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Chemical Engineering Journal 474 (2023) 146011

Contents lists available at ScienceDirect

Chemical Engineering Journal


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

Review

3D-printed flexible sensors for food monitoring


Danyao Song a, 1, Xujun Chen a, 1, Meng Wang a, 1, Zihao Wu a, Xinqing Xiao a, *
a
College of Engineering, China Agricultural University, Beijing, 100083, PR China

A R T I C L E I N F O A B S T R A C T

Keywords: In recent years, the convergence of 3D printing technology and flexible sensors has played a crucial role in
3D printing various fields, particularly in industrial production. The widespread development of 3D printing technology and
Print material flexible sensors has become more evident, with a specific focus on food analysis and monitoring, which is closely
Flexible Sensors
linked to human health. The utilization of 3D-printed flexible sensors in the realm of food analysis and moni­
Food Monitoring
toring offers flexibility, adaptability, and high sensitivity. These sensors enable real-time monitoring and accu­
rate detection, providing cost-effective solutions for ensuring food safety. This review begins by analyzing the
advantages of the 3D printing process in fabricating flexible sensors, followed by an introduction to the benefits
of 3D printing materials and hydrogel materials in sensor fabrication. Subsequently, the review delves into the
detailed discussion of food monitoring applications, specifically the monitoring of gases, microorganisms, and
non-gaseous compounds in food. Each application is thoroughly analyzed, considering its advantages, disad­
vantages, and potential scenarios.

1. Introduction strength, impact resistance, heat resistance, hardness, and aging resis­
tance are superior to plastics [6]. 3D-printed metal materials are avail­
3D printing technology is an additive manufacturing technology, able in the form of metal powder, metal foil, and metal wire. Common
also known as additive manufacturing. 3D printing technology is usually metal materials include titanium alloys, stainless steel, cobalt-chromium
based on digital models, and then powdered metals, plastics, and other alloys, and aluminum alloys [7]. Ceramic materials have excellent
materials with adhesive properties are printed layer by layer to create properties such as high strength, high hardness, high-temperature
the final composition of the object technology [1]. The 3D printing resistance, low density, good chemical stability, and good corrosion
methods we currently use include multi-jet fusion (MJF), fused deposi­ resistance, and are widely used in aerospace, automotive, biological,
tion modeling (FDM), direct metal laser sintering (DMLS), electron beam and home improvement materials [8]. In addition, hydrogel materials
melting (EBM), digital light processing (DLP), and direct ink writing are widely used in 3D bioprinting, and the outstanding physicochemical
(DIW). In recent years, 3D printing technology has developed rapidly in properties of the hydrogel as a representative bioink make it occupy an
the manufacturing industry [2]. Compared with traditional important position in the food and pharmaceutical fields [9].
manufacturing, 3D printing has obvious advantages, mainly in terms of Due to the technological advances of the times, traditional sensors
reduced major costs, shorter product manufacturing time, the combi­ are becoming modular, networked, miniaturized, self-energizing, and
nation of materials used in the product, and unique product design [3]. green and are beginning to be replaced by flexible sensors in many fields
In addition, 3D bioprinting technology is also maturing and playing a [10]. Flexible sensors are sensors made of flexible materials, which are
huge role in food and medicine. flexible and ductile and can be freely bent or even folded. Due to the
3D printing material is an important factor that affects the perfor­ flexible material and structure, flexible sensors can be arranged arbi­
mance of the final product [4]. The printing materials are different, and trarily according to the application scenario and can easily detect the
the performance of the printing materials is also different, and the unit under monitor [11]. Flexible sensors are still essentially sensors, the
current printing materials are mainly divided into polymer materials, earliest flexible sensors for flexible substrates, generally requiring ma­
metal materials, ceramic materials, etc. [5]. Polymers are currently the terials with thin, transparent, stretchable, bendable, corrosion-resistant
most widely used 3D printing materials in FDM devices, and their properties [12]. Polydimethylsiloxane (PDMS) is a relatively common

* Corresponding author.
E-mail address: xxqjd@cau.edu.cn (X. Xiao).
1
Danyao Song, Xujun Chen and Meng Wang contributed equally to this work.

https://doi.org/10.1016/j.cej.2023.146011
Received 3 June 2023; Received in revised form 6 September 2023; Accepted 9 September 2023
Available online 11 September 2023
1385-8947/© 2023 Elsevier B.V. All rights reserved.
D. Song et al. Chemical Engineering Journal 474 (2023) 146011

