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Elec ochemis y Communica ions
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3D-p in ed elec odes o he de ec ion o myco oxins in ood
Muhammad Za i Mohamad Nasi
a
, Filip No o ný
b
, Osamah Alduhaish
c
, Ma in Pume a
b,c,d,e,⁎
a
Di ision o Chemis y and Biological Chemis y, School o Physical and Ma hema ical Sciences, Nanyang Technological Uni e si y, Singapo e 637371, Singapo e
b
Cen e o Ad anced Func ional Nano obo s, Depa men o Ino ganic Chemis y, Facul y o Chemical Technology, Uni e si y o Chemis y and Technology P ague,
Technická 5, 166 28 P ague 6, Czech Republic
c
Chemis y Depa men P.O. Box 2455, College o Science, King Saud Uni e si y, Riyadh 11451, Saudi A abia
d
Depa men o Medical Resea ch, China Medical Uni e si y Hospi al, China Medical Uni e si y, No. 91 Hsueh-Shih Road, Taichung, Taiwan
e
Fu u e Ene gy and Inno a ion Labo a o y, Cen al Eu opean Ins i u e o Technology, B no Uni e si y o Technology, Pu kyňo a 656/123, B no CZ-616 00, Czech
Republic
ARTICLE INFO
Keywo ds:
3D p in ing
G aphene elec ode
Fused deposi ion modelling
Food sa e y
ABSTRACT
Addi i e manu ac u ing, also e med 3D p in ing, enables economical, dynamic and apid ab ica ion o cus-
omisable h ee-dimensional (3D) de ices ca e ing o specialised unc ions. He ein, we epo he ab ica ion o
3D-p in ed g aphene elec odes by used deposi ion modelling (FDM), which we e hen used o he elec o-
chemical de ec ion o he myco oxin zea alenone (ZEA). Chemical and elec ochemical p e- ea men p ocedu es
we e applied o emo e he ine polylac ic acid ex e nal laye om he g aphene elec odes, exposing and
ac i a ing he inne g aphene su ace. These p ocedu es enhanced he sensi i i y o he elec odes owa ds
elec ochemical de ec ion o ZEA. The ac i a ed 3D-p in ed g aphene elec odes displayed a good linea e-
sponse ( = 0.995) o e a wide concen a ion ange (10 o 300 µM). This p oo -o -concep applica ion opens up
a wide ange o possibili ies o he ab ica ion o 3D-p in ed elec ochemical de ices o use in ood analysis and
ood sa e y.
1. In oduc ion
Food secu i y and sa e y ha e become inc easingly impo an opics
o discussion among in e na ional and egional agencies, pa icula ly
in iew o he po en ial h ea s om e o ism as well as new s ains o
esis an pa hogens. Addi ionally, wi h he sp ead o ungi, bac e ia and
o he mic oo ganisms, ood inspec o s and egula o y bodies a e pla-
cing inc easing emphasis on he shel li e o ood p oduc s. One class o
compounds which is o high in e es is ha o myco oxins. Myco oxins
a e poisonous seconda y me aboli es o low molecula weigh p oduced
by na u ally occu ing ungi which cause ood p oduc s o u n mouldy
unde ce ain condi ions [1]. Consump ion o such compounds is
known o ad e sely a ec human heal h, possibly leading o cance and
e en dea h. As such, s ingen egula ions ha e been pu in place o
mi iga e he sp ead o myco oxins in oods u s. Zea alenone (ZEA) is a
myco oxin p oduced by he Fusa ium species o ungi and is ound
mainly in maize p oduc s and ce eals such as whea [2]. I is c ucial o
ha e eliable and apid me hods o de ec ing ZEA in ood samples o
enable he ele an au ho i ies and ood inspec o s o ake p omp ac-
ion o mi iga e he sp ead o ZEA, especially in ood s o age acili ies.
The inc easing emphasis on accu a e and sensi i e de ec ion o
myco oxins has spu ed esea che s o de elop a a ie y o me hodologies
wi h he aim o lowe ing de ec ion limi s and imp o ing analy ical de-
ec ion. One such app oach in ol es he use o elec ochemical echniques.
