Research Article

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An Electrically Conductive Oleogel Paste for Edible Electronics

Pietro Cataldi,* Leonardo Lamanna, Claudia Bertei, Federica Arena, Pietro Rossi, Mufeng Liu,
Fabio Di Fonzo, Dimitrios G. Papageorgiou, Alessandro Luzio, and Mario Caironi*

1. Introduction
Edible electronics will facilitate point-of-care testing through safe devices
digested/degraded in the body/environment after performing a specific A myriad of applications related to
drug delivery, food tagging, and human
function. This technology, to thrive, requires a library of materials that are
health monitoring would benefit from
the basic building blocks for eatable platforms. Edible electrical conductors a class of electronic devices that are
fabricated with green methods and at a large scale and composed of food safely edible.[1–3] In this context, ingest-
derivatives, ingestible in large amounts without risk for human health are ible electronics (IE) represent a pow-
needed. Here, conductive pastes made with materials with a high tolerable erful tool in preventing, screening, and
upper intake limit (≥mg kg−1 body weight per day) are proposed. Conductive treating diseases via innovative swallow-
able devices.[4,5] As such, IE delivered
oleogel composites, made with biodegradable and food-grade materials like
breakthroughs from the 1950s till today,
natural waxes, oils, and activated carbon conductive fillers, are presented. such as pH-endoradiosonde,[6,7] ingestible
The proposed pastes are compatible with manufacturing processes such as pressure,[8] motion,[9] temperature,[10] and
direct ink writing and thus are suitable for an industrial scale-up. These con- gas sensors,[11] energy sources to power
ductors are built without using solvents and with tunable electromechanical ingestible devices,[12,13] detectors for the
ingestion of capsules or tablets,[14] and
features and adhesion depending on the composition. They have antibacte-
cameras[15] and microphones[16] for vital
rial and hydrophobic properties so that they can be used in contact with food sign monitoring, to cite a few. IE ensures
preventing contamination and preserving its organoleptic properties. As a high performance since it uses standard
proof-of-principle application, the edible conductive pastes are demonstrated electronics components but simultane-
to be effective edible contacts for food impedance analysis, to be integrated, ously faces limitations because it is built
for example, in smart fruit labels for ripening monitoring. mainly on materials that are not degra-
dable in the body. Indeed, after inges-
tion, the non-digestible and bulky nature
P. Cataldi, L. Lamanna, F. Arena, P. Rossi, F. Di Fonzo, A. Luzio, M. Caironi of standard materials for electronics poses a risk of retention
Center for Nano Science and Technology @PoliMi for the patients, requiring medical supervision.[9] Moreover,
Istituto Italiano di Tecnologia besides the cost that may force their reuse, the non-degra-
Via Giovanni Pascoli, 70/3, Milano 20133, Italy dable, long-lasting, and sometimes poisoning characteristics
E-mail: [email protected]; [email protected]
to the environment impose their recollection after expulsion.
C. Bertei, D. G. Papageorgiou
School of Engineering and Materials Science
Lastly, IE materials and devices employ energy-intensive man-
Queen Mary University of London ufacturing that is not sustainable for the single-use desirable
Mile End Road, London E1 4NS, UK for food monitoring purposes.[17]
F. Arena Edible electronics aim to bridge ingestible with green elec-
Department of Energy tronics and shift from swallowable to fully digestible and not
Politecnico di Milano hazardous components.[18] Therefore, their implementation
Via Lambruschini 4, Milano 20156, Italy
will ensure a safe administration without medical supervi-
P. Rossi
Department of Physics sion and enable point-of-care testing since the device will
Politecnico di Milano safely degrade in the body/environment after performing a
P.zza Leonardo da Vinci 32, Milano 20133, Italy specific task.[17] Edible electronics envision realizing all the
M. Liu passive and active electronic components exploiting food
National Graphene Institute derivatives with green and large-scale production methods
Henry Royce Institute and Department of Materials
University of Manchester
and enabling sustainable, safe, and cheap devices. Nowa-
Oxford Road, Manchester M13 9PL, UK days, the most urgent need for edible electronics to thrive
depends on creating a library of materials that function as
The ORCID identification number(s) for the author(s) of this article
can be found under https://doi.org/10.1002/adfm.202113417.
the basic building blocks for eatable technologies. The isola-
tion, the design, and the realization of edible insulators, con-
© 2022 The Authors. Advanced Functional Materials published by Wiley- ductors, and semiconductors that are non-toxic, sustainable,
VCH GmbH. This is an open access article under the terms of the Creative and completely safe for ingestion even in large amounts (i.e.,
Commons Attribution License, which permits use, distribution and repro-
duction in any medium, provided the original work is properly cited. ≥ mg per kg body weight [bw] per day), that are produced
through simple and cost-effective processes and exhibit satis-
DOI: 10.1002/adfm.202113417 fying electrical properties are needed as a first step.