flexible substrate material that not only has these properties but is also thicker parts that are difficult to meet the specific requirements of
easily available and chemically stable [13]. Then there are conductive flexible sensors. FDM, DIW, SLA, and DLP are more common and pop­
materials, that is, metallic materials, mainly for the manufacture of ular in the manufacturing of flexible sensors [29]. Fig. 1 shows the flow
electrodes and wires, generally, flexible sensors do not use ordinary and application of these three printing processes. As shown in Fig. 2 is
metals, but metal nanoparticles or nanowires, which have better con­ the 3D printing flow chart, which summarizes the general process flow
ductivity and are easy to achieve in thin films [14]. Flexible sensors will of 3D printing.
also use carbon materials, mainly graphene and carbon nanotubes. In addition to this, 3D bioprinting is an emerging biomanufacturing
Flexible sensors are one of the important landed applications of gra­ technology, a new field that combines traditional 3D printing with
phene materials, which are thin, transparent, and well-conductive. And biology, a special 3D printing technology [34]. 3D bioprinting tech­
these can be achieved by 3D printing, so it is very suitable for 3D nologies have developed rapidly in recent years and are widely used in
printing [15]. The combination of flexible sensors and 3D printing will various fields. These 3D printing technologies can provide more flexible
become a hot issue in the future, which will promote technological and efficient production methods, and therefore their use in flexible
innovation in various fields [16]. sensor manufacturing is becoming more and more common [35]. Bio-3D
The food health industry is directly related to the issue of dietary printing is the fabrication of biomaterials or biological units (cells/
health of all human beings, and the first step in maintaining human proteins, etc.) with complex structures and functions, as well as
health status is to grasp the relationship between diseases from the personalized biomaterial 3D structures or in vitro 3D bio-functional
mouth [17]. Currently, there are many methods of food analysis and bodies by additive manufacturing methods [34], as shown in Fig. 3.
monitoring, including sensory monitoring methods, physical monitoring Bio-3D printing technology allows the fabrication of a diversity of
methods, chemical analysis, and instrumental monitoring methods [18]. flexible sensors that, in the case of biomedical sensors, can be adapted to
In the food industry, instrumentation is commonly used and sensors are the individual needs of medical devices [36]. The manufactured flexible
the main way and means of obtaining information in the production sensors are more biocompatible and biologically accessible, allowing for
field, and with the gradual increase in the importance of food moni­ better adaptation to environmental changes and the physiological state
toring, the field of application of monitoring technology will be further of the human body, leading to better exploration and biological
expanded [19]. The combination of 3D printing and flexible sensors is an research. Bio-3D printing technology also allows for high precision and
emerging area of research in today’s world, where the production of high-resolution printing, which allows for greater accuracy and control
flexible sensors through 3D printing is simpler, and the choice of ma­ in small and fine sensors [37]. Among the most commonly used printing
terials is more diverse than traditional manufacturing methods [20]. The methods for bio-3D printing are three: inkjet bioprinting, micro-
combination of 3D printing and flexible sensors will have a very wide extrusion molding bioprinting, and laser-assisted bioprinting. As
range of applications in the field of food health [21]. This paper de­ shown in Fig. 4, the three types of bio-3D printing are displayed [38].
scribes the current state of development and application of 3D printing
and flexible sensors, followed by the development of the potential of 3D 2.2. 3D printing for flexible sensors
printing technology for manufacturing flexible sensors for food inspec­
tion applications. Flexible sensors are sensors that can bend and deform on curved
surfaces and are widely used in medicine, robotics, smart wearables, and
2. 3D printing technology for flexible sensors other fields. And 3D printing technology provides a flexible, efficient,
and customizable method for manufacturing flexible sensors. In this
Flexible sensors are sensors that provide reliable measurement of section, we will focus on the practical applications of the above
physical quantities with high accuracy, fast response time, and appli­ commonly used 3D printing processes and methods for flexible sensors.
cability to a variety of applications [22]. However, traditional We will take flexible pressure sensors, flexible temperature sensors,
manufacturing methods often struggle to meet the demands of cost, flexible pH sensors, and bio-3D printed biosensors as examples to discuss
manufacturability, and design freedom, limiting the application of their applications in detail.
flexible sensors. And with the continuous development of 3D printing Flexible pressure sensors have a wide range of applications in med­
technology, the manufacturing of flexible sensors has been revolution­ icine, robotics, smart wearables, and other fields. For food monitoring,
ized [23]. 3D printing technology is a new manufacturing and pro­ the sensor can be adjusted to accommodate food samples of various
cessing process that allows the production of complex shapes and shapes and curved surfaces, ensuring a better fit and adaptability. Its
structures, saves materials, increases productivity, eliminates the need flexible design enables accurate detection of pressure changes in food
for additional products after processing, enables personalization and samples. The sensor’s high sensitivity enables precise measurement of
customization needs [24]. 3D printing technology is used in various even small pressure changes, thereby providing accurate data for food
fields such as architecture, aerospace, transportation and travel, monitoring. Sinha et al. fabricated tactile fingertip sensors for smart
biomedicine, art, and education [25]. gloves, which consist of piezoresistive pressure sensing elements sand­
wiched between 3D printed silver nanoparticle electrodes on a poly­
2.1. 3D printing processes and methods imide layer, similar to human earth skin [39]. The sensor array is
mounted on smart gloves for recognizing sharp and blunt objects with
Inkjet printing and aerosol jetting are two methods of 3D printing. In high accuracy. The sensor’s ultra-low cost, no crosstalk, fast response,
making flexible sensors, inkjet printing makes the conductive electrodes and wide sensing range give it great potential for applications. Li et al.
of the flexible sensor [26]. This method allows for high resolution and discussed a 3D printing method using FDM to fabricate flexible strain
flexibility and is suitable for making fine sensor structures [27]. Aerosol sensors [30]. The sensors are made from a blend of thermoplastic
spraying can be used to make sensitive material layers for flexible sen­ polyurethane elastomeric polymers and conductive carbon black parti­
sors for detecting physical quantities such as pressure and strain. Aerosol cles to form a composite filament. The sensor is then printed in a unique
spraying can achieve high precision and uniformity and is suitable for periodic configuration using fine filaments, thereby increasing its flex­
making flexible sensors with high sensitivity [28]. Common 3D printing ibility. The sensors can detect strain and can be adjusted for sensitivity
methods include MJF, FDM, DMLS, EBM, DLP, SLA, and DIW. Among by changing their geometric configuration. New manufacturing tech­
them, MJF, DMLS, and EBM are less used in flexible sensor applications. niques facilitate the use of new materials and broaden the innovation
These three advanced 3D printing technologies are mainly used to path for flexible sensors. Ma et al. prepared flexible multimodal tactile
manufacture metal and plastic parts. Flexible sensors need to be soft and sensors with different sensing characteristics at different printing speeds
thin, and these three 3D printing technologies typically produce harder, by the DIW technique [33]. By examining the response of the sensor to

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Fig. 1. The process and application of the four printing processes. a. Flowchart of flexible sensor fabrication using FDM3D printing process; b. Schematic of strain
sensing behavior test method for FDM printed CBP/TPU sensor with periodic configuration and flexible TPU film substrate[30]; c. Processing workflow comprising
SLA 3D printing and GNP dip-coating to fabricate piezoresistive pressure sensor[31]; d. Flowchart of DLP 3D printing process; e. DLP 3D printed capacitive sensor; f.
Capacitive sensor Principle diagram[32]; g. Flow chart of DIW preparation of flexible multimodal haptic sensor; h. Photograph of the printed conductive path on
PDMS substrate; i. Response of flexible haptic multimodal sensor to finger flexion and extension, finger press, thermal airflow, plantar pressure, and knee joint
motion, respectively[33].