Resea ch in o imp o ing elec ochemical de ec ion o myco oxins has
p ima ily ocused on imp o ing he limi s o de ec ion and sensi i i y
h ough he de elopmen o elec ochemical me hodologies [3] such as
he op imisa ion o immunoassay sys ems [3–6] as well as he in-
co po a ion o no el ansduce pla o ms [7–9] The de ec ion o ood
con aminan s is o he u mos impo ance and he e olu ion o echniques
has o keep pace wi h ad ances in echnology. In his espec , addi i e
manu ac u ing, also known as h ee-dimensional (3D) p in ing, can be
seen as a use ul ool o p in ing cus omisable elec odes o he selec i e
de ec ion o myco oxins. Addi i e manu ac u ing allows o he apid
p in ing o 3D objec s designed using 3D modelling so wa e. The 3D
objec is ab ica ed by digi ally con olled deposi ion o successi e laye s
o ma e ials un il he inal s uc u e is c ea ed. The use o 3D p in ing in
elec ochemis y has been widely epo ed o applica ions in ene gy de-
ices [10,11] and biomedical applica ions [12–15]. Howe e , o he bes
o ou knowledge, he e ha e no been any epo ed applica ions o 3D
p in ing in elec ochemical ood analysis, o mo e speci ically o he de-
ec ion o myco oxins.
h ps://doi.o g/10.1016/j.elecom.2020.106735
Recei ed 16 Ma ch 2020; Recei ed in e ised o m 22 Ap il 2020; Accep ed 22 Ap il 2020
⁎
Co esponding au ho .
E-mail add ess: [email p o ec ed] (M. Pume a).
Elec ochemis y Communica ions 115 (2020) 106735
A ailable online 27 Ap il 2020
1388-2481/ © 2020 The Au ho (s). Published by Else ie B.V. This is an open access a icle unde he CC BY-NC-ND license
(h p://c ea i ecommons.o g/licenses/BY-NC-ND/4.0/).
T
A 3D-p in ed de ec o would be a use ul al e na i e o cu en de-
ec ion me hodologies, wi h he possibili y o ab ica ing cus omisable
on-si e poin -o -ca e diagnos ic de ices a lowe cos while in-
co po a ing complex designs [16]. 3D-p in ed me al elec odes ha e
been shown o pe o m eliably o he elec ochemical de ec ion o
mul iple pollu an s and con aminan s [17–19]. He ein, he de ec ion o
ZEA using a 3D-p in ed g aphene elec ode is s udied as a p oo -o -
concep o a cus omisable elec ode o apid poin -o -ca e de ec ion o
myco oxins in ood samples. The g aphene elec odes we e ab ica ed
by used deposi ion modelling (FDM) and hen subjec ed o chemical
and elec ochemical p e- ea men s be o e being es ed o he elec-
ochemical de ec ion o ZEA.
2. Expe imen al
2.1. Ma e ials and appa a us
Zea alenone (ZEA) and phospha e bu e saline (PBS) in able o m
we e pu chased om Sigma-Ald ich (Singapo e). N,N-dime hyl o ma-
mide (DMF) and ace oni ile (ACN) we e ob ained om Me ck
(Singapo e). G aphene/polylac ic acid (PLA) ilamen s we e ob ained
om Black Magic 3D, New Yo k. Deionised wa e (DI) pu i ied using
he Milli-Q sys em (Millipo e, MA, USA) wi h esis i i y o 18.2 MΩ cm
was used. A s ock solu ion o ZEA was p epa ed in ACN and s o ed in
he da k a 4 °C. Wo king solu ions we e p epa ed daily by dilu ing
sui able amoun s o s ock solu ion wi h PBS, which se es as he sup-
po ing elec oly e.
The Ag/AgCl e e ence elec ode, pla inum coun e elec ode and
glassy ca bon (GC) wo king elec ode (diame e 3 mm) we e ob ained
om CH Ins umen s (Texas, USA). Edge-plane py oly ic g aphi e
(EPPG) (diame e 3 mm) was ob ained om Au olab (The Ne he lands).
The su aces o he EPPG and GC elec odes we e enewed by polishing
wi h alumina pa icles using a polishing pad.
2.2. Elec ochemical p ocedu es
Vol amme ic measu emen s we e pe o med a oom empe a u e
(25 °C) using a h ee-elec ode con igu a ion and an Au olab Type III
elec ochemical analyse (Eco Chemie, The Ne he lands) con olled by
NOVA 1.10 so wa e (Eco Chemie). Cyclic ol amme y (CV) expe i-
men s we e pe o med a a scan a e o 100 mV s
−1
unless o he wise
s a ed.
2.3. Fab ica ion o 3D-p in ed g aphene elec odes
G aphene/polylac ic acid ilamen s we e used o p in he elec-
odes, which we e designed using Fusion 360 CAD so wa e
(Au odesk). The design o he elec odes was inspi ed by ou p e ious
wo ks and consis s o a 1.6 mm hick disc (diame e 8 mm) a ached o
a ec angula s em. The design was expo ed o a .s l ile, sliced and
con e ed o a .gcode ile using Slic3 so wa e. 3D p in ing was pe -
o med using a P usa i3 MK3 p in e (P usa Resea ch) wi h a Olsson
Ruby uby- ipped 0.4 mm nozzle (3DVe ks an, Sweden). The nozzle
and bed empe a u es we e se o 220 °C and 60 °C, espec i ely. The
es o he p in ing pa ame e s we e adop ed om he P usa Slic3
con igu a ion known as PLA.