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Insulators that are safely edible in large amounts without any An edible conductor that is producible on a large scale and
adverse impact on human health are plentiful.[17,19–29] Edible at a low cost through green manufacturing methods that are
conductors and semiconductors that are not simply ingestible, compatible with existing production plants is undocumented.
but are non-toxic, and with good and stable performances are Such edible conductor needs to take advantage of the electronic
extremely challenging to be developed.[18,30–32] Studies and tech- properties of food and food derivatives that are eatable in large
nologies entirely dedicated to designing and advancing edible amounts (i.e., ≥ mg per kg bw per day) without any potential
conductors and semiconductors with the features required for adverse impact on human health. It should exhibit stabilities
edible electronics are rare. Nevertheless, these classes of mate- of the electrical properties even in exotic environments such as
rials are necessary to enable all the edible passive and active high humidity environments and water-based ones such as the
electronic components. GI tract. Such electrodes should be compliant and adhesive to
State-of-the-art edible conductors can be categorized into different surfaces, including food and pills.
ionic and electronic ones, although mixed conductive behav- Such an edible conductor would be ideal for food quality
iors exist. Edible ionic conductors rely mostly on hydrogels. monitoring.[54–56] In particular, monitoring the aging of fruits
For example, a gel of gellan gum and salted gelatin and com- through electrical impedance spectroscopy (EIS) is a potentially
mercially available food spread such as Vegemite and Marmite disruptive technology to improve the agricultural sector’s effi-
were proposed as 3D printable edible electrodes.[33,34] Trans- ciency and reduce food waste.[57] EIS on fruit may enable quick,
parent protein-based films of silk/laponite[35] and elastomeric on the ground, quantitative, and portable analysis of fruits
bovine serum albumin[36] were proposed as ionic conductors ripening and aging. Thus, it has the potential to substantially
applied in human-machine interaction and electrophysiological improve devices proposed so far, which check the aging through
signal sensing, respectively. Melanin thin films and melanin smart labels on food packaging and are mainly constituted con-
nanoparticles-based composites exhibit a hybrid electronic stituted by time and temperature indicators or gas sensors.[58–61]
and ionic conduction mechanism and were suggested as eat- Here we present a conductive composite paste made with
able electrodes.[37–41] Yet, edible hydrogels have ionic conductive materials with a highly tolerable upper intake limit (≥ mg per
properties that cannot sustain a constant electronic current in a kg bw per day). The matrix is constituted by a biodegradable
circuit. Furthermore, the ionic conduction features depend on oleogel of food-grade beeswax and vegetable oil. Conductivity
the environment because relying on hydration. is provided by adding micrometric-sized AC particles. The
Typical edible electronic conductors with daily intake in the composite paste is the first designed specifically for edible elec-
range of µg per kg bw per day are metals, such as magnesium, tronics. This conductor, displaying a resistivity in the order of
zinc, iron, silver, or gold. The first three are often used as thin 100 Ω cm, is fabricated without employing solvents and at low
films (i.e., 100 nm–10 µm) in transient biodegradable electronics temperature, not exceeding 100 °C, ensuring green manufac-
applications due to their ability to dissolve at different rates in turing. The paste exhibits tunable electromechanical features
contact with water-based liquids.[42–45] Magnesium[46] and silver[47] and adhesion depending on the composition. The different
were applied as electrodes for current collection in edible and formulations of the composite are potentially compatible with
biodegradable triboelectric nanogenerators. Silver and gold thin large-scale production processes such as direct ink writing,
films are implemented in miniaturized electronic devices such extrusion, and injection molding and thus are ideal for an
as honey-gated transistors[18] and transferable on food/pills.[17] industrial scale-up. Moreover, the paste shows antibacterial
Low quantities of gold are also used as current collectors for activity and is hydrophobic, thus avoiding eventual food con-
cheese-[48] and gelatin-[49] based supercapacitors. Nevertheless, tamination when used in contact with it and possessing elec-
metals are pricy and are not compatible with bulk and versatile trical properties robust to air and aqueous environments. To
production methods proper of the polymer industry. According provide an example of the many possible practical uses of the
to the European Food Safety Agency (EFSA), they can be eaten proposed edible conductive paste in the future, we have demon-
safely only in small amounts in the range of 1–100 µg per kg bw strated that it enables effective edible contacts for food imped-
per day. Moreover, they are often nanometer-sized.[50] Thus, they ance analysis, to be integrated in smart fruit labels for aging
should be handled with attention in edible applications due to monitoring.
the chance of accumulation in the gastrointestinal (GI) tract that
normally increases with decreasing particle size and depending
on the particle shape.[1,50] Another material exploitable as an 2. Results and Discussion
edible electronic conductor is activated carbon (AC, also known
as activated charcoal and vegetable carbon, E 153) that has a The edible conductor was designed using only food-grade mate-
daily intake in the order of g per kg bw per day.[1] AC-based elec- rials eatable in large amounts (i.e., ≥ mg per kg bw per day)
trodes were proposed for edible electrochemical sensors,[51] for without toxic adverse effects. In particular, beeswax (E 901,
sensing glucose in the gastrointestinal tract,[52] and to realize conservative exposure estimate by EFSA 22 mg per kg bw per
edible supercapacitors.[48–49] AC was also proposed as anode and day),[62] sunflower oil, and activated carbon (E 153, ≥ 500 mg
cathode for edible biofuel cells.[53] Generally, AC is readily avail- per kg bw per day)[1,63] were selected (Figure 1a). The adopted
able on the market at a low price (≈0.01–0.3 € g−1) and is pro- AC was micrometric sized (10–100 microns, see Figure S1, Sup-
duced on a large scale in powder form, approved by EFSA and porting Information) to avoid any eventual toxicity effect of
Food and Drug Administration. Nevertheless, its powdery form nanomaterials.[50] The wax and the oil were melt-mixed, adding
makes it not easy to handle and, as-is, does not present satisfying the desired amount of AC afterward. Solvents were avoided,
mechanical and adhesion properties. and the temperature reached during the production process