finger flexion and extension, pressure, and thermal airflow, its potential fabrication methods. Meanwhile, Mu et al. used DLP technology to
application in multimodal sensing was verified. Kamat et al. fabricated fabricate flexible sensors made of polymeric nanocomposites [32]. The
flexible piezoresistive pressure sensors with superior performance using inks used in the printing process were a mixture of light-curing resins
SLA-printed body-centered cubic structures, a method that allows for and multi-walled carbon nanotubes (MWCNT), which provide conduc­
better control of the microstructure in the sensors [31]. Kim et al. pre­ tivity to the printed objects. DLP printing technology provides a fast way
pared piezoelectric photopolymer-based polyvinylidene difluoride to create sensor arrays in an integrated system that can detect force,
(PVDF) blends using SLA printing to improve the piezoelectric coupling strain, and level changes. Dankoco et al. fabricated flexible temperature
coefficient [40]. Designing different process variables to achieve sensors by inkjet printing to monitor the surface temperature of the
optimal dissolution, 3D printability and piezoelectric properties for human body, the sensors were fabricated by depositing thermistors
PVDF is optimal and promotes the development of flexible pressure consisting of silver on a polyimide substrate [42]. The sensor has good
sensors. linearity and less than 1% hysteresis and has great potential in the field
Flexible temperature sensors have an important role in temperature of temperature sensing.
monitoring, smart home, automotive, and other fields. The flexible Flexible pH sensors have a wide range of applications in environ­
design allows the sensor to be in close contact with the food surface, mental monitoring, food safety, medical diagnostics, and other fields.
providing more accurate temperature measurements. Flexible sensors For food monitoring, the flexible design allows for more accurate pH
can be adapted to different shapes and sizes of food samples, providing a measurements and a wider range of applications. With high sensitivity
wider range of applications. With fast response and high sensitivity, and fast response, flexible sensors can monitor pH changes in food
flexible sensors can monitor temperature changes in food products in a samples in real-time, providing timely food quality monitoring and
timely manner to ensure food safety and quality. Song et al. used fused safety assurance. Shweta et al. fabricated a flexible pH sensor using CNT
deposition modeling 3D printing technology for the one-step fabrication material by aerosol jet printing [43]. The chemo-resistive pH sensor has
of capacitive force sensors and resistive temperature sensors [41]. the sensing element printed on top of a silver electrode. This printing
Capacitive force sensors and resistive temperature sensors are made by method allows high-resolution printing and its fabricated pH sensors
fused deposition modeling 3D printing technology using conductive and have good sensitivity and reproducibility. Qin et al. developed an inkjet
dielectric material wires, respectively. The capacitive force sensor with a printing process to produce a flexible pH sensor [44]. Similar pH sensing
parallel plate structure can achieve a relative sensitivity of 0.088%/N, behavior can be obtained by printing carbon nanotubes on a flexible
and the resistive temperature sensor can achieve a relative sensitivity of polymer substrate. The developed inkjet printing process and pH sensing
2.2%/◦ C. This fabrication method is simpler than conventional electrode provide a cost-effective solution for future electrochemical

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Fig. 2. General process of 3D printing manufacturing.

Fig. 3. Schematic diagram of biological 3D printing.

monitoring systems. technology to fabricate flexible sensors that can be used to monitor the
Biosensors have an important role in medical diagnostics, biological growth and behavior of skin cells [45]. These sensors, made using silver
research, and other fields. Flexible biosensors allow for customized nanoparticles and SU-8 on a flexible substrate, are cell-compatible,
design and production, providing high sensitivity and stability for food which means they do not harm the cells being monitored and are a
monitoring capabilities. Mojena-Medina et al. used inkjet printing low-cost solution for monitoring cell growth and migration in real time.

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Fig. 4. Three types of bioprinting.

And these sensors have potential use in monitoring laboratory-grown suitable for bio-3D printing [47]. The properties of various materials are
skin tissue and wound healing. Rabbani et al. investigated the effect of shown in Fig. 5. These materials have excellent repeatability, adapt­
substrate material, printing density, printing pattern, and color intensity ability, and customizability. It enables the fabrication of arbitrarily
on the number of bacteria recovered [46]. The results showed that laser complex shapes, which is ideal for the manufacture of flexible sensors.
printers can be effectively used for transferring bacteria onto paper
substrates and for manufacturing biosensors. Selection of the appro­
priate number of printed bacteria using printing capacity and a novel 3.1. Polymer materials
toner bio-powder to adapt the printing substrate for the fabrication of
bacterial biosensors. As the most widely used class of 3D printing materials today, Ther­
moplastic elastomers, polymer composites, etc. are commonly used in
3. 3D printed materials of flexible sensors the manufacture of flexible sensors. The main characteristics of such
polymers are their excellent flexibility and elasticity, along with some
At present, the materials used to manufacture flexible sensors using electrical conductivity and mechanical strength. This makes elastic
3D printing technology mainly include polymer materials, metal mate­ polymers one of the common choices for manufacturing flexible sensors
rials, ceramic materials, etc. In addition, there are hydrogel materials [52]. Some polymer materials have good gas barrier properties and can
be made into food packaging sensors that can extend the freshness of

Fig. 5. Properties of various materials. a. The PEDOT: PSS patterned layer on a flexible substrate; b. Microscopic strain measurements; c. Sensor time response[48];
d. Perspective view of a flexible multifunctional inductive sensor; e. Excellent tensile and bending properties of the sensor[49]; f. The fabrication process of the TiO2
nanofibrous network; g. A photograph of an ultrathin TiO2 nanofibrous network; h. Cyclic bending and cyclic compression tests of TiO2[50]; i. Schematic diagram of
hydrogel preparation; j. Tensile stress–strain curves[51].

