Rheological and structural properties of K-carrageenan/xanthan gum gummies architected with a new natural additive

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Polyme s o Ad anced Technologies, 2025; 36:e70101
h ps://doi.o g/10.1002/pa .70101
Polyme s o Ad anced Technologies
REVIEW ARTICLE
Rheological and S uc u al P ope ies o
k- Ca ageenan/Xan han Gum Gummies A chi ec ed
Wi h a New Na u al Addi i e
Ge manAyalaValencia1 | IzabelC is inaF ei asMo aes2 | Gab ielCoelhoLeand o1 | LoicHilliou3
1Depa men o Chemical and Food Enginee ing, Fede al Uni e si y o San a Ca a ina, Flo ianópolis, B azil | 2Depa men o Food Enginee ing, School
o Animal Science and Food Enginee ing (FZEA), Uni e si y o São Paulo, Pos g adua e P og am in Ma e ials Science and Enginee ing, Pi assununga,
B azil | 3Ins i u e o Polyme s and Composi es (IPC), Uni e si y o Minho, Guima ães, Po ugal
Co espondence: Ge man Ayala Valencia (g.ayala. alenci[email p o ec ed] )
Recei ed: 19 Decembe 2024 | Re ised: 26 Janua y 2025 | Accep ed: 27 Janua y 2025
Funding: This wo k was suppo ed by he Conselho Nacional de Desen ol imen o Cien í ico e Tecnológico, 302434/2022- 4, FCT, CEECINST/00156/2018,
UID/CTM/50025/2020, Coo denação de Ape eiçoamen o de Pessoal de Ní el Supe io , 88887.878787/2023- 00, 88887.936575/2024- 00.
Keywo ds: ca ageenan| na u al addi i es| heology| so ma e ials| xan han gum
ABSTRACT
Biohyb ids (BHs)based on ben oni e and an hocyanins can be p oduced as al e na i es o syn he ic colo an s. Howe e , no in o -
ma ion is a ailable on he in e ac ion o biohyb id wi h ood sys em. This esea ch s udies he heological p ope ies o gummies
con aining k- ca ageenan and xan han gum inco po a ed wi h a BH. The inco po a ion o BH (≤ 2% w/w) inc eased he low
consis ency index and shea hinning e ec in mel ed gummies a 85°C. Du ing cooling om 90°C o 25°C, he p esence o BH
al e ed he sol–gel ansi ion empe a u e ypical in ca ageenan sys ems, p obably by he o ma ion o ca ageenan complexes.
A 25°C, all gummies had a solid- like esponse wi h elas ic modulus (G') highe han iscous modulus (G"). G' alues inc eased
linea ly wi h BH concen a ion, and he linea iscoelas ic egion and b eaking s ain dec eased wi h BH concen a ion, indica -
ing ha his na u al addi i e ac ed as a ein o cing ma e ial.
1 | In oduc ion
The use o syn he ic colo an s in ood o mula ions has been
associa ed wi h oxic and alle gic e ec s, as well as a en ion-
de ici hype ac i i y diso de in child en [1, 2]. In his way,
na u al colo an s ha e eme ged as an al e na i e o syn he ic
colo an s in ood p oduc s. Fu he mo e, he use o na u al col-
o an s can inc ease ood accep ance because consume s ha e
ecen ly demanded heal hie ood p oduc s wi h clean labels,
o e he ecen yea s [3].
An hocyanins a e na u al and non- oxic pigmen s esponsible
o he ed, blue, and pu ple colo s in ui s and ege ables[3].
In ecen yea s, mo e s udies ha e ocused on eco e ing an-
hocyanins om ag i- ood was es (e.g., pomace and peels) [4].
The eco e y o an hocyanins has been appoin ed as an al e -
na i e o he sus ainable p oduc ion o ood colo an s in consid-
e a ion o he di e en Sus ainable De elopmen Goals o he
Uni ed Na ions (SDGs- UN) [5].