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Figure 1. Edible conductor composition, manufacturing, and micrometric structure. a) Raw materials that constitute the composite paste: sunflower
oil, beeswax, and activated carbon (AC). b) Pliability of the edible conductor and demonstration of its potential for direct ink writing techniques (inset).
c,d) Scanning electron microscopy of the pure wax–oil matrix at 1:1 ratio and edible conductor made adding 30 wt% of AC to the matrix, respectively.

was 100 °C, ensuring a green and straightforward methodology. Information), on the one hand, leads to a more uneven texture
The thermogravimetric analysis (TGA) demonstrates that the owing to the incorporation of the filler inside the matrix. On
processing temperature leaves the materials intact, as shown the other, due to the AC intrinsic porosity that absorbs the oil,
in Figure S2, Supporting Information. Indeed, all the samples the wax microcrystals are more evident with AC inclusion, as it
start to degrade above 200 °C. At the same time, a temperature is possible to notice comparing Figure 1c,d (see also scanning
of 100 °C ensures a complete melting of the wax, as shown in electron microscopy (SEM) at variable AC content in Figure S5,
the differential scanning calorimetry (DSC) analysis presented Supporting Information).
in Figure S3, Supporting Information, enabling an efficient mix The ability to adapt and tune the rheology of composite
with oil and AC. Lastly, the employed temperature leaves the pastes through variation of matrix and particle compositions
chemical fingerprint of wax and oil intact after samples fab- can deliver materials that can be produced with many manu-
rication, as shown by the Fourier transform infrared spectro­ facturing techniques, which display multiple functionalities and
scopy (FT-IR) analysis of Figure S4, Supporting Information, are easily adaptable to a specific application.[67–69] Therefore, the
ensuring unaltered edibility and organoleptic properties of the rheological properties of the WaxOil (1:1) and the oleogels real-
pastes. The material resulting from this procedure is a com- ized by adding different amounts of AC (from 0 to 40 wt%), were
posite paste that is pliable and can be shaped as required, as tested. The samples with AC were labeled simply referring to the
shown in Figure 1b and Video S1, Supporting Information. The wt.% (% from now on) of the AC added to the wax-oil matrix.
fabrication process can be easily scaled up with uncomplicated Frequency sweep analyses of several rheological parameters
industrial appliances since the materials used are produced (Figure 2a–d and Figure S6, Supporting Information) were per-
on a large scale and the composite paste is compatible with formed between 1 and 100 Hz at three different temperatures:
polymer manufacturing techniques such as direct ink writing ambient temperature (25 °C), 37 °C to simulate proximity with
(inset Figure 1b). All the data reported below refers to samples the human body, and 45 °C to simulate a hot natural environ-
produced by melt mixing. ment (e.g., a very warm summer). All the oleogels including
The micromorphology of the wax-oil mixture (weight ratio AC show a solid gel-like viscoelastic behavior with storage
1:1, named WaxOil (1:1) from now on) is displayed in Figure 1c. modulus G′ > G″ (loss modulus), G′ increasing similarly to
Wax-oil blends are termed oleogels, and the gelation mecha- G″ with increasing frequency, and a phase shift consistently
nism is connected to the arrangement of chemical species below 45°, as noticeable comparing Figure 2a,b, and Figure S6,
such as wax esters and alkanes into micrometric plate-like wax Table S1, Supporting Information. The only sample character-
assemblies, which aggregate to form 3D networks of crystals of ized by a fluid state is the pure WaxOil (1:1) oleogel at 45 °C,
wax that entraps liquid oils.[64,65] Such microcrystal platelets are which displays a phase shift of ≈51 °, as appreciable in Table S1,
evident in the beeswax sunflower oil mixture and are respon- Supporting Information. Interestingly, the G′ and G″ tuning
sible for the micrometric size roughness.[66] Adding the AC is achieved by changing the percent of AC filler inside the oil
filler that has a size range of 10–100 µm (Figure S1, Supporting wax matrix. Indeed the WaxOil (1:1) oleogel at 25 °C shows a

