C for 2 h. A blank determination also

X. Chen et al.

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