Advances in protein-based microcapsules and their applications: A review

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International Journal of Biological Macromolecules 263 (2024) 129742

Available online 24 January 2024

Review

Advances in protein-based microcapsules and their applications: A review

Donghui Ma

, Bingjie Yang

, Jing Zhao

, Dongdong Yuan

, Quanhong Li

College of Food Science and Nutritional Engineering, China Agricultural University, Beijing 100083, China

China National Engineering Research Center for Fruit & Vegetable Processing, Beijing 100083, China

CAU-SCCD Advanced Agricultural & Industrial Institute, Chengdu 611400, China

Beijing Advanced Innovation Center for Food Nutrition and Human Health, Beijing Engineering and Technology Research Center of Food Additives, Beijing Technology

and Business University, Beijing 100048, China

ARTICLE INFO

Keywords:

Protein

Microcapsules

Nutrient encapsulation

Food industry

ABSTRACT

Due to their excellent emulsication, biocompatibility, and biological activity, proteins are widely used as

microcapsule wall materials for encapsulating drugs, natural bioactive substances, essential oils, probiotics, etc.

In this review, we summarize the protein-based microcapsules, discussing the types of proteins utilized in

microcapsule wall materials, the preparation process, and the main factors that inuence their properties.

Additionally, we conclude with examples of the vital role of protein-based microcapsules in advancing the food

industry from primary processing to deep processing and their potential applications in the biomedical, chemical,

and textile industries. However, the low stability and controllability of protein wall materials lead to degraded

performance and quality of microcapsules. Protein complexes with polysaccharides or modications to proteins

are often used to improve the thermal instability, pH sensitivity, encapsulation efciency and antioxidant ca-

pacity of microcapsules. In addition, factors such as wall material composition, wall material ratio, the ratio of

core to wall material, pH, and preparation method all play critical roles in the preparation and performance of

microcapsules. The application area and scope of protein-based microcapsules can be further expanded by

optimizing the preparation process and studying the microcapsule release mechanism and control strategy.

1. Introduction

Microcapsule technology has gained signicant attention since the

pioneering research conducted by Green in 1955 [1]. In recent years, it

has found widespread application across various industries, including

food, biomedical, cosmetic, and textile, showing promising outcomes.

The primary objective of microcapsules is to shield the core material

from external environmental factors, such as light, oxygen, and water,

while precisely controlling the release of the core material, concealing

its odor and color, modifying its dispersion performance, solubility, and

other physical and chemical properties, and expanding its potential uses

[2]. With the ongoing development of microcapsule technology, a

multitude of materials and methods have been developed and optimized

[3]. When selecting microcapsule wall materials, it is essential to adhere

to principles that ensure stable and long-term protection for the core

material, prevent reactions with the core material, prioritize

harmlessness to the human body, minimize environmental impact, and

ensure cost-effectiveness and easy availability [4].

Biocompatible and biodegradable proteins are abundant renewable

natural materials with excellent emulsifying properties, lm-forming

properties, and high nutritional value [5,6]. Several independent re-

views have demonstrated the feasibility of using proteins as materials for

the walls of microcapsules. For instance, Sun et al. outlined the latest

advances in zein-based delivery systems, systematically introducing

strategies to improve the performance of zein assemblies and various

types of zein delivery systems [7]. Hadidi et al. discussed emerging plant

proteins as favorable wall materials for bioactive substances in food,

protecting and targeting their delivery and enhancing stability and shelf

life [8]. Vieira et al. focused on applying acidic proteins in multi-

particulate drug delivery systems, advocating for using these materials

in delivering anti-inammatory drugs [9]. Sridhar et al. reviewed recent

studies on modifying the functional properties of legume proteins using

Abbreviations: MD, maltodextrin; GA, gum Arabic; EE, encapsulation efciency; SPI, soy protein isolate; WPC, whey protein concentrate; WPI, whey protein

isolate; TGase, transglutaminase.

* Corresponding author at: College of Food Science and Nutritional Engineering, China Agricultural University, Beijing 100083, China.

E-mail address: quanhong_li@hotmail.com (Q. Li).

These authors contributed equally to this work.

Contents lists available at ScienceDirect

International Journal of Biological Macromolecules

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

https://doi.org/10.1016/j.ijbiomac.2024.129742

Received 20 October 2023; Received in revised form 7 January 2024; Accepted 23 January 2024

International Journal of Biological Macromolecules 263 (2024) 129742

high-pressure and ultrasound technologies to enhance encapsulation

[10]. They delved into applying legume protein microcapsules in novel

food design and bioavailability enhancement. In conclusion, as crucial

macromolecular polymers in the food industry, proteins can serve as

excellent wall materials for microcapsules. However, serving as the

primary constituents of microcapsule wall materials, proteins from an-

imals and plants exhibit fundamentally distinct structures. Varied

polypeptide sequences and diverse secondary structures result in

distinct tertiary structures, inuencing the manifestation of specic

functional properties in proteins, including solubility, gelation, emulsi-

cation, and foaming [11]. In contrast to proteins from animal sources,

vegetable proteins, particularly those derived from legumes, exhibit

lower solubility, insufcient emulsication properties, and restricted

responsiveness to pH, ionic strength, and temperature. Simultaneously,

plant proteins possess a high molecular weight and intricate structure,

with certain amino acids or functional groups concealed within the

protein core, potentially impeding interactions with charged poly-

saccharides [10,12]. Additionally, these structural distinctions

contribute to the varied application characteristics of microcapsules.