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Figure 2. Rheological and adhesion features of the composite paste. In parts (a)–(d) and (f), the pure beeswax (Wax), the wax vegetable oil matrix at
a 1:1 ratio (WaxOil [1:1]), and the samples realized adding different amounts of activated carbon (AC, from 0 to 40 wt%) are tested. a,b) The samples’
storage moduli (G′) at 25 and 37 °C, respectively. c,d) The complex viscosity η at 25 and 37 °C, respectively. e) Tunable η of the composite paste loaded
with 40% AC and diverse wax:oil ratios (1:1, 1:3, 1:9). f) Adhesive shear strength of the sample as a function of the composition.

storage modulus of ≈18 MPa at 1 Hz, gradually reaching a value with increasing temperature because of the proximity of the
of ≈45 MPa by increasing the filler loading to 40% AC, very melting temperature (≈62 °C – Figure S3, Supporting Informa-
close to the one of pure beeswax at ≈47 MPa, as appreciable in tion) to the testing temperature. These moduli are comparable
Figure 2a. A similar tunability but at lower G′ values is observed with those of pasta dough that shows G′ in the order of 0.1 MPa
for the samples at 37 °C. In this case, the WaxOil (1:1) sample at similar testing parameters.[70,71]
exhibits a storage modulus of ≈2.6 MPa, while the sample filled The complex viscosity (η) of all the samples shows a shear-
with 40% AC displays a modulus of ≈11 MPa, as shown in thinning behavior, as shown in Figure S8, Supporting Informa-
Figure 2b. The same trend is observed for the rheological tests tion, a feature particularly relevant for pastes, which need to
at 45 °C but with even lower values of G′ and G″, with G′ in be soft and easily pliable when used or processed, while they
the order of 0.1 MPa at 1 Hz (see Figure S6, Supporting Infor- need to show high viscosity at rest after application to prevent
mation). The moduli of the samples are significantly decreased spreading.[72] η can be fine-tuned with respect to the wt.% of

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AC, and in general, it decreases with increasing frequency, as The inclusion of conductive fillers inside insulating matrixes
shown in Figure 2c,d. At 1 Hz, it increases from ≈3.0 106 to is effective toward inducing electrical conductivity in the
7.3 106 Pa s at 25 °C and from 4.9 105 to 1.8 106 Pa s at 37 °C, resulting composites.[76] The minimum filler loading required
going from the WaxOil (1:1) sample to the 40% AC one. to switch the composite from an insulator to a conductor is the
A critical problem of the composites loaded with a high electrical percolation threshold.[77–79] The current–voltage (I–V)
amount of filler is the difficulty in the mixing and fabrication; curves of the edible pastes are ohmic from 20% AC concentra-
in this case, the pronouncedly increased viscosity may result in tions, as shown in Figure S10, Supporting Information, and
brittle and not self-standing materials after fabrication. The 40% the majority charge carriers are determined to be holes given
AC sample presents a “paste-powder” form and the abovemen- the positive measured Seebeck coefficients, typical of graphitic
tioned issues. The brittleness of the composite is confirmed materials,[80] as shown in Table S2, Supporting Information.
by SEM images, which display a texture with multiple micro- The edible paste resistance is measured against the weight of
metric cracks, as shown in Figure S7, Supporting Informa- AC filler incorporated inside the wax-oil matrix and converted
tion. The tuning of the rheological properties for this sample is to resistivity following the formula reported in the methods
achieved by changing the wax and oil ratio, which improves the part. At filler loadings up to 16%, the direct current resistivity
paste melt-miscibility and conformability. For example, at 37 °C of the oleogel is above 109 Ω cm, corresponding to the resolu-
(Figure 2e), changing the wax:oil ratio to 1:3 and 1:9 is effective tion limit of the adopted instrument. At 20% AC, electrical per-
in decreasing the complex viscosity of one and two orders of colation is reached, and the resistivity dropped to ≈1 MΩ cm.
magnitude, respectively. A similar dependence of the viscosity Increasing the filler content to 40% permits it to reach values
on the wax:oil ratio is observed at 25 °C and 45 °C (Figure S6, of 101 ± 2 Ω cm, as shown in Figure 3a. The micrometric fillers
Supporting Information). Accordingly, as shown in Figure S7, inside the matrix at low loadings (i.e., lower than 20% AC) are
Supporting Information, the cracks are absent for the 40% AC- not densely packed and thus do not create an electrical con-
loaded oleogels with 1:3 and 1:9 wax-oil ratios. As such, the self- duction network. On the other hand, after reaching the elec-
standing nature of the paste with 40% AC is restored. trical percolation threshold, an electrically conductive path is
Another desirable feature of pastes is the adhesion to var- available for the charge carrier, as schematically drawn in the
ious surfaces. Therefore, adhesion on a standard plastic sub- bottom of Figure 3a. All the samples with 40% AC filler dis-
strate (polymethyl methacrylate, PMMA) and glass is tested for play equal resistivity values independently on the ratio between
the pure wax, the WaxOil (1:1), and the samples with diverse the wax and the oil in the matrix (see Figure S11, Supporting
AC content, as shown in Figure 2f (PMMA substrate) and Information), indicating that similar dispersions of the fillers
Figure S9, Supporting Information (glass substrate). In par- are obtained for all of them after fabrication. The obtained
ticular, shear adhesive strength tests demonstrate that the resistivity values are comparable with other reports that employ
adhesion strength of the wax-oil matrix could be tuned by solely activated carbon as an edible electrode (range of resis-
the inclusion of different amounts of AC inside the composite tivity 0.5–1000 Ω cm),[1] here with the added advantages of
formulation. Indeed, the pure oleogel displays an adhesive a paste such as pliability, conformability, and compatibility
strength of ≈3.3 kPa on PMMA, and adding AC from 8 till with large scale production methods proper of the composite
30% enhances the paste adhesion from ≈3.7 to ≈12.4 kPa, a industry. The conductivity of the 40% AC-loaded sample is suf-
value close to pure wax that reaches ≈16.4 kPa. The tunability ficiently low to enable the powering of a light-emitting diode
of the adhesive strength with AC inclusion is achieved thanks (LED) electrically connected through the paste, as shown in the
to the porosity of the AC filler that “dries” the oil component inset of Figure 3a and Video S1, Supporting Information.
of the paste, enhancing the available “free” wax fraction in the For practical applications, a desirable property for an edible
paste. As a consequence, adherence improves, while a self- conductor is the stability of the electrical conduction properties
standing structure is maintained. At 40% AC concentration, the even in contact with water-based liquids.[81] Thus, the pastes
“dry phase” (which consists of the AC and the wax) becomes were immersed in water for more than 50 h, and their weight
predominant, and the sample powdery nature negatively influ- and electrical resistance variation were monitored. Throughout
ences its adhesive properties (Figure S7, Supporting Informa- this period, the weight variation is negligible and the elec-
tion). The sample with 40% AC inclusion does not display trical resistance increased by less than 6% of the initial value,
any adhesive properties, but by increasing the oil component as shown in Figure S12, Supporting Information. These two
in the matrix, and adhesion strength in the order of kPa can factors reveal a weak interaction of the samples with water,
be re-established, because the complete absorption of the wax- in agreement with the water contact angles on pastes above
oil phase by the AC is prevented. In particular, tuning the wax 90° (see Figure S13, Supporting Information). Such features
to oil ratio to 1:3 and 1:9 restores an adhesion strength for the improve the stability to water immersion of the state-of-the-art
sample containing 40% AC of ≈3.0 and ≈1.4 kPa, respectively. that relies on water-soluble metallic particles.[1,81]
The same behavior is measured on glass substrates, but with The electrical impedance modulus (|Z|) and the phase of the
slightly lower adhesive strength (Figure S9 and Video S1, Sup- edible pastes different formulations in the frequency range 102–
porting Information). Changing the ratio of wax and oil permits 106 Hz are presented in Figure 3b–c, respectively. The pastes with
the restoration of adhesive properties fundamental for practical filler loadings below 20 wt. % AC behave as insulators, exhibiting
applications. The measured adhesive strength values are com- the same curve of an open circuit, therefore implying |Z| > 108 Ω
parable, for example, with polymer-based degradable adhesives at a frequency of 100 Hz. Starting from 20% AC, the paste starts
used for surgery and tissue engineering (range 1–100 kPa)[73,74] to display a resistive behavior: from 25% AC, |Z| is constant
and polyurethane-based adhesive for wood (≈80 kPa).[75] and in the order of 100 kΩ (up to 5 × 103 Hz, after which the