2.4. P e- ea men o 3D-p in ed elec odes
A chemical p e- ea men was pe o med by soaking he 3D-p in ed
g aphene elec odes in DMF o 10 min [20]. Subsequen ly, he ea ed
elec odes we e washed wi h e hanol and deionised wa e be o e d ying
o e nigh unde ambien condi ions. Elec ochemical ac i a ion was
hen pe o med in 0.01 M PBS (pH 7.2) by applying a cons an po en ial
o 2.5 V ( s.Ag/AgCl) o 250 s [21].
3. Resul s and discussion
P e- ea men ac i a ion is c ucial o enhancing he sensi i i y and
de ec ion capabili ies o he ab ica ed elec odes [22–24]. Fo g a-
phene elec odes p in ed om comme cially a ailable g aphene/poly-
lac ic acid ilamen s, p e- ea men o ac i a e he unde lying g aphene
laye s o elec ochemical applica ions by emo ing he polylac ic acid
laye on he su ace g ea ly enhances he pe o mance o he 3D-p in ed
g aphene elec odes [20]. The elec ochemical esponse has been e-
po ed o be u he enhanced by a combina ion o chemical and elec-
ochemical p e- ea men s [21]. The use o speci ic enzymes has also
been epo ed o expose he unde lying g aphene laye o po en ial
biosensing applica ions [24]. In his s udy, a p e iously epo ed che-
mical and elec ochemical p e- ea men p ocedu e [20] was adop ed
as i p oduces signi ican ly imp o ed ou pu signals which would po-
en ially maximise ol amme ic measu emen s o he de ec ion o ZEA
(Scheme 1). In summa y, he elec odes we e i s designed using he
3D ske ch-up modelling so wa e be o e being p in ed ia used de-
posi ion modelling (FDM). The p in ed g aphene elec odes we e hen
soaked in N,N-dime hyl o mamide (DMF). Chemical p e- ea men e-
sul ed in he co osion o he ou e polylac ic laye , as is e iden om
he black pa icula e ma e ha appea ed in he DMF solu ion (Fig.
S1). A e washing and d ying, elec ochemical ac i a ion was pe -
o med a a cons an po en ial o 2.5 V ( s. Ag/AgCl) in phospha e
bu e solu ion. Fu he de ails o he p e- ea men p ocedu es a e
ou lined in he Sec ion 2. The 3D-p in ed g aphene elec odes we e o
uni o m dimensions wi h a leng h o ~4.5 cm and wi h a ci cula closed
disc a one end (Fig. S2). The end wi h he ci cula closed disk was
imme sed in he sample solu ion du ing all elec ochemical s udies
epo ed in his pape .
The elec ochemical sensing pe o mance o he ac i a ed 3D-
p in ed elec odes was compa ed wi h hose o ba e glassy ca bon (GC)
and edge-plane py oly ic g aphi e (EPPG) elec odes, o analyse any
appa en di e ences in cu en signals ob ained owa ds he de ec ion
o ZEA. Addi ionally, he ol amme ic signals ob ained om he GC
and EPPG elec odes p o ide a baseline compa ison wi h an ine
elec ode and a sensi i e elec ode su ace wi h eac i e edge plane
si es, espec i ely. I can be seen om Fig. 1 ha b oad anodic peaks
cen ed a ~0.7 V ( s. Ag/AgCl) and 0.75 V ( s.Ag/AgCl) we e ob-
se ed o he GC and EPPG elec odes, espec i ely. A de ined anodic
peak was obse ed when expe imen s we e pe o med wi h he ac i-
a ed 3D-p in ed g aphene elec ode. Howe e , he ol amme ic signal
shi ed o a highe po en ial o ~0.9 V ( s.Ag/AgCl). The 3D-p in ed
g aphene elec ode appea s o be less elec oac i e han he GC and
EPPG elec odes. Despi e ha , he p esence o an anodic peak demon-
s a es i s abili y o elec ochemically de ec ZEA. Po assium hyd oxide
was conside ed as an alkaline al e na i e o DMF in he chemical p e-
ea men p ocess in an a emp o imp o e he ol amme ic signals.