Although the aforementioned reviews have provided insights into

the utilization of specic proteins as microcapsule wall materials, a

systematic review of protein-based microcapsules is still needed to fully

encompass this eld's breadth. Protein-based microcapsules, fabricated

using various wall materials and preparation methods, exhibit distinct

structures and properties, making them versatile for different applica-

tions [13]. Therefore, a comprehensive and up-to-date review of the

preparation and application of protein-based microcapsules would be

precious for researchers, enabling them to design microcapsules with

enhanced performance and broader uses. This review aims to provide a

thorough overview of the diverse types of proteins used in microcapsule

wall materials, the preparation processes involved, the key factors

inuencing their properties, and the wide-ranging applications of

protein-based microcapsules based on prior research. Its goal is to

facilitate a deeper understanding of this eld and offer practical rec-

ommendations for the adequate preparation and application of protein-

based microcapsules.

2. Structure of protein-based microcapsules

The “microcapsule” is generally dened as particles featuring be-

tween 1 and 1000

m in size with a shell-core structure [14,15]. Protein-

based microcapsules are commonly characterized by a spherical or

irregular shape and possess a shell-core or matrix structure, as noted in

previous literature (Fig. 1) [16]. These microcapsules can be classied

based on the number of cores present, with single-core or multi-core

microcapsules being the two main categories [17,18]. The number of

capsule wall layers can also be used to categorize microcapsules, with

mono-layer or multi-layer microcapsules being the two main types.

Multi-layer microcapsules are typically produced through a layer-by-

layer process [19]. The core of a microcapsule can consist of one or

more substances, which can either be encased within the inner core or

dispersed within the wall material [20–22]. Protein-based

microcapsules exhibit diverse surface morphologies, including smooth,

concave, crumpled, cracked, and microporous surfaces. Nevertheless,

surface pores and cracks may result in the unregulated release of the

payload. To enhance microcapsule stability and enable controlled

release, a shell is typically incorporated onto the surface or cross-linked

using chemical or biological cross-linkers [23,24]. The characteristics of

microcapsules, including their surface morphology, size, shape, and

structure, are determined by various factors such as the core and wall

materials used and the preparation techniques employed. Microcapsules

produced by spray-drying are typically found to have concave and

wrinkled surfaces [25]. The structure of microcapsules confers distinct

properties and application possibilities. For example, single-core single-

shell microcapsules possess a simple structure and a large core volume,

resulting in higher drug loading. However, once the shell is ruptured, the

contents are rapidly released. Conversely, multi-layer microcapsules

offer better stability during thermal treatment and other processes,

thereby enhancing the encapsulated substances' protection. Further-

more, multi-layer and multi-core microcapsules allow for the slow and

continuous release of substances, making them ideal for applications

such as controlled drug release, avor release, and food preservation

[26]. This research direction holds a prominent position, driving re-

searchers to explore the most suitable wall materials and preparation

methods for various purposes, potentially revolutionizing advancements

in microencapsulation and opening new avenues for applications.

3. Microcapsule wall materials

Protein-based microcapsules can be divided into three categories

based on their wall material composition: single protein microcapsules,

which utilize a single type of protein as the sole material; composite

protein microcapsules, which incorporate a combination of protein and

other components for enhanced properties; and modied protein mi-

crocapsules, where the protein structure is chemically or structurally

modied to achieve specic characteristics (Figs. 2 and 3).

3.1. Single protein

Legume protein solutions, including soy protein [35], pea protein

isolate [36], and faba bean protein [37], can undergo self-assembly into

hollow microcapsules with pH and ionic strength dependence through

thermal treatment. Zhao et al. proposed a mechanism for ion-induced

phase separation and thermally induced microcapsule formation by

observing morphological changes during the self-assembly of soy 11s

protein [38]. Specically, sodium chloride induces phase separation of

soy 11s protein. The presence of sodium ions neutralizes the protein's

surface charge, reducing electrostatic repulsion. This leads to forming

protein clusters and irregular protein ocs through weak non-covalent

bonding interactions such as hydrogen bonds, van der Waals forces, or

hydrophobic interactions. Subsequently, when the proteins are heated

to 80 ◦C, they start to denature. The protein ocs gradually gel, forming

spherical hollow microcapsules within 60 s. This process is accompanied

by the exposure of hydrophobic groups (portions of the protein structure

Fig. 1. Schematic illustration of main morphologies of protein-based microcapsules.

D. Ma et al.

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