Na u al and syn he ic clays ha e been used o eco e an hocya-
nins om ag i- ood was e. The eco e y o an hocyanins in ol es
adso p ion, whe e he pigmen is s abilized h ough physical in-
e ac ion wi h clay pla ele s. In his way, an hocyanins om egg-
plan (Solanum melongena) and jambolan (Syzygium cumini) peel
ex ac s ha e been eco e ed using a syn he ic clay called Laponi e
(Lap). The adso p ion p ocess was ca ied ou a oom empe a-
u e and pH 1, and 93% o he an hocyanins om he ex ac we e
adso bed on he clay su ace. In bo h s udies, i was possible o ab-
so b app oxima ely 15 mg o an hocyanins pe g am o Lap [6, 7],
© 2025 John Wiley & Sons L d.
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and he esul ing ma e ial was named biohyb id (BH) because i
is composed o o ganic (an hocyanins) and ino ganic (nanoclay)
ma e ials. The s abiliza ion o an hocyanins on o he clay su ace
is due o a chemical eac ion be ween an hocyanin ions and he
unc ional g oups p esen on he clay su ace [8]. Recen ly, Koop
e al. [8] used ben oni e o eco e an hocyanins om jambolan (S.
cumini) peel ex ac s and concluded ha he adso p ion p ocess
was simila o ha obse ed wi h Lap. Howe e , he adso p ion
capaci y o ben oni e was highe han ha o Lap. Hence, he ad-
so p ion capaci y was 212 mg o an hocyanins pe g am o ben-
oni e, sugges ing ha his clay has po en ial o ood applica ions.
Ben oni e is a colloidal- hyd a ed aluminum silica e con aining
a ying quan i ies o i on, alkalies, and alkaline ea h. This min-
e al is conside ed a GRAS (gene ally ecognized as sa e) ing edi-
en o ood applica ions [9].
Recen ly, Caicedo Chacon e al. [10] de eloped a biohyb id (BH)
based on ben oni e and he phenolic compounds om p opolis ex-
ac . The au ho s concluded ha his BH can be used as a na u-
al addi i e in ca ageenan hyd ogels. Ca ageenan hyd ogels a e
o en blended wi h xan han gum o imp o e he mechanical p op-
e ies o he esul ing hyd ogel aiming a ood applica ions as egan
gummies [11]. Gummies a e a class o ood widely consumed by
he en i e popula ion and a e usually colo ed wi h syn he ic addi-
i es [12].
To da e, no s udy has explo ed he ood applica ion o ben oni e
adso bing an hocyanins (BH), as well as he s abili y and in e -
ac ion when mixed wi h ood sys ems based on biopolyme s.
The e o e, he cu en esea ch s udy aimed o p oduce gum-
mies based on ca ageenan and xan han gum con aining BH
and o in es iga e he chemical in e ac ions and s uc u es in
gummies in iew o a ionalize he e ec o BH concen a ion
on he heological beha io o gummies.
2 | Ma e ials and Me hods
2.1 | Raw Ma e ials
Jambolan ui s we e ha es ed manually in a ully ipe s age,
in Flo ianopolis ci y, SC, B azil (−27.5999, −48.5219). The ui s
we e immedia ely washed, and he pulp and skin we e man-
ually sepa a ed om he seeds and s o ed a −18°C ± 2°C [8].
Ben oni e (CP31- Ben onisa, B azil) was used as he adso ben
clay. Dis illed wa e was used as he sol en . K- ca ageenan
(Sigma Ald ich, 22048- 100G- F) and xan han gum (Fluka,
95465; bo h 1053246) we e used as he mac omolecules. All e-
agen s we e o analy ical g ade.
2.2 | BH P oduc ion
The BH was p oduced ollowing he p o ocol in o med by Koop
e al. [8]. BH was ob ained by adding ben oni e o he an hocy-
anin ex ac a a a io o 0.027 g o ben oni e pe mg o an hocy-
anins and keeping i unde agi a ion a 500 .p.m. by mechanical
s i ing o 15 min in he absence o ligh . The mix u e was
s o ed o e nigh a 4°C o sedimen he BH. A e emo ing
he supe na an , BH was d ied a 35°C o 24 h in a con ec i e
o en be o e being s o ed in desicca o s con aining silica gel un il
analysis. A comple e cha ac e iza ion o he BH was p e iously
epo ed by Koop e al. [8]. A commen a y cha ac e iza ion o
BH was pe o med in ela ion o i s mo phology and pa icle size
(see Suppo ing In o ma ion).