Howe e , no anodic peaks co esponding o ZEA we e obse ed, wi h a
s ong backg ound signal p oduced (Fig. S3). Fu he modi ica ions
migh ha e o be made o imp o e and op imise he pe o mance o he
3D-p in ed elec ode.
Scheme 1. Schema ic ep esen a ion o he ab ica ion om g aphene/poly-
lac ic acid ilamen s o 3D-p in ed g aphene elec odes and hei p e- ea men
o he de ec ion o ZEA.
M. Za i Mohamad Nasi , e al. Elec ochemis y Communica ions 115 (2020) 106735
2
Ha ing asce ained he abili y o he 3D-p in ed g aphene elec ode
o elec ochemically de ec ZEA, we nex in es iga ed he eusabili y o
he 3D-p in ed elec odes by washing wi h di e en sol en s (deionised
wa e and ace one). 3D-p in ed elec odes which did no unde go his
washing s ep we e also e-used o in es iga e he signi icance o he
washing s ep. F om Fig. 2, i is no ed ha he absence o a washing s ep
esul ed in a b oade anodic peak which had shi ed o a highe
ol amme ic po en ial. This could be due o he de ec ion o oxidised
o ms o ZEA which had p e iously adhe ed o he elec ode su ace.
Thus, i is ecommended o pe o m a washing s ep be ween measu e-
men s o mi iga e he collec ion o unwan ed side p oduc s. The ol-
amme ic signals ob ained om used 3D-p in ed elec odes washed wi h
DI wa e did no display signi ican de ia ions. The oxida i e peak ob-
ained was simila o ha o a newly ac i a ed 3D-p in ed elec ode,
al hough he obse ed peak heigh was lowe . The numbe o ac i e si es
on he elec ode su ace could ha e been educed p io o he second
measu emen , which could ha e p oduced he obse ed dec ease in he
cu en signal. None heless, he ol amme ic p o iles we e simila .
Howe e , he ol amme ic signal ob ained on washing wi h ace one
esul ed in a ol ammog am wi h spikes a ibu ed o he backg ound
noise. Fu he mo e, no appa en anodic peaks we e obse ed. Upon
close analysis, he ol amme ic p o ile ob ained was simila o ha o
an unwashed eused 3D-p in ed elec ode. The ace one used o washing
migh ha e pa ially co oded and eac ed wi h he ac i a ed g aphene
laye , esul ing in a ‘noisy’ ol amme ic signal which hinde s he ap-
plica ion o he 3D-p in ed g aphene elec ode o de ec ion pu poses.
Hence, i migh no be app op ia e o wash g aphene-based elec odes
wi h ha sh chemicals in o de o p ese e he s uc u al in eg i y o he
su ace laye . The esul s ob ained show ha a washing s ep be ween
measu emen s is ad an ageous and c ucial o ob aining ep oducible
esul s. Addi ionally, deionised wa e u ns ou o be an ideal sol en o
washing used 3D-p in ed ac i a ed g aphene elec odes.
Ha ing es ablished he p e- ea men and washing p ocedu e o he
3D-p in ed elec odes, he esponse o he 3D-p in ed elec ode was
analysed using ol amme y. ZEA has been epo ed o adso b on o he
su aces o he elec odes be o e unde going elec ochemical oxida ion
[25–27]. The pe o mance was compa ed o ha o a con en ional GC
elec ode. Linea plo s o ZEA concen a ions be ween 10 and 300 μM
we e ob ained o bo h GC (Fig. 3A) and ac i a ed 3D-p in ed g aphene
elec odes (Fig. 3B). The ac i a ed 3D-p in ed g aphene elec odes
displayed good pe o mance and linea i y ( = 0.995) owa ds he
de ec ion o ZEA, compa able o ha o he con en ional GC elec ode
( = 0.967). The limi o de ec ion (LOD) was calcula ed by mul iplying
by 3 he quo ien o he s anda d de ia ion o he peak heigh o he
lowes concen a ion o ZEA and g adien o he calib a ion g aph,
while he limi o quan i ica ion (LOQ) was ob ained by mul iplying he
same quo ien abo e by 10 [28–32]. The LOD ob ained o he GC
elec ode was 0.0683 μM wi h a LOQ o 0.228 μM. Howe e , he ac i-
a ed 3D-p in ed g aphene elec ode had a highe LOD alue o
0.340 μM wi h a LOQ o 1.13 μM. The LOD alue achie ed is g ea e
han he de ec ion limi s epo ed p e iously (nanomola concen a ion
le els) [26,27,33] and he maximum de ec able amoun o ZEA pe -
missible in ood samples [34–36]. Despi e his, he esul s p o ide a
p oo -o -concep insigh in o he po en ial inco po a ion o ac i a ed
3D-p in ed g aphene elec odes [37] o he elec ochemical de ec ion
o myco oxins in ood samples [39].