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food. Polymer materials can usually prepare adsorbent materials, the material and have the advantage of being able to be reinforced by heat
sensor can be made to detect pesticides and other ingredients in food. treatment. In addition, ceramic materials can be optimized for flexible
Latessa et al. developed a low-cost flexible polymer sensor in which a sensors by controlling composition, microstructure, and other aspects to
polymer poly(3,4-ethylene-dioxythienyl) polystyrene sulfonate achieve a variety of property modifications [59]. The high hardness and
(PEDOT: PSS) film was exfoliated and deposited on a polyimide sub­ toughness of ceramic materials can be achieved by simultaneously
strate by electrochemical synthesis [48]. The strain coefficient of this inhibiting grain growth and exerting grain boundary hardness; special
sensor is much higher than the general flexible strain gauge, and the properties such as damping and electrical conductivity can also be
dynamic response is good. Young et al. describe a method for fabricating achieved by selecting appropriate additives [60]. Ceramics have good
flexible gas sensors using carbon nanotubes and polymer substrates heat and corrosion resistance and can be used to manufacture food
[53]. The researchers transferred high-density carbon nanotubes from packaging types of sensors to protect food from external contamination
silica/silicon substrates to flexible substrates for large-scale production and oxidation, as well as storing high-temperature or acidic food, and
of such sensors. The sensor exhibited high sensitivity to ethanol gas at high-temperature cooking conditions for food status monitoring.
room temperature and showed good reproducibility. Sun et al. describe Jin et al. fabricated two silicon nitride ceramic dot matrix structures,
the use of elastic poly(dimethyl-siloxane) carriers to fabricate single- Gyroid and Octet truss structures, using DLP technology [59]. Varying
crystal semiconductor nanoribbons in stretchable geometries [54]. The the design parameters of the structures can change their compressive
surfaces of these ribbons were chemically bonded to PDMS supports, strength, elastic modulus, and energy absorption capacity, and the
resulting in a level of mechanical stretchability that exceeded the Gyroid structure exhibits superior mechanical properties for the same
intrinsic strain at the breaking level of the ribbon material itself. dimensions. Shen et al. fabricated 0–3 piezoelectric composites with
polydimethylsiloxane as the matrix and lead zirconate titanate as the
3.2. Metal materials piezoelectric phase [60]. The effect of different solid phase contents on
the rheological properties of the slurry, which is a ceramic slurry, was
The strength and wear resistance of metallic materials are usually investigated, and it was verified experimentally which case after 3D
higher than those of plastic and fiber materials, and therefore they have printing is more suitable to be made into flexible sensors. This material
a wide range of applications in flexible sensor manufacturing. The has a promising future in flexible electronic devices. Fu et al. fabricated
process of using metallic materials to fabricate flexible sensors typically a flexible capacitive pressure sensor with high structural elasticity using
employs electrochemical deposition techniques. This technique can be ceramic materials [50]. The sensor has high stability because of the
performed by depositing a layer of metal onto a thin polymer substrate excellent mechanical stability of the ceramic nanofiber network. The
to produce a thin, flexible metal film. The metal film can be easily bent, sensor can be used for real-time health monitoring and motion detec­
twisted, and stretched, which makes it ideal for flexible sensor fabrica­ tion. Because of the high-temperature resistance of ceramic, it can
tion and can effectively reduce sensor manufacturing costs and increase operate properly at 370 ◦ C and thus shows great promise for harsh
production efficiency [55]. Metallic materials can also be used to 3D environment applications.
print metal particles to fabricate flexible sensors. By adding metal par­
ticles such as copper and iron or printing materials with various high- 3.4. Hydrogel
strength metal fibers, flexible sensors with high strength, high elec­
trical conductivity, and high resistance to water evaporation can be Hydrogel has properties such as flexibility and transparency, which
fabricated [56]. These metallic materials can produce 3D coatings dur­ allow it to be precisely manufactured in arbitrary shapes by 3D printing
ing the flexible sensor manufacturing process, which means that metal technology. Hydrogels also have a high level of biocompatibility, which
films can be fabricated with precise and highly complex surface shapes makes them particularly important in 3D-printed biomaterials [61]. By
and structures to enable special sensor functions, such as precision exploiting these characteristics, we can create more flexible and more
pressure sensors. Metallic materials are used to make the electrode and adaptable flexible sensors that bring significant value to a variety of
wire portion of the flexible sensor to determine the amount of salt or applications. The adsorption properties of hydrogel can enable the
other dissolved substances in the food by measuring the conductivity of fabricated sensors to monitor the chemical composition in food, and the
the food. Due to the good thermal conductivity of metallic materials, introduction of bioreceptors on its surface can also be used for the
temperature sensors can also be made to monitor changes in food tem­ detection of microorganisms such as bacteria and molds in food, which
perature during cold chain transportation. can help in the management of food safety and the prevention of bac­
Zhou et al. used liquid metal to make a new 3D printed multifunc­ terial contamination. Current hydrogels for 3D bioprinting include
tional inductive flexible and stretchable sensor that is capable of single-component hydrogels, interpenetrating network hydrogels, su­
measuring axial tension and curvature [49]. The sensor was fabricated pramolecular hydrogels, nanocomposite hydrogels, composite hydro­
using a developed coaxial liquid metal 3D printer by co-printing silicone gels, polyurethane and ionic gels [62].
rubber and liquid metal, which provides excellent stability and reli­ One-component hydrogels are single natural or modified hydrogels
ability. Liu et al. fabricated strain sensors and bending sensors by 3D that form hydrogels on their own in the presence of initiators, etc. This
printing technology using liquid metal microchannels [57]. Later, they type of hydrogel has been widely used for 3D bioprinting, for example,
integrated them into the sensing glove of human bodies to detect the hydrogels based on sodium alginate, gelatin, and collagen [63]. Wu et al.
gestures of human hands and integrated the bending sensors into the used rigid gelatin as one of the main raw materials to make a hydrogel
robotic hands to control the movement of the soft robotic hands, which with high mechanical strength, rapid self-recovery, fatigue resistance,
finally realized the human–computer interaction. and excellent anti-swelling properties [64]. The results of this study
provide a new idea for the preparation of gelatin-based hydrogels with
3.3. Ceramic materials anti-swelling properties. It has a prominent role as a bio-3D printing ink
for flexible sensors, drug detection, etc.
Ceramic materials are special inorganic materials with high strength Interpenetrating network hydrogels are unique hydrogel mixtures
and high-temperature stability as well as good corrosion resistance, formed by entangling two or more hydrogel components together in the
protection, and biomedical acceptability, which makes them promising form of network interpenetration, and their morphological features such
for a wide range of applications in 3D printing for manufacturing flex­ as cell-like structure, interfacial interpenetration, and biphasic conti­
ible sensors [58]. Ceramic materials can be used for 3D printing flexible nuity give the hydrogels good mechanical strength and responsiveness
sensors by rapid sintering techniques (e.g., microwave sintering tech­ [65]. Huang et al. altered the spatial conformation of bovine serum al­
niques). Sensors of various shapes can be easily fabricated using this bumin by unfolding, and subsequently, the fully exposed peptide chains