2.3 | Gum P oduc ion
Ca ageenan/xan han gummies we e p oduced as p oposed by
Song e al. [13], who used hese biopolyme s o p oduce gummy
candies. Gummies we e p epa ed by dispe sing ca ageenan
(2 g) and xan han gum (1 g) in 100 mL o dis illed wa e ollowed
by s i ing and hea ing (70°C) o 30 min. In sequence, BH was
added based on he weigh o he o mula ion (0%, 0.5%, 1%, and
2%). The esul ing dispe sions con aining BH we e s i ed a 50°C
o 15 min be o e cha ac e iza ion. Gummies con aining only ca -
ageenan (2%) we e also p oduced and used as con ols. The ad-
di ion o BH did no exceed 2% o he o mula ion weigh o he
o mula ion, as p oposed by he legisla ion o ood addi i es [14].
2.4 | Gum Cha ac e iza ion
2.4.1 | Mo phology
The mo phology o he gummies was s udied using op ical ans-
mission mic oscopy (Olympus BH2, Olympus, Tokyo, Japan,
20×) coupled o a LEICA DFC 280 digi al came a. Mel samples
(≈85°C) we e placed on mic oscope slabs, gen ly squeezed wi h
a glass co e , and cooled o 25°C.
2.4.2 | Chemical Bonds and C ys alline S uc u e
The chemical bonds o he d ied gummies a 40°C o 30 min
we e s udied using an FTIR spec ome e (Spec um,
Pe kinElme , Wal ham, MA, USA) equipped wi h a Uni e sal
A enua ed To al Re lec ion (ATR). FTIR spec a we e ob ained
in he in a ed egion be ween 1800 and 600 cm−1 wi h 16 scans,
a esolu ion o 1 cm−1 [15].
X- ay Di ac ion (XRD) o he d ied gummies was pe o med
using an X- ay di ac ome e (D8 Disco e , B uke , Bille iica,
MA, USA), ope a ing a 40 kV and 15 mA (CuKα 1 = 1.5406 Å
adia ion). Di ac og ams we e ob ained a oom empe a u e
in he di ac ion ange (2θ) be ween 4.5° and 70°, wi h a scan
a e o 2°/min and a s ep size o 0.04°. The in e plana dis ance
d (nm) was calcula ed using B agg's law equa ion (Equa ion1)
wi h he angle o di ac ion θ a he maximum in ensi y o he
peak obse ed in he di ac og am as ollows:
whe e
𝜆
is he wa eleng h (nm), and
n
is he e lec ion o de
(
n
= 1, dimensionless).
2.4.3 | Rheome y
2.4.3.1 | Flow Cu e. The low cu es o he mel ed gum-
mies we e ca ied ou using a modula compac heome e (MCR
(1)
n×𝜆=2×d×sin(θ)
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302, An on Paa , G az, Aus alia) wi h a 40- mm pa allel- pla e
geome y and a gap o 230 μm. Samples we e s udied a 85°C in
a shea a e ange be ween 1 and 1000 s−1, using he ollowing
expe imen al p o ocol: i s , a cons an s ain o 10% wi h a e-
quency o 1 Hz was applied o 5 min o e ase any low his o y
and eju ena e he mel ed sample, hus ensu ing es ep oduc-
ibili y. La e inc easing and dec easing shea a e sweeps we e
applied o s udy he heological beha io o samples [16]. The
Powe law (Equa ion2) was used o calcula e he heological
pa ame e s o appa en iscosi y (η) e sus shea a e (
𝛾
):
whe e
K
is he low consis ency index (Pa∙sn) and
n
is he low
beha io index (dimensionless) [17].
2.4.3.2 | Viscoelas ic P ope ies. The iscoelas ic p op-
e ies we e measu ed using a o a ional heome e (AR G2, TA
Ins umen s, New Cas le, DE, USA) equipped wi h a 25- mm
pa allel- pla e geome y and a gap o 500 μm. A empe a u e
sweep es om 90°C o 25°C was ca ied ou o in es iga e
he e ec o BH on he ca ageenan sol–gel ansi ion empe a-
u e. The applied s ain ampli ude and equency we e se a
0.5% and 1.0 Hz, espec i ely. Wa e e apo a ion in he samples
was a oided using an oil (dodecane 44030- 1L, Sigma- Ald ich).
