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Figure 2. Scanning electron micrographs of pine starch (PS) and pine starch nanoparticles (PSNPs).
(between April and August) is the main factor limiting its food
application.[10,11]
Figure 4. X-ray diffractograms a) and Fourier-transform infrared spectra b) of pine starch (PS) and pine starch nanoparticles (PSNPs).
2.3. Moisture Content and Water Activity differences could be correlated with the RC values in the native
starches, hence, the RC values of cassava (22%) and potato (15%)
PS had a moisture content (MC) of 21.33% ± 1.32% when con- starches were higher when compared with PS (9.2% ± 0.2%).[16]
ditioned under 58% RH, this value is in agreement with MC val- From a technological viewpoint, amorphous starch nanoparti-
ues informed for the same starch stored in similar RH.[31] A re- cles are desired since these materials can be dispersed in water
duction in the MC (15.29% ± 1.48%) was observed in PSNPs at room temperature and they are applied in food formulations
and could be correlated with the amorphization of PS during sensitive to heat.[19] In this way, native PS could be considered
ASP.[30] as a potential source to produce starch nanomaterials since this
PS and PSNPs conditioned at 58% RH had intermediate aw starch has a low RC value.
values, oscillating between 0.61 and 0.62 in both samples, which Images from polarized light confirmed the crystalline struc-
are typical of biological stable materials.[32] Starch nanoparticles ture of PS since the Maltese cross located at the center of each
with lower aw (0.16–0.39) values have been informed in the granule (image inserted in Figure 4a) was observed. PSNPs did
literature, however, these nanomaterials have been conditioned not have a maltase-cross confirming the amorphous structure of
in RH < 10%.[15] Based on MC and aw results, PS and PSNPs these materials (results not shown).
can be classified as products which are not susceptible to Seven peaks typical of amylaceous materials were observed
microorganism growth when stored at 58% RH.[32] in Fourier transform infrared spectra (FTIR) of PS and PSNPs
(Figure 4b). Vibration of –OH and C–H groups were detected at
3440 and 2921 cm−1 , respectively. The vibration of –OH groups
2.4. Crystalline Structure and Chemical Bonds associated to absorbed water molecules on the materials was ob-
served at 1649 cm−1 . Other bands centered at 1158, 1082, 1000,
Diffraction peaks centered at 15° (d = 0.59 nm), 17° (d = and 928 cm−1 were correlated with the CO bonds stretching of
0.52 nm), 18° (d = 0.49 nm), and 23° (d = 0.39 nm) were ob- carbohydrates, stretching of C=O groups, intramolecular hydro-
served in the XRD diffractogram of PS (Figure 4a), and correlated gen bonding of the hydroxyl groups at C-6, and symmetric elon-
with the presence of A-type crystalline structure in the starch gation of C–O–C groups, respectively (Figure 4b).[16] FTIR of
granules. Furthermore, PS has amylose–lipid complex since a PSNPs showed a decrease in the peak centered at 1649 cm−1 , sug-
small peak centered at 20° (d = 0.44 nm) was observed in the gesting that this material has less water molecules hydrating its
same diffractogram (Figure 4a).[28] The relative crystallinity (RC) structure when compared to PS. FTIR results confirmed no for-
value of PS was 9.2% ± 0.2%, suggesting that this starch has mation of new chemical bonds during the production of PSNPs
low crystallinity. XRD results for PS are in accordance with the by ASP.