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were able to induce in situ polystyrene sulfonic acid conductive sensitive to external forces, pressures, deformations, and other physical
hydrogels to form interpenetrating network conductive hydrogels in one quantities through its elastic properties.
step and rapidly [66]. Its excellent properties combined with 3D printing Ionic gels are gel systems formed in water using ion exchange ma­
technology make it promising for the 3D printing of flexible sensing terials like polyelectrolytes. These gels can create a network by
electronics. absorbing water and possess excellent water adsorption and retention
Supramolecular hydrogels are self-assembled hydrogels formed by properties. Peng et al. prepared light-curing resins of ionic liquids and
networks of low molecular weight molecules, oligomers, or polymers hydrogen-bonded acrylate monomers, and the resulting sensors exhibi­
that self-assemble into larger fibers or some sort of ordered superstruc­ ted high-pressure sensitivity, low hysteresis, and stable signals over time
ture within minutes to hours through non-covalent interactions and then [74]. The sensors are currently used to monitor pulse, finger, gait, and
cross-link and entangle through covalent or non-covalent interactions other human movements, but could be extended to monitor food prod­
[67]. Ma et al. applied the principle of supramolecular structure design ucts due to their antimicrobial properties and accurate temperature
to cross-link conducting polymers and flexible template polymers with change detection. Ionic gels usually have good biocompatibility and
dynamic chemical bonds to form high-strength electroactive hydrogels tunable physicochemical properties, and thus have a wide range of ap­
with dynamic network structures [68]. The designed polyaniline- plications in the field of flexible biosensors.
polyvinyl alcohol supramolecular hydrogel has a tensile strength of Hydrogels are considered to be the best candidates for flexible sen­
5.3 MPa, an elongation at break of more than 250%, a specific capaci­ sors due to their high biocompatibility and adjustable mechanical
tance value of more than 1000F/g, and a specific capacitance retention properties. With the increasing application of 3D printing, the “ink” for
rate of 90% after 1000 charge/discharge cycles, which substantially 3D printing is no longer limited to inorganic substances such as plastic
exceeds existing electroactive hydrogels. Based on this, combined with powder. With its excellent biocompatibility and the cross-fertilization of
3D printing technology, it provides an idea for the manufacturing of 3D printing technology, “bio-ink” will achieve great success in the fields
high-performance capacitive flexible sensors. of medical health, food safety, and life science.
Nanocomposite hydrogel is a hydrogel with added nanoparticles
[69]. The addition of nanoparticles to the hydrogel can change the 4. Applications in the field of food monitoring
physical, chemical, and biological properties of the hydrogel matrix, and
the hydrogel with the addition of nanoparticles has better printing At present, there are many methods for food analysis and moni­
properties, mechanical properties, thermal stability, etc. Zhang et al. toring. One is the sensory monitoring method, which is used to assess the
prepared a sustainable hydrogel from natural glyoxylic acid (GL) and quality characteristics of food such as color, aroma, taste, shape, and
biocompatible polyvinyl alcohol (PVA) in a water/glycerol solvent [51]. texture, as well as people’s tendency to prefer food through human
The hydrogel has a high molecular weight, high mechanical properties, sensory organs [75]. The second is the physical monitoring method,
good biocompatibility, frost resistance, and anti-drying ability. Inspired through the measurement of physical quantities to understand the tissue
by the reducing properties of GL, a gradient silver nanoparticle layer can composition and content of food [76]. The third is the chemical analysis
be constructed in situ on the hydrogel surface without the addition of method, through the chemical properties of the food tissue composition
reducing agents. It not only provides UV shielding and an antibacterial as the basis for analysis [77]. The fourth is the instrument monitoring
effect to the hydrogel but also effectively improves the sensing proper­ method, also known as the physical and chemical monitoring method,
ties. The desired properties were also achieved so that the hydrogels which is based on the physical and chemical properties of food, using
could be assembled into sensors to detect the full range of human motion sophisticated analytical instruments and various sensors for food
with high sensitivity, stability, and durability. Combined with 3D monitoring, which has the advantages of simplicity, sensitivity, speed,
printing technology, it provides ideas for designing high-performance, accuracy and so on [78]. The application of sensors in food monitoring
multifunctional, and sustainable flexible sensors. has been widely used in the instrumental monitoring method, which has
Composite hydrogels are heterogeneous hydrogels formed by the led to the full improvement of the automated process of food. Flexible
interaction of multiple hydrogels, and the combination of multiple sensors fabricated using 3D printing technology have been developed in
materials and cells can print complex three-dimensional biological the fields of food monitoring, analyzing ingredients in food, food
structures with multiple morphologies, structures, mechanical proper­ packaging, etc., depending on the method of food detection we cate­
ties, and multifunctional components, thus establishing multiple bio­ gorize the overview according to gases, microorganisms, and non-gas
logical structures with bio-nano-morphological structures and compounds, as shown in Table 1 and Fig. 6.
functional properties [70]. Liu et al. added nano cellulose to gelatin and
polyacrylamide and then replaced the water molecules in the hydrogels 4.1. Gases monitoring method
with a mixture of zwitterionic betaine and ammonium sulfate using a
simple solution substitution method [71]. The new composite hydrogel In the field of food safety, the application of gas sensors is very
has properties such as toughness, high electrical conductivity, and freeze important. By 3D printing flexible sensors, we can realize the rapid
protection. The prepared hydrogels have excellent mechanical proper­ detection and monitoring of harmful gases in food, so as to protect the
ties due to the introduction of nano cellulose and the “salting” effect of health and safety of consumers. Ma et al. investigated the development
gelatin and ammonium sulfate. In the future, combined with 3D printing of a gas sensor using a nanostructured conducting polymer that detects
technology, flexible sensors made of this amphoteric hydrogel will be biogenic amines, such as spoilage and cadaverine, which are indicators
able to adapt to low-temperature environments and be used in more of meat spoilage [82]. This is a sensor that monitors gases for food
industrial production. monitoring. The sensor can act as a switch in near-field communication
Polyurethane is an elastomer with good flexibility and stretchability, (NFC) tagging circuits. It has a high sensitivity to 5 ppm ammonia NH3.
making it one of the ideal materials for preparing flexible sensors. Peng The sensitivity is ΔR/R0 = 225% for 5 ppm ammonia NH3 and 46% and
et al. utilized polyurethane and carbon nanotube composite casting to 17% for 5 ppm humic and cadaveric amines, respectively. Nano­
make a porous flexible strain sensor, which has great potential for structured polyaniline (PAni), the switching material in the sensor, is
wearable devices [72]. Meanwhile, Zeng et al. fabricated light-healing inherently non-toxic and has good in vitro and in vivo biocompatibility.
polyurethane by molecular design, which has excellent mechanical This technology can be used to create smart sensing for food condition
strength and healing rate, and has a wide range of applications [73]. In monitoring applications in daily life, storage, and supply chain. Lv et al.
flexible sensors, polyurethane can be used as the base material of the investigated the preparation and characterization of an ammonia sensor
sensor to provide soft support and protection. At the same time, poly­ based on a PEDOT: PSS film containing iron chloride (FeCl3) additive
urethane can also be used as the sensing layer of the sensor, which is [79]. The sensor monitors food with ammonia as the key analyte. This