Du ing cooling, he heome e 's gap was compensa ed
o he he mal expansion o he pla es, and he no mal o ce
was kep o 0 ± 0.1 N o accommoda e o he possible change
o olume occu ing du ing he sol o gel ansi ion [18].
In sequence, he mechanical spec a o he hyd ogels a 25°C was
measu ed wi h a equency sweep om 100 o 0.01 Hz pe o med
using a s ain ampli ude o 0.5%. Finally, he linea and la ge de-
o ma ion iscoelas ic beha io s o he hyd ogels we e de e mined
a 25°C by pe o ming an oscilla o y shea s ain ampli ude sweep
be ween 0.01% and 1000% and a a equency o 1 Hz [16, 19].
All heological esul s we e analyzed using he Rheology
Ad an age Da a Analysis so wa e (TA Ins umen , New Cas le,
DE, USA).
2.5 | S a is ical Analyses
All es s we e pe o med in iplica e, and he esul s a e ex-
p essed as means ± s anda d de ia ion. Analysis o a iance
(ANOVA) and Tukey's es wi h a 5% signi icance le el we e
pe o med using TIBCO S a is ica so wa e, e sion 13.5.0.17.
Fi ing o he models o da a was pe o med using a dedica ed
so wa e (O iginP o, e sion 8.5, O iginLab, USA).
3 | Resul s and Discussion
3.1 | Mo phology
Gummies based on ca ageenan and ca ageenan/xan han
gum displayed a homogeneous mac oscopic isual appea ance
(Figu e 1a,b). The o ma ion o ca ageenan- based gels is ac-
companied by he agg ega ion o polyme chains and he sepa-
a ion om he sol en , which may lead o mic oscopic spa ial
he e ogenei ies [20, 21]. In his way, a mic oscopic scale, zones
wi h g ay and whi e colo s could be co ela ed wi h he phase
sepa a ion (he e ogenei ies) be ween he polyme s and wa e
(Figu e1), sugges ing ha mac omolecula agg ega es and/o
possible xan han- ich egions a e wi h size smalle han he es-
olu ion achie ed by op ical mic oscopy.
Gummies con aining BH had a homogeneous isual aspec and
exhibi ed wine colo , independen ly o he BH concen a ion
(Figu e1c,d). Op ical mic oscopy images e ealed agg ega es o
BH in he gummy ma ix. These agg ega es had a ed colo , i eg-
ula shapes, and pa icle sizes be ween 4 and 42 μm (Figu e1c–e).
Scanning elec on mic og aphs e ealed ha he BH is composed
o agg ega es o pa icles a he mic oscale (Figu eS1). When dis-
pe sed in dis illed wa e , he BH had a imodal dis ibu ion wi h
pa icle sizes be ween 0.13–0.18, 0.20–0.55, and 0.57–0.64 μm
(Figu eS2). Pa icula ly, he second pa icle size dis ibu ion o BH
(0.20–0.55 μm) was he mos ep esen a i e in his addi i e (see cu-
mula i e esul s in Figu eS2). Ben oni e has pla ele s shapes wi h
a b oad dis ibu ion o pa icle sizes anging om 0.8 o 2000 μm
[22, 23]. Disc epancies be ween pa icle shapes and pa icle size
dis ibu ion obse ed in he BH when compa ed wi h ben oni e
p obably we e due o he clay modi ica ion du ing he adso p ion
o an hocyanins [8], and he dispe sion me hods used o quan i y
pa icles sizes. Resul s om pa icle size dis ibu ion o BH in wa e
(Figu eS2) and op ical mic oscopy o gummies (Figu e1c–e) e-
ealed ha , in spi e o he good dis ibu i e mixing, he BH was
no well dispe sed du ing he gummy p oduc ion in con as o he
good dispe sion achie ed by he mixing o sample be o e pa icle
size cha ac e iza ion. Despi e he poo dispe sion o BH in o he
ca ageenan/xan han gum ma ix, i was possible o ob ain gum-
mies wi h a homogeneous isual appea ance (Figu e1).