literature.[10,14]
After ASP, the obtained nanomaterials displayed V6h -type crys-
talline structure with a small diffraction peak at 13° (d = 0.68 nm) 2.5. Thermal Properties
and a halo centered at 20° (d = 0.44 nm) (Figure 4a). The V6h -type
crystalline structure is composed of six glucose units per helical Thermal properties were investigated in the temperature range of
turn and it has been observed in starch nanoparticles produced −30 and 95 °C. PS suspensions in water exhibited an endother-
by ASP.[15,16,30] Furthermore, the RC in PSNPs was 1.6% ± 0.2%, mic peak associated with the starch gelatinization, this thermal
being lower when compared with starch nanoparticles produced transition had onset, peak, and conclusion temperatures of 56.68
from cassava (RC ≥ 5.7%) and potato (RC ≥ 4.8%) starches. These ± 0.76, 60.40 ± 0.15, and 64.34 ± 1.24 °C, respectively, as well as
Table 1. Solubility in water (SW), swelling factor (SF), oil absorption capacity (OAC), and water absorption capacity (WAC) of pine starch (PS) and pine
starch nanoparticles (PSNPs).
PS 4.00 ± 3.61Aa 2.62 ± 0.12Aa 35.50 ± 6.37Ab 39.85 ± 3.11Ab 1.10 ± 0.08A 1.62 ± 0.12A
PSNPs 51.67 ± 4.04Ba 5.21 ± 1.35Aa 83.33 ± 1.53Bb 12.37 ± 1.40Bb 1.82 ± 0.13B 4.21 ± 1.35B
Means within the same column followed by different capital letters are significantly different (p < 0.05) for the same property (SW or SF) and temperature. Means within the
same row followed by different lowercase are significantly different (p < 0.05) for the same material (PS or PSNPs) and same property (SW or SF) at different temperatures.
Figure 6. Stability in water of pine starch (PS) and pine starch nanoparticles (PSNPs) as a function of time.
applied as an ingredient in food formulations which are prepared mechanical agitator (300 rpm). In sequence, acidified ethanol (100:1 v/v,
at room temperature (e.g., soups and sauces) in the food industry. ethanol to HCl) was added dropwise to the gelatinized starch at a rate of
0.77 mL min−1 while being kept under agitation at 300 rpm.
The resulting mixture was kept under agitation by means of a mag-
netic stirrer for 12 h before being centrifuged at 4000 rpm for 15 min.
3. Conclusions Then, PSNPs were kept at 30 °C for 24 h in order to evaporate the ethanol
and afterwards freeze dried (Liotop L101, Brazil) for 24 h. The result-
In this research, PS was used to produce nanomaterials by ASP. ing PSNPs were macerated and stored in desiccators with silica gel until
The transformation of PS to PSNPs had a high production yield analysis (RH ≤ 0%). The NPY (%) was calculated using Equation (1):
(84.44% ± 2.12%). PSNPs displayed monomodal particle size dis-
tribution with particle sizes oscillating between 230 and 1300 nm, mf
NPY = 100 × (1)
surface charge of −9.25 ± 0.83 mV, and amorphous structure. mi
Furthermore, PSNPs showed a higher SW at 25 and 90 °C, as where mf is the final mass obtained after freeze drying (g) and mi is the
well as higher oil and water absorption capacities at 25 °C when mass of starch at the beginning of the process (g).
compared with PS. Although PSNPs had low surface charge, Starch extraction from pine seeds and the production of PSNPs were
this nanomaterial had a high stability when dispersed in water carried out in triplicate.
(30% w/v) at 25 °C. Thus, PSNPs could be used as an additive in Morphology, Particle Size Distribution, and Surface Charge: The mor-
food formulations and as an adsorbent for both hydrophilic and phology of PS and PSNPs was analyzed using scanning electron mi-
croscopy (SEM, JSM-6390LV, JEOL, Japan) at accelerating voltage of 10 kV.
hydrophobic molecules.