Fig. 1. Cyclic ol ammog ams o glassy ca bon (GC), edge-plane py oly ic
g aphi e (EPPG) and 3D-p in ed elec odes ( he la e ab ica ed om g a-
phene/polylac ic acid ilamen s) in he de ec ion o 100 µM ZEA ( s.Ag/AgCl).
Condi ions: 0.01 M phospha e bu e solu ion (pH 7.2) as elec oly e, scan a e
100 mV s
−1
.
Fig. 2. Vol ammog ams o 3D-p in ed ac i a ed g aphene elec odes washed
wi h di e en sol en s owa ds he de ec ion o 100 µM ZEA ( s.Ag/AgCl).
Condi ions: 0.01 M phospha e bu e solu ion (pH 7.2) as elec oly e, scan a e
100 mV s
−1
.
Fig. 3. Calib a ion plo s o (A) glassy ca bon (GC) and (B) ac i a ed 3D-p in ed g aphene elec odes. Condi ions: 0.01 M phospha e bu e solu ion (pH 7.2) as
elec oly e, scan a e 100 mV s
−1
.
M. Za i Mohamad Nasi , e al. Elec ochemis y Communica ions 115 (2020) 106735
3
This no el app oach o elec ochemical de ec ion o myco oxins
opens up new a enues due o he inco po a ion o 3D-p in ing ech-
nology in elec ochemical senso s. Fu he su ace modi ica ions o he
3D-p in ed elec odes can be explo ed, inco po a ing and p in ing
biological elemen s [24,38] o imp o e hei de ec ion capabili ies.
Addi ionally, he elec ode design could be op imised and imp o ed by
he use o al e na i e conduc i e ma e ials o imp o e he sensi i i y
and elec ochemical esponse o 3D-p in ed elec odes in u u e appli-
ca ions. One such possibili y is he use o ansi ion me al dichalco-
genides (TMDs) [38], which ha e been epo ed o be good conduc i e
ma e ials wi h nume ous applica ions in elec ochemis y. These pos-
sibili ies a e also la gely dependen on u he de elopmen s in 3D
p in ing echnology and expe imen al op imisa ion [40–42]. Fu he
wo k is also equi ed o es he p in ed elec odes in eal samples and
s udy he possible e ec s o in e e ences on de ec ion signals and
sensi i i ies.
4. Conclusion
Addi i e manu ac u ing, be e known as 3D p in ing, has been used
o p oduce elec odes om g aphene/polylac ic acid ilamen s, which
ha e been applied o de ec he myco oxin zea alenone (ZEA) by elec-
ochemical means. A chemical p e- ea men complemen ed by elec-
ochemical ac i a ion o he 3D-p in ed g aphene elec odes has been
shown o p o ide a cheap and e ec i e me hod o he de ec ion o ZEA
wi hin a wide ange (10 o 300 µM) wi h good linea i y ( = 0.995).
The ac i a ed 3D-p in ed elec odes achie ed a LOD o 0.340 μM wi h a
LOQ o 1.13 μM. Despi e hese alues being highe han he maximum
app o ed le els, he esul s ob ained p o ide a pe spec i e ega ding
he applicabili y o 3D-p in ing echnology in ood egula ion and in-
spec ion. This s udy opens he doo o u u e imp o emen s o 3D-
p in ed elec odes o maximise hei pe o mance h ough be e elec-
ode design, be e choice o ma e ials and u he unc ionalisa ion
p ocesses. Addi ionally, his p oo -o -concep wo k opens he possibili y
o on-si e cus omised ab ica ion o de ec ion de ices o ood sa e y
and inspec ion.
Au ho con ibu ions
M.Z.N.M. pe o med elec ochemical expe imen s and da a analysis.
F.N. ab ica ed and cha ac e ized he elec odes. M.P. concei ed and
supe ised he esea ch. All au ho s discussed he da a and he im-
plica ions o he da a. All au ho s con ibu ed o w i ing o he manu-
sc ip .
Decla a ion o Compe ing In e es
The au ho s decla e ha hey ha e no known compe ing inancial
in e es s o pe sonal ela ionships ha could ha e appea ed o in lu-
ence he wo k epo ed in his pape .
Acknowledgemen
This wo k was suppo ed by he Dis inguished Scien is Fellowship
P og am (DSFP) o King Saud Uni e si y, Riyadh, Saudi A abia.
Appendix A. Supplemen a y da a
Supplemen a y da a o his a icle can be ound online a h ps://
doi.o g/10.1016/j.elecom.2020.106735.
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