3.2 | Chemical Bonds and C ys alline S uc u e
D ied samples had FTIR spec a ypical o ca ageenan
(Figu e 2a), being obse ed he s e ching o : ca boxyla e an-
ions (1638 cm−1), sul a e es e s (1225 cm−1), glycosidic g oups
(10 07 cm−1), 3,6- anhyd o- galac ose (920 cm−1), and sul a ed CO
(842 cm−1) [24, 25]. D ied gummies con aining xan han gum had
a shi o he band p e iously obse ed a 1638 cm−1 o he igh
(1620 cm−1) due o he in e ac ions be ween ca boxyla e anions
(RCOO−) and ca boxyl g oups (ROOH) om ca ageenan and
xan han gum, espec i ely (Figu es2a and S3) [26]. Fu he mo e,
he inco po a ion o xan han gum shi ed he band p e iously
obse ed a 1225 cm−1 o he le (1232 cm−1), indica ing ha he
sul a e es e g oups o ca ageenan in e ac ed wi h xan han gum
(Figu e2a). The inco po a ion o BH did no al e he FTIR spec-
a o gums, sugges ing ha his ma e ial can in e ac wi h mac-
omolecules by means o hyd ogen bonds [15, 27, 28].
X- ay di ac og ams o d ied ca ageenan gummies displayed
a small e lec ion cen e ed a 2θ = 7.4° (
d01
= 11.9 Å) and a b oad
band cen e ed a 2θ = 21° (
d02
= 4.2 Å) (Figu e 2b), which we e
associa ed wi h he c oss- linking domain in double helix and
he amo phous s uc u e o his mac omolecule, espec i ely
[29–31]. The blending wi h xan han gum did no modi y he
c ys alline s uc u e p e iously obse ed in ca ageenan gum-
mies (Figu e2b), his esul was due o he amo phous na u e o
xan han gum [32], and o he ac ha in case o phase sepa a-
ion, his occu s on la ge scales han hose esol ed by WAXD.
(2)
𝜂=K𝛾(n−1).
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4 o 10 Polyme s o Ad anced Technologies, 2025
The inco po a ion o BH led o a displacemen o he
d01
om
2θ = 7.4° o 5.7° (
d01
= 15.5 Å) due o he in e cala ion o bio-
polyme s in o clay pla ele s and hei in e ac ion by means o
hyd ogen bonds [28, 33]. Fu he mo e, wo di ac ion peaks
cen e ed a 2θ = 20.9° (
d
= 4.2 Å) and 2θ = 26.7° (
d
= 3.3 Å)
we e obse ed in gummies con aining BH (Figu e2b), his
FIGURE 1 | Visual appea ance and op ical mic oscopy o ca ageenan gummy (a) and gummies based on ca ageenan and xan han gum inco -
po a ed wi h: (b) 0, (c) 0.5, (d) 1, and (e) 2% o BH (biohyb id). (Fo in e p e a ion o he e e ences o colo in his igu e legend, he eade is e e ed
o he Web e sion o his a icle.)
FIGURE 2 | Fou ie - ans o m in a ed spec a (a) and X- ay di ac og ams (b) o gummies. Ca ageenan gummies (i) and gummies based on
ca ageenan/xan han gum inco po a ed wi h: (ii) 0, (iii) 0.5, (i ) 1, and ( ) 2% o BH (biohyb id).
10991581, 2025, 2, Downloaded om h ps://onlinelib a y.wiley.com/doi/10.1002/pa .70101 by Uni e sidade Do Minho, Wiley Online Lib a y on [11/02/2025]. See he Te ms and Condi ions (h ps://onlinelib a y.wiley.com/ e ms-and-condi ions) on Wiley Online Lib a y o ules o use; OA a icles a e go e ned by he applicable C ea i e Commons License
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di ac ion peaks a e ypical o ben oni e and inc eased wi h
BH [34].
3.3 | Flow P ope ies
The low cu e o he 2% w/w ca ageenan solu ion exhibi s a
New onian iscosi y pla eau a low shea a e and a dec eas-
ing iscosi y a highe shea a es (Figu e3). This o e all non-
New onian beha io indica ed ha ca ageenan chains we e in
he semi- dilu ed o en angled egime, whe e polyme –polyme
in e ac ions and low- induced chain o ien a ion we e esponsi-
ble o he shea a e dependence o he iscosi y. In he cu en
esea ch, ca ageenan chains could be in he helical con o ma-
ion e en a such high empe a u e as sugges ed by Wes be y
e al. [35]. As such, he shea hinning beha io was expec ed
since his was eminiscen om he heological beha io o non-
dilu e solu ions o wo m- like chains (Figu e3).