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instrumental response dominates), with a phase close to zero, as

shown in Figure 3c. |Z| further decreases by increasing the AC
content maintaining a phase close to zero, showing two orders
of magnitude reduction with increasing filler loading up to 40%.
These measurements confirm the quasi-static resistance meas-
urements (Figure 3a): the electrical percolation threshold for this
conductive oleogel is close to 20% AC, and pastes have purely
resistive electrical properties after percolation.
As a proof-of-principle of one of the many possible applica-
tions of the proposed conductive paste, we have tested it as
an electrode in a label made of edible materials to monitor
fruit aging through EIS.[82–86] Indeed, a crucial component to
realize an enabling technology for food monitoring based on
EIS are the electrodes. The reported studies exploit Ag/AgCl
electrodes or other metallic ones.[57,85,87] An essential opera-
tional part of these electrodes is the electrolyte gels applied
between the electrodes and fruits.[85] The hydrogel improves
the adhesion and contains free chloride ions such that the
charge can be carried to the electrodes. Although these devices
are a standard in electrochemistry and clinical practice (e.g.,
electrocardiogram, electroencephalogram, electromyography),
they show drawbacks if applied to food chain supply moni-
toring. Indeed, ideally, electrodes for EIS on food require two
main features:
– Edibility for safe implementation: the tag is attached directly
on fruit and should be removed before eating the monitored
food. As such, it could release some residue on the food. Such
residue should be safely edible without any possible adverse
effects.
– Low cost to provide a widespread usage.
The Ag/AgCl electrodes own none of these characteristics.
Indeed, Ag is a noble metal (≈0.6 € g−1), and its acceptable daily
intake is low (µg per kg bw per day),[1] making Ag/AgCl elec-
trodes not suitable for this technology.
The formulation with 40% AC and a ratio of wax to oil of
1:3 was selected to fabricate the edible electrodes since it shows
the best compromise in rheological properties, adhesion, and
electrical conductivity. Apples were selected as model fruits
because they are among the most common ones tested so far
with EIS.[82–86] The fabrication steps for the edible label com-
prise the sticking of two conductive electrodes on the fruit, their
wiring, and the encapsulation with pure beeswax, as shown in
Figure 4a–c. The electrodes are compliant on the apple sur-
face, as shown in Figure 4d. The obtained tag with an area of
1 cm2 thoroughly adheres to the fruit to support the weight of
the apple itself (≈100 g) without detaching (see Figure S14, Sup-
porting Information).
The modulus (|Z|) and the phase of the impedance of the
apple measured in the frequency range between 102 and 106 Hz
through the edible electrodes are presented in Figure 4e–f,
respectively. In 14 days, the impedance increases for the edible
composite. Such a trend is already found in previous reports
on EIS on fruits.[57,86,88] Noteworthy, the EIS performed with

Figure 3. Resistivity and impedance of the edible composites. a) Electrical a matrix. b) Modulus of the sample impedance with different amounts
resistivity as a function of the AC content inside the wax–oil oleogel matrix. of activated carbon included inside the wax–oil paste. The pure matrix
In the inset, the powering of a green LED through the eatable paste, with (WaxOil [1:1]) and the open circuit measurements are reported as refer-
12 V applied. Below, the schematic of the percolation of a filler inside ences. c) Phase of the impedance of the sample reported in (b).

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Figure 4. The fabrication process of a proof of concept label for electrical impedance spectroscopy (EIS) on fruits and its performances. a–c) Photos
of the steps needed to assemble the sensors on an apple and d) of its cross-section. e) Shows the modulus of the impedance of the apples recorded
for 14 days through EIS made with the edible tags on the fruit. f) Displays the phase of the impedance of the apples recorded through EIS. The phase
is constant for 14 days. g) A focus of the time dependent impedance of the apple at 100 kHz recorded with the edible tag (gray column) and using
silver paint (red column) as a comparison.

edible conductor shows a predominant capacitive behavior presence of the samples containing activated carbon with a bac-
(phase ≈80°) unvaried during the 14 days (Figure 4f). At a fixed terial survival of about 2–4 × 106 CFU mL−1, corresponding to
frequency of 100 kHz (Figure 4g), the label made with the P ≥ 2 Log. The better antibacterial response of the composite
edible paste gives a value of |Z| of the apple of ≈18 kΩ at the material gives evidence of the biocidal activity that is mainly
starting time and reaches a value of ≈30 kΩ after 14 days. A driven by the activated carbon contribution.
similar starting value is recorded with a silver paint electrode
painted on the same apple and measured simultaneously,
reaching ≈23 kΩ after 14 days. 3. Conclusion
In Table 2, the list of ingredients of the edible label is
reported. Noteworthy, all the components are below the limit Edible electrical conductive pastes made with food-grade mate-
of daily intake suggested by EFSA. Therefore, after removal, the rials have been successfully demonstrated. The edible conduc-
toxicity risk is negligible even if there is a bulky residue of the tors advance the state-of-the-art of edible electronics by being
label still attached on food. eatable in large amounts (≥ mg per kg bw per day). Further-
An additional benefit of using beeswax is that it may provide more, they are produced with green methods that do not
natural antibacterial activity,[89] a property that avoids food con- involve solvents and display low energy consumption, that is,
tamination. E. coli represents one of the most widespread food temperatures up to 100 °C for a short amount of time, while
contaminants.[90] The results of antimicrobial tests performed
on the Gram-negative bacterium E. coli are shown in Table 1,
reporting the bacterial survival rate for the wax vegetable oil Table 1. Logarithm of the number of viable bacteria recovered after
matrix at a 1:1 ratio, and the samples realized adding different 24 h and antimicrobial activity P against Escherichia coli calculated by
Equation (2).
amounts of activated carbon (8%, 30%, and 40%). After 24 h of
incubation time, the uncoated petri dish made of polystyrene Sample Log CFU mL−1 Antibacterial activity [P]
plastic allows the growth of E. coli strain until an increment in
Uncoated plastic 8.42 ± 0.05
the colony-forming unit of 8.44 × 108 CFU mL−1. A moderate
biocidal effect against E. coli is observed when the wax vege- WaxOil (1:1) 7.00 ± 0.04 1.42 ± 0.06

table oil matrix is used. After 24 h, a low decrement in the cell AC 8% 6.20 ± 0.15 2.22 ± 0.14
density is observed on the petri dish, confirming moderate anti- AC 30% 6.42 ± 0.13 2.00 ± 0.12
bacterial activity (P) lower than 2 Log (see Equation [2] in the AC 40% 6.40 ± 0.03 2.02 ± 0.05
methods section for details on the definition of P). In contrast,
the results demonstrate a remarkable bactericidal effect in the Data are reported as the mean ± standard deviation.

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they are compatible with large-scale production processes. for 2 min, cooled down to 30 °C at 10 °C min−1, held at 30 °C for 2 min,
The materials are made with pure food and additives that then heated up again to 170 °C at 10 °C min−1. An empty aluminum pan
are already employed in large scales in the food industry and was used as reference.
Rheology experiments were performed using a Discovery HR-3
pharmacology. Rheometer (TA Instruments) equipped with a Peltier plate temperature
An oleogel matrix made with biodegradable and digestible system. An aluminum parallel plate geometry with a diameter of 20 mm
ingredients such as natural waxes and oils and a micrometric was used as upper geometry, and a gap width of 1.5 mm was maintained
eatable conductive filler such as activated carbon constitutes for each sample. Samples were prepared on the Peltier plate at 45 C
the conductors. These composites can reach a resistivity as low to allow optimal shaping and trimmed prior to analysis. Oscillatory
as 100 Ω cm. Such resistivity does not change upon air and amplitude sweep and frequency sweep tests were performed on each
sample at 3 different temperatures: 25, 37, and 45 °C. First, amplitude
water contact. They exhibit tunable electromechanical features
sweep tests were performed to determine the linear viscoelastic region
and adhesion depending on the composition. In particular, the in which the G′ and G″ are independent of the strain amplitude. The
activated carbon concentration and the wax to oil ratio ensure tests were conducted at a constant frequency of 1 Hz while varying
precise control of the paste’s rheological, adhesive, and elec- the torque from 10 to 5000 µN m (which was translated in oscillation
trical properties. In addition, they are conformable, pliable, and strain % for a better understanding of the results). A non-Newtonian
can adhere to curved surfaces. They feature antibacterial and behavior was determined with a steep decrease of the moduli beyond
the linear viscoelastic region. Second, frequency sweep measurements
hydrophobic properties, avoiding food corruption and possible
were conducted at a constant torque of 1000 µN m while varying the
adverse effect upon ingestion and the variation of their proper- frequency from 1 to 100 Hz (which was translated in oscillation frequency
ties upon the interaction with the body. The edible conductors for better understanding of the results). Each measurement was
are assembled as a proof-of-concept food label that can monitor performed after 3 min of soaking at the desired temperature to allow the
fruits aging through simple electrical impedance measure- sample to stabilize. Before the beginning of each run, a constant force
ments. Such green and sustainable technology could constitute of 2 N was applied to the sample and maintained throughout the test in
the first building block towards large-scale eatable conductors order to keep the sample in place and avoid slipping. The only exception
was made for high-load-AC samples, which required a 10 N axial force to
and monitoring the fruit production chain from the farm to avoid slipping during measurements at 25 °C.
fork, as well as finding wide applications in the pharmacolog- Infrared spectra of the samples were collected through an attenuated
ical and healthcare sector. total reflectance (ATR) device (Bruker-VERTEX 70v FT-IR Spectrometer).
All measurements were recorded with a resolution of 4 cm−1, and
collecting 128 scans. During measurements, the samples were placed on
the spot of the ATR device and gently pressed.
4. Experimental Section SEM measurements were performed using a Jeol JSM-6010LV
Materials: Refined beeswax was bought from Sigma Aldrich (E 901). operating at an acceleration voltage of 10 kV and recording the secondary
Activated carbon was purchased by the same supplier (Supelco, puriss. electron emission. The distance between the samples and the SEM
P.a., powder, E 153). Sunflower Oil and apples were acquired in a local aperture was 0.5 cm. After immersion at −195.79 °C in liquid nitrogen,
supermarket. These materials were used as received without any further the samples were cut by tearing them with two tweezers to preserve the
process needed. original morphology.
To prepare the samples, the wax and the oil were first melted and The measurement of adhesive shear strengths was followed with
mixed at 100 °C for 20–30 min. Afterward, the required amount of AC ASTM D3163, regarding bond adhesive of rigid plastic. The adhesive
was added and mixed at the same temperature and time. The obtained samples studied in this work were stuck onto surfaces of both PMMA and
samples were pastes that can be shaped on demand and were proven to glass slides. The speed of the crosshead was set to be 1.3 mm min−1 for all
be direct ink writable. samples as suggested by the standard. The values of force were recorded
To manufacture the proof of principle edible label on fruits, two throughout the measurement and then converted into strength with an
conductive electrodes were stuck on the apple, wired, and then area of adhesion of approximately 200 mm2 for all the samples tested.
encapsulated with pure beeswax. The encapsulating wax layer acts as The electrical resistance (R) of the pastes was measured using a
protection and enhances the tag adhesion on the fruits (see Figure 4 and source-meter from Keithley (model 2450) in the four-probe arrangement.
Figure S14, Supporting Information). The electrodes were fully compliant Silver paste (RS pro, product number 186–3600) was painted, forming
on different surfaces. The amount of the material used for such an 10 mm wide contacts (W) spaced by 10 mm (L) on rectangular shaped
application was weighted and is summarized in Table 2. Note that if we specimens 1 mm thick (t) sticking on glass slides. Resistivity (ρ) was then
consider the average weight of an adult person to be 70 kg, the entire tag calculated considering the described geometry through the equation:
could be safely eaten.
Methods: TGA was performed using a TGA Q500 (TA Instruments) W· t
ρ =R (1)
equipped with platinum pans. Each sample was weighted and heated up L
to 600 °C at 10 °C min−1 in nitrogen atmosphere.
DSC was performed using a DSC 25 (TA Instruments) previously The same setup was used for the measurements underwater but
calibrated with indium. The samples (20.0 ± 1 mg) were hermetically wiring the contacts and encapsulating them with protective beeswax.
closed in aluminum pans and underwent a series of heating and cooling The electrical impedance of the composites was measured on
steps. Each sample was heated up to 170 °C at 10 °C min−1, held at 170 °C specimens with the same dimensions and silver contacts described
above. All the measurements were undertaken with Precision Impedance
Table 2. Amount of the materials used for the tag on the fruit. analyzer Agilent 4294A. The frequency of alternating current for the
measurement was at a range of 102 to 106 Hz. In the manuscript, we
Sample Wax [g] Oil [g] Activated carbon [g] report the impedance modulus and phase.
The I–V curves were measured by means of Semiconductor Parameter
Electrodes 0.012 ± 0.003 0.035 ± 0.006 0.019 ± 0.003 Analyzer Agilent B1500A, in four-probe arrangement, employing the
Wax 0.868 ± 0.093 NA NA same sample described above.
The Seebeck coefficient was determined using the custom-built
The composition used was with 40% AC and a wax:oil ratio of 1:3. set-up extensively described in our previous report.[91] Samples were

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prepared spreading a uniform layer of conductive paste on a glass Data Availability Statement
substrate (2 × 1.5 cm) used as a support. To ensure optimal electrical
contact, two electrodes were patterned above the film using silver The data that support the findings of this study are available from the
paint (RS PRO Conductive Paint) at a distance of 0.5 cm to comply corresponding author upon reasonable request.
with the set-up geometry. The measurements were performed at room
temperature (25 °C) and in vacuum (10–3 bar) to reduce undesired
thermal convection and conduction phenomena.
Static water contact angles of the pastes were measured by an optical Keywords
contact angle device (DataPhysics). Ten microliters of deionized water
activated carbon, edible electronics, edible oil, green electronics, natural
were deposited on the samples.
wax
The biocidal effect of the wax vegetable oil matrix at a 1:1 ratio (WaxOil
(1:1)) and the samples realized adding different amounts of activated
Received: December 31, 2021
carbon (8%, 30%, and 40%) on microorganism survival was evaluated
Revised: February 14, 2022
as described in the ISO 22196. Briefly, E. coli was pre-inoculated
Published online: February 26, 2022
aerobically for 12 h at 37 °C in Luria–Bertani (LB), with constant shaking
at 210 rpm. Bacteria were collected by centrifugation for 10 min at 3500 g
and re-suspended at a cellular density of about 105 colony forming units
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