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D. Song et al. Chemical Engineering Journal 474 (2023) 146011

Table 1
3D printing for food monitoring.
Food monitoring Monitoring Design content Based on Advantages Applications References
methodology targets

Gases Monitoring NH3 A gas sensor using nanostructured Nanostructured High sensitivity The technology can be [82]
Method conducting polymers conductive polymers used to create intelligent
sensing for food condition
monitoring applications
in everyday life, storage,
and supply chains
NH3 It investigated the preparation and PEDOT with iron chloride Ten-fold increase in It has potential [79]
characterization of ammonia (FeCl3) additive: PSS film response value and a 30- applications for
sensors based on PEDOT: PSS films fold reduction in monitoring NH3 gas
containing iron chloride (FeCl3) response time under ambient conditions
additives and can also be used as an
indicator of food spoilage
C₂H₅OH、 A new method for fabricating fully Flexible polymer foil Good response and It has great potential for [83]
NH3、CO inkjet-printed gas sensors on sensitivity to different smart food packaging and
flexible polymer foils concentrations of premature disease
ethanol, ammonia, and detection
carbon monoxide gases
at 300 ◦ C
TVB-N A hydrogel that protects Water, agar, and purple Good stability and anti- For smart food packaging [84]
anthocyanins from leaching sweet potato leaching properties
anthocyanins
Microorganisms Escherichia coli A method for detecting disease- Magnetic Nanoparticle High sensitivity It can be developed for [85]
Monitoring causing bacteria in food using Cluster the detection of food
Method magnetic nanoparticle clusters pathogens.
(MNC) and 3D-printed spiral
microchannels
Escherichia coli Development of a transparent, Transparent cyclic olefin Stable during the shelf Packaging solution for [80]
durable, and flexible sensing polymer (COP) films life of perishable real-time monitoring of
surface packaged foods pathogens
Non-gas Carbohydrate Bionic “intestinal microcapsules” Copper oxide Specific and accurate There is also a wide range [86]
Compounds electrochemical cell sensors nanoparticles detection of wheat of application prospects
Monitoring fabricated by 3D printing alcohol-soluble protein in food monitoring
Method H2O2 A three-dimensional printable Conductive polymers of Linear responses at 61.3 It provides a promising [87]
paper sensor made of a conductive poly(3,4-ethylene- × 10− 9 and 61.3 × 10− 6 approach for the
polymer called poly(3,4-ethylene- dioxythiophene) development of flexible
dioxythiophene) polystyrene polystyrene sulfonate and cost-effective sensors
sulfonate (PEDOT: PSS) (PEDOT: PSS) for food detection.
Chlorpyrifos, A lateral flow biosensor using a Fluorescent aptamer Improved sensitivity and Portable and practical [81]
Diazinon, and fluorescent aptamer-based zero background tool for on-site detection
Malathion biosensor integrated with a of multiple pesticides in
smartphone spectrum reader food samples
C6H12O6 A new technique for fabricating PDMS Good uniformity, Laboratory Glucose [88]
microelectrodes on conductivity, and Biosensing System
polydimethylsiloxane (PDMS) to excellent adhesion to
form biosensors in microchannels PDMS
H2O An integrated multimodal flexible Stacked Znin2s4 Durable and stable Real-time monitoring of [89]
sensor system for plant growth nanosheets performance monitoring food freshness and
management of humidity quality, providing real-
time information on the
condition of food
Methane- Design and preparation of long- Long-range ordered Good specificity, The potential value in [90]
phosphonic range ordered macro-porous anti- macro-porous anti- selectivity, and establishing pesticide
opaline hydrogel particles with opaline hydrogel particles significant reflection detection systems in food
methane-phosphonic acid with methane- peak shift for methane- safety
imprinting sites phosphonic acid blotting phosphonic acid
sites