Adding xan han gum o ca ageenan enhanced he iscos-
i y and he shea hinning o he solu ions, which in in-
sically con ain mo e polyme s (Figu e 3). Howe e , he
non- ep oducibili y a lowe shea a es be ween he low
cu es measu ed by sweeping up o down he shea a es
sugges ed ime and low- his o y dependences in he mea-
su ed iscosi y, p obably ela ed o he spa ial he e ogenei y
p e iously obse ed in op ical mic oscopy esul s (Figu e1b).
Addi ional heological es ing and mo phological cha ac e i-
za ion o possible low- induced s uc u es would be needed o
FIGURE 3 | Flow cu es o ca ageenan, ca ageenan/xan han gum (con ol), and ca ageenan/xan han gum con aining di e en BH (biohy-
b id) concen a ions.
TABLE 1 | Rheological pa ame e s (upwa d cu e) o mel ed
gummies.
Gummy sample K (Pa∙sn)n R2
Ca ageenan 0.26 ± 0.00e0.85 ± 0.01a0.9508
Ca ageenan/
xan han gum
3.45 ± 0.03d0.56 ± 0.01b0.9974
Ca ageenan/
xan han gum wi h
0.5% BH
6.17 ± 0.00c0.27 ± 0.00c0.9999
Ca ageenan/
xan han gum wi h
1% BH
8.67 ± 0.05b0.13 ± 0.01d0.9995
Ca ageenan/
xan han gum wi h
2% BH
9.06 ± 0.07a0.01 ± 0.00e0.9990
No e: Means in he same column ollowed by di e en lowe case a e
signi ican ly di e en (p < 0.05).
Abb e ia ions: BH = biohyb id,
K
= low consis ency index;
n
= low beha io
index.
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6 o 10 Polyme s o Ad anced Technologies, 2025
ela e such beha io wi h possible hixo opy, ime- dependen
chain agg ega ion, o low- induced demixing/mixing be ween
he wo componen s.
Mel ed gummies con aining xan han gum and BH also had
a shea - hinning beha io , wi h highe η alues a
𝛾
= 1 s−1
(Figu e3). The low cu es we e well desc ibed by he Powe
law model (Table1) as no New onian pla eau is measu ed a
lowe shea a es, and esul s a e o e all insensi i e o amp-
ing up o down he shea es. The inco po a ion o BH d as i-
cally inc eased he low consis ency index and shea hinning
e ec (
n
< 1) in mel ed gummies, see Table1. In addi ion, gum-
mies con aining BH show a linea inc ease o
K
alues o BH
concen a ions be ween 0% and 1%, whe eas
n
dec eased ex-
ponen ially o he whole BH concen a ion ange (Figu eS4).
Bo h e ec s could be due o he inc ease in solid con en , he
linea inc ease in K being eminiscen om a S okes–Eins ein
e ec o solids on he ma ix iscosi y, whe eas he inc eased
shea hinning ela es o inc eased local shea a es be ween
lowing pa icles.
3.4 | Gel P ope ies
Gummies showed an inc ease in he elas ic (G') and iscous (G")
moduli as he samples we e cooled om 90°C o 25°C (Figu e4).