Powders were fixed on aluminum stubs by carbon tape and then coated
with a thin gold layer before SEM analyses. Five micrographs were taken
at random sample spots with 1000× and 5000× magnification.[19]
4. Experimental Section Particle size distribution and mean particle size of PS was calculated
by dispersing samples in glycerol 50% (w/w, glycerol to H2 O) over mi-
Production of Starch Nanoparticles and Nanoparticle Production Yield: croscope slides and covering with coverslips. The diameter of 145 starch
Starch was isolated from pine seeds following Costa et al.[20] methodology granules were measured using a light microscope (L-2000a , Bioval, Brazil)
with slight modifications. Seeds were cut longitudinally and transversally with the aid of the software Image J, v1.53k (National Institute Health,
in order to remove the exterior peel and then mixed with distilled water in Bethesda, MD, USA).[21]
a 1:2 (w/w, peeled seed to H2 O) proportion using a blender. The formed PSNPs size distribution was carried out using a LUMiSizer (LUM
slurry was filtered using a cloth filter followed and afterwards mixed with GmbH, Germany). PSNPs (0.01 g) were dispersed in 10 mL of ethanol
distilled water in a 1:1 (w/w slurry to H2 O) proportion before being filtered and sonicated for 5 min prior to analysis.[22]
again. The permeate of both filtrations was kept in a refrigerator at 4 °C Surface charge of samples was analyzed using a Zetasizer Nano ZS
for 24 h in order to precipitate the starch. The decanted material was later (Malvern, England). PS and PSNPs were dispersed in deionized water
separated from the supernatant and washed with distilled water once be- (0.01% w/v) and then their pH were adjusted to 6 and sonicated for 30 min
fore being one more time decanted, separated, and dried in a convective prior to analysis.[23]
oven at 30 °C. The dried starch was then milled and stored in desiccators Moisture Content and Water Activity: PS and PSNPs were kept in desic-
until analysis. cators with RH of 58% during 7 days prior to analysis. MC (g of water g−1
PSNPs were produced by ASP as described by Alves et al.[15] with slight of sample) was measured by heating samples to 120 °C using a moisture
modifications. Firstly, 2.5 g of PS were dispersed in 50 mL of distilled wa- analyzer (MOC63u, Shimadzu, Japan). Water activity (aw , dimensionless)
ter and hydrated for 30 min before being agitated with a mechanical ag- was analyzed using a water activity analyzer (AquaLab 4TE, METER Group,
itator (300 rpm) at 90 °C for 30 min to achieve the starch gelatinization. USA).[19]
Afterwards, the evaporated water was added to the slurry to guarantee the Crystalline Structure and Chemical Bonds: The crystalline structure of
starch concentration and then cooled to room temperature using the same PS and PSNPs was analyzed using an X-ray diffractometer (XRD, Rigaku
MiniFlex600, Japan), operating at 40 kV and 15 mA (CuK𝛼 1 𝜆 = 1.54056 Å WAC (g of water g−1 of sample, d.b.) was performed similarly to OAC,
radiation). The diffractograms were recorded at 20 °C, between 2𝜃 = 5° with water being used in place of oil.[27] However, the WAC was calculated
and 50°, at 1° min−1 with a step size of 0.02°.[24] The interplanar distance d using Equation (7):
(nm) was calculated from the diffraction angle at the maximum intensity of
the peak found in the XRD diffractograms and using Equation (2) (Brag’s Sd − (Si − Sr )
WAC = (7)
law): S i − Sr
Acknowledgements
where Ac is the peak area, or crystalline area, and At is the total area.
The crystallinity of the samples was also analyzed under polarized light. The authors are grateful to the Fundação de Amparo à Pesquisa e In-
Samples of PS and PSNPs were dispersed in glycerol 50% (w/w, glycerol ovação do Estado de Santa Catarina (FAPESC) for the MsC fellowship
to H2 O) over microscope slides and covered with a coverslip. Samples (48/2021) of the first author. G. A. V. would like to thank the FAPESC
were photographed using a polarizing light microscope (ML-9400, Meiji, (grants 2021TR000418 and 2021TR001887) and National Council for Sci-
Japan) with 100× and 200× magnification.[21] entific and Technological Development (CNPq) (grant 302434/2022-4) for
The chemical bonds of PS and PSNPs were analyzed by means of