sensor was prepared using inkjet printing on a flexible polyimide film, was converted to a stable ink and inkjet printed on the gold electrode.
Polyimide film is non-toxic, stable, and suitable for use in medical and Electrical measurements of the printed sensor characterized the
food industries. The addition of FeCl3 to the PEDOT: PSS film signifi­ response and sensitivity to different concentrations of ethanol,
cantly improved the NH3 sensing performance of the sensor with a ammonia, and carbon monoxide gases at an operating temperature of
tenfold increase in response value and a 30-fold reduction in response 300 ◦ C in dry and humid air. With ethanol, ammonia, and carbon
time compared to the pure PEDOT: PSS film. The thin-film sensor has monoxide as the key analytes, this sensor is extremely sensitive to lower-
potential applications for monitoring NH3 gas under ambient conditions, range chemical gases and is reversible. The sensor is stable and can be
and because ammonia is a common by-product of protein breakdown in packaged for applications in the food monitoring industry. It has great
food, it can be used as an indicator of food spoilage. Kassem et al. potential for smart food packaging and premature disease detection.
describe a new method for fabricating a fully inkjet-printed gas sensor Zhai et al. developed a novel colorimetric film for real-time monitoring
on a flexible polymer foil [83]. The sensor was made by printing a of fish freshness based on the combination of starch/polyvinyl alcohol
platinum heater and gold electrodes on top of a substrate separated by a (SPVA) and rosehips anthocyanins (RACNs), fixed in the headspace of
thin layer of printed polyimide insulation. The researchers used a hy­ the packaged fish [84]. These colorimetric films, which were immobi­
drosol gel process to synthesize a nanoscale tin dioxide-based sol, which lized in the headspace of the packaged fish, presented a gas-based sensor

8
D. Song et al. Chemical Engineering Journal 474 (2023) 146011

Fig. 6. Different monitoring methods. a. Illustration of the fabrication process for PEDOT: PSS based film sensors; b. Schematic diagram of the gas sensing per­
formance measuring system; c. Schematic illustration of sensing mechanism of FeCl3-PEDOT: PSS hybrid[79]; d. Illustration of highly sensitive DNAzyme sensors
cleaving in the presence of live E. coli cells; e. Meat and apple samples wrapped in film containing sensors; f. Representative bright-field (top) and fluorescence
(bottom) images of sensors on the solid food sample wrapped in food packaging. Food samples were inoculated with a bacteria mixture of E. coli (right) and the same
bacteria mixture without E. coli (left) at 4 ◦ C[80]; g. Mobile phone fluorescence spectrum reader; h. Smartphone-based fluorescence detection principle[81].

in the form of a gas sensor when reacting with the total volatile salt The sensor is stable for at least 9 days at various pH conditions (pH 14–3)
nitrogen (TVB-N) These colorimetric films exhibit specific color changes and can detect E. coli in meat and apple juice at concentrations as low as
based on gas sensors when reacting with TVB-N. The films are stable for 103 CFU/Ml. The stability of the developed biosensor is much greater
up to 14 days at refrigerated and room temperatures, with a relative than the shelf life of packaged food products, is simple and requires
color change of less than 5%, and are safer and more environmentally minimal user intervention, is compatible with packaging materials
friendly due to the natural pigments in the films. The colorimetric film currently in use, and since the DNA zyme probe can be generated by in
can reflect the freshness of fish food in real time with high sensitivity. vitro selection to react to different bacteria, this sensor has great po­
This kind of sensor has great application value in the packaging of fish. tential for application in food packaging and creating surfaces that can
specifically detect and report the presence of target bacteria in complex
environments.
4.2. Microorganisms monitoring method

Microbial contamination is a major food safety concern. Using 3D 4.3. Non-gas compounds monitoring method
printed flexible sensors, highly sensitive microbial sensors can be
developed to rapidly and accurately detect microbial contamination Chemical residues in food are an important issue for food safety.
such as bacteria and molds in food products, providing real-time Utilizing 3D-printed flexible sensors, high-sensitivity compound sensors
monitoring and control means for food production and processing. Lee can be developed that can rapidly detect pesticides, heavy metals, and
et al. presented a method for the isolation and monitoring of pathogenic other harmful compounds in food, providing an effective means for food
bacteria from foodstuffs using magnetic nanoparticle clusters (MNCs) quality monitoring and food safety management. Jiang et al. fabricated a
and 3D-printed helical microchannels for the detection of pathogenic bionic “intestinal microcapsule” electrochemical cellular sensor by 3D
bacteria from foodstuffs without the need for complex pre-treatment printing, which could specifically and accurately detect wheat alcohol-
[85]. This method can detect the presence of pathogenic bacteria in soluble proteins [86]. Subsequently, self-assembled flower-like copper
10 mL of milk samples with a sensitivity of 100 cfu/mL (colony forming oxide nanoparticles were synthesized and multi-walled carbon nano­
units per mL), and the efficient and safe isolation and monitoring tubes were functionalized with hydrazide to improve the performance of
mechanism makes it highly applicable in the field of food monitoring. the sensor. This sensor reduces the error of manually modified screen-
The sensor developed by Yousefi and other researchers and scholars was printed electrodes, and the cellular sensor loaded with 1 ×106 cells/
fabricated by covalently attaching picoliter-sized microarrays of an E. mL of cell suspension and immobilized for 10 min can sensitively detect
coli-specific RNA-cleaving fluorescent DNA enzyme probe (RFD-EC1) to wheat alcohol-soluble proteins. Conductive bio-composite hydrogels
a thin, flexible, and transparent cyclic olefin polymer (COP) film [80]. have also been prepared since then, and such hydrogels have also been

9
D. Song et al. Chemical Engineering Journal 474 (2023) 146011

widely used in food monitoring. A three-dimensional printable paper quickly. 3D printing technology allows precise control of the sensor
sensor made of a conductive polymer called poly(3,4-ethylene- manufacturing process, making the performance and response of each
dioxythienyl) polystyrene sulfonate was presented by Giaretta et al sensor very consistent and repeatable, which is of great value in mass
[87]. Paper-based sensors have the advantages of non-pollution, good production [92]. The sensors can be easily mounted on food surfaces or
flexibility, lower cost, and a wide range of raw material sources. The other areas to be monitored, and are also easy to remove and clean,
detection of hydrogen peroxide (H2O2), a by-product of enzymatic re­ reducing operational difficulties and costs. Thus, 3D printed sensors are
actions, is of great interest in food and medical applications. The linear an inevitable process in sensor development and a triumph of 3D
response of the sensor is in the range of 61.3 × 10− 9 and 61.3 × 10− 6, printing technology in the sensor field. However, even though 3D-
and the correlation between drug resistance and H2O2 concentration printed sensors have a promising future, there are still significant chal­
depends to a large extent on the level of integrase. It provides a prom­ lenges that limit the production of future sensors. First is the use of 3D
ising approach for the development of flexible and cost-effective sensors printing, material issues can limit the performance and reliability of
for food detection. Cheng and colleagues proposed a new method for printed sensors, and sensors may fail or fail after a long period of use, so
detecting multiple pesticides in food samples using a fluorescent better design and manufacturing processes are needed to improve their
aptamer-based lateral flow biosensor integrated with a smartphone reliability, it is especially important to study the ideal material, un­
spectrum reader [81]. The detection limits of this sensor for chlorpyri­ suitable materials can sometimes have a huge impact [93]. Second,
fos, diazinon, and malathion were 0.73 ng/mL, 6.7 ng/mL, and 0.74 ng/ there is still a lack of information on the lifetime of 3D-printed sensors
mL, respectively. reduced the detection limits of pesticide residue levels and it is impossible to know how long a 3D-printed product can be used
in food, and the recoveries of vegetable samples were estimated to be in [94]. In addition, each sensor may have slightly different response
the range of 82.4%–112.8% in practical applications. The biosensor also characteristics and therefore needs to be calibrated to ensure its accu­
uses a novel fluorescent inhibitor nano pair to perform “signal on” rather racy and repeatability. Finally, there is a lack of standards and specifi­
than “signal off”, resulting in increased sensitivity and zero background. cations for 3D-printed flexible sensors in food inspection, which need to
The biosensor is integrated with a 3D-printed smartphone reader, be developed to ensure their safety and effectiveness.
making it a portable and practical tool for in situ detection of multiple 3D printed sensors, although more widely developed, are not yet
pesticides in food samples. A new technique for fabricating microelec­ widely used in food analysis and monitoring. Food analysis and moni­
trodes on polydimethylsiloxane (PDMS) to form biosensors in micro­ toring are particularly important for food safety and are closely related
channels has been proposed by Wu et al [88]. Using inkjet-printed silver to human health. The sensor has the advantages of fast analysis, high
nanoparticles and modifying the surface of PDMS with a chemical called accuracy, and low price in the field of food analysis and monitoring, and
(3-Mercaptoplico) tri-methoxy silane (MPTMS) to improve its surface can detect substances that cannot be detected by other methods, and the
wettability and adhesion to silver, the resulting silver patterns exhibited sensor can also be tested online, making a significant contribution to
good uniformity, electrical conductivity, and excellent adhesion to food composition analysis and predicting the shelf life of food [95].
PDMS. Successful fabrication of a three-electrode electrochemical Currently, sensors can accurately detect proteins, organic acids, amino
biosensor and its integration into a lab-on-a-chip glucose biosensing acids, as well as some food additives, minerals, alcohols, etc. in the field
system. Lu et al. present an integrated multimodal flexible sensor system of food monitoring. In addition, they can measure the freshness of food
for plant growth management that uses stacked Znin2s4 (ZIS) nano­ as well as detect microorganisms and various harmful substances con­
sheets as the core sensing medium to rapidly sense light illumination and tained in food to ensure food safety. Despite the many advantages of 3D
monitor humidity with durable and stable performance [89]. The pro­ printed sensors, if they are to be used for food monitoring, attention
posed ZIS-based flexible sensor can not only sense light illumination must be paid to the non-toxicity of the printed materials, which should
with fast response (~4 ms), but also monitor humidity with long-lasting guide future research. Although the application of 3D-printed sensors in
stable performance, and using 3D printing technology, this flexible food inspection is not yet perfect, it has to be said that there is a huge
sensor can be printed on food packaging materials, which can monitor potential for future development.
the freshness and quality of food products in real-time, and provide real-
time information about the condition of food products. Huang et al.
designed and prepared long-range ordered macro-porous anti-opaline Declaration of Competing Interest
hydrogel particles with methane-phosphonic acid imprinting sites [90].
The sensor enables a redshift of >120 nm from green to red, which can The authors declare that they have no known competing financial
be recognized by the naked eye in less than five minutes. It can be easily interests or personal relationships that could have appeared to influence
recognized without any complex and time-consuming instrumentation. the work reported in this paper.
The detection limit is as low as 1 × 10− 6 mol/l. This work provides an
excellent strategy for designing highly sensitive colorimetric sensors for Data availability
phosphorus pesticide detection, and the safety level can be classified by
adjusting the size of the hydrogel particles. It has promising applications Data will be made available on request.
as a colorimetric sensor for food safety, ecological pollution determi­
nation, and rapid detection of nerve gases. Acknowledgment

5. Conclusions and prospects This research is supported by the 2115 talent development program
of China Agricultural University.
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