Howe e , he heological beha io o each gummy was impac ed
by i s o mula ion. Gummies based on ca ageenan and ca a-
geenan/xan han gum (blended) had G" > G' a 90°C, as expec ed
om he da a displayed in Figu e3. Bo h moduli inc eased wi h
dec easing empe a u e and had a c osso e poin (G' = G") a
45.7°C ± 1.0°C and 40.6°C ± 0.8°C in ca ageenan and blended
gummies (p < 0.05), espec i ely (Figu e 4). This c osso e
poin is ypical o physical gels ha unde go sol–gel (Tsol–gel)
ansi ions when he sys ems a e cooled [36, 37]. Acco ding o
he li e a u e, below Tsol–gel, helices om ca ageenan mole-
cules a e o med and consequen ly agg ega e in o highe - o de
assemblies o c ea e a h ee- dimensional ne wo k and conse-
quen ly elas ic gels [36, 38]. The educ ion o Tsol–gel in blended
gummies when compa ed wi h ca ageenan gel could be a -
ibu ed o he physical–chemical in e ac ions be ween hese
mac omolecules as seen in FTIR spec a, o simply o a change
FIGURE 4 | Examples o cu es o iscoelas ic moduli (G' and G") o ca ageenan gummies, ca ageenan/xan han gum (con ol) gummies, and
ca ageenan/xan han gum gummies con aining di e en BH (biohyb id) concen a ions as a unc ion o empe a u e. (Fo in e p e a ion o he e -
e ences o colo in his igu e legend, he eade is e e ed o he Web e sion o his a icle.)
10991581, 2025, 2, Downloaded om h ps://onlinelib a y.wiley.com/doi/10.1002/pa .70101 by Uni e sidade Do Minho, Wiley Online Lib a y on [11/02/2025]. See he Te ms and Condi ions (h ps://onlinelib a y.wiley.com/ e ms-and-condi ions) on Wiley Online Lib a y o ules o use; OA a icles a e go e ned by he applicable C ea i e Commons License
7 o 10
FIGURE 5 | (a) Typical mechanical spec a o ca ageenan gummies, ca ageenan/xan han gum (con ol) gummies, and ca ageenan/xan han
gum gummies con aining di e en BH (biohyb id) concen a ions; (b) a e age elas ic modulus (G') as a unc ion o BH concen a ion. (Fo in e p e-
a ion o he e e ences o colo in his igu e legend, he eade is e e ed o he Web e sion o his a icle).
10991581, 2025, 2, Downloaded om h ps://onlinelib a y.wiley.com/doi/10.1002/pa .70101 by Uni e sidade Do Minho, Wiley Online Lib a y on [11/02/2025]. See he Te ms and Condi ions (h ps://onlinelib a y.wiley.com/ e ms-and-condi ions) on Wiley Online Lib a y o ules o use; OA a icles a e go e ned by he applicable C ea i e Commons License
8 o 10 Polyme s o Ad anced Technologies, 2025
in sol en - ca ageenan elec os a ic in e ac ions, educing he
a e o gela ion in ca ageenan (see Sec ion3.2). No e he e ha
he inc ease in he sol iscosi y a la ge empe a u es (see also
Figu e3) canno explain he shi in he c oss- o e be ween G'
and G", since he slope o G' wi h empe a u e is also a ec ed a
lowe empe a u e below he onse o gela ion.
The addi ion o BH s ongly a ec s he he mal beha io o
blended gummies (Figu e 4). The e o e, gummies con aining
0.5% and 1% BH had G" = G' a 90°C, whe eas gummies wi h 2%
BH showed G' > G" o he en i e empe a u e ange es ed. This
beha io could be due o addi ional elas ici y o igina ing om
BH- BH con ac s a highes BH concen a ion. Fo 0.5% BH, he
shea moduli a highe empe a u e a e smalle han he shea
moduli o he suspending ma ix. In ligh o he ein o cing be-
ha io in e ed om he low cu es, his d op in shea moduli
a la ge empe a u e can only be explained by he la ge e-
quency dependence o G' and G". The mechanism unde lying he
shi o he gel se ing o illed gummies o lowe empe a u es
wi h mo e added BH is howe e less clea .
The mechanical spec a o he gummies e ealed ha hese sys-
ems had a solid- like esponse a 25°C wi h G' > G" o he en i e
equency ange es ed (Figu e5a). Fu he mo e, all gummies
had la ge moduli wi h weak equency dependence o he
whole ange o es ed equencies, whe e G' was cons an and
signi ican ly la ge han G" (Figu e5a), ypical o ca ageenan
gels [39]. Fu he mo e, G' inc eased linea ly wi h BH concen a-
ion (Figu e5b), sugges ing ha his addi i e played he ole o
a ein o cing ille in he dilu ed egime, ha is, wi hou ille –
ille in e ac ion.
The la ge de o ma ion beha io o gummies e ealed ha ca -
ageenan gels had he onse o s ain so ening (end o linea
iscoelas ic egion, LVR) occu ing a 2.5% s ain (Figu e6),
ollowed by an ab up d op in he moduli ypical o kappa-
based ca ageenan sys ems [21, 40]. A c osso e be ween G'
and G" is measu ed o a shea s ain (b eaking s ain) in he
ange o 11%, which sugges s a luidiza ion p ocess whe e he
heological esponse o he shea ed gummy was domina ed by
he shea loss modulus G" (Figu e6). The addi ion o xan han
gum is accompanied by inc eased in he LVR and b eaking
s ain o app oxima ely 5% and 107%, espec i ely. These e-
sul s sugges ha he xan han gum, in addi ion o inc easing
G' alues (Figu e5a), also inc eased he esis ance o de o -
ma ion (Figu e 6). In con as , he inco po a ion o BH led
FIGURE 6 | Viscoelas ic moduli (G') as a unc ion s ain o ca ageenan gummies, ca ageenan/xan han gum (con ol) gummies, and ca a-
geenan/xan han gum gummies con aining di e en BH (biohyb id) concen a ions. (Fo in e p e a ion o he e e ences o colo in his igu e leg-
end, he eade is e e ed o he Web e sion o his a icle.)
10991581, 2025, 2, Downloaded om h ps://onlinelib a y.wiley.com/doi/10.1002/pa .70101 by Uni e sidade Do Minho, Wiley Online Lib a y on [11/02/2025]. See he Te ms and Condi ions (h ps://onlinelib a y.wiley.com/ e ms-and-condi ions) on Wiley Online Lib a y o ules o use; OA a icles a e go e ned by he applicable C ea i e Commons License
9 o 10
o a dec ease in bo h pa ame e s (LVR and b eaking s ain),
sugges ing ha his addi i e ac ed as a ein o cing ma e ial
whe e only G' was imp o ed, whe eas BH/ma ix in e ace
was no s ong enough o sus ain la ge s ain han he ma ix
s ain esis ance. In o he wo ds, BH pa icles ac as s ess-
weakening poin s.
4 | Conclusions
This esea ch epo s, o he i s ime, he p oduc ion and
s uc u al- heological cha ac e iza ion o egan gummies based
on ca ageenan and xan han gum inco po a ed as a new BH.
Gummies wi h homogeneous isual appea ance and wine colo
we e ob ained a e BH inco po a ion. BH was dispe sed in o
biopolyme chains wi h good spa ial dis ibu ion, and no spe-
ci ic chemical in e ac ion wi h he biopolyme ma ix could
be in e ed om FTIR analysis. Impo an modi ica ions we e
obse ed in he heological p ope ies o gummies a e BH in-
co po a ion, sugges ing ha his na u al addi i e can be used
o impa colo and modula e bo h linea and nonlinea elas ic
p ope ies in ood o mula ions.
Acknowledgmen s
This wo k was suppo ed by he Fundação pa a a Ciência e Tecnologia
(FCT), h ough he E2B2- PHACAR p ojec , g an numbe : PTDC/BII-
BIO/5626/2020 (h p:// doi. o g/ 10. 54499/ PTDC/ BII- BIO/ 5626/ 2020).
G. A. Valencia would like o hank he Na ional Council o Scien i ic
and Technological De elopmen (CNPq) (g an 302434/2022- 4) and
CAPES (88887.936575/2024- 00) o inancial suppo . I.C.F. Mo aes
also hanks CAPES (88887.878787/2023- 00) o inancial suppo . G.
C. Leand o g a e ully acknowledges he CAPES o he PhD ellow-
ship. L. Hilliou acknowledges he inancial suppo by he FCT unde
he amewo k o S a egic Funding g an : UID/CTM/50025/2020 and
g an CEECINST/00156/2018. The au ho s g a e ully acknowledge
he Cen al Labo a o y o Elec onic Mic oscopy (LCME—UFSC) and
he LINDEN (UFSC) nano echnology o he SEM and LDS analyses,
espec i ely.
Con lic s o In e es
The au ho s decla e no con lic s o in e es .
Da a A ailabili y S a emen
The da a ha suppo he indings o his s udy a e a ailable om he
co esponding au ho upon easonable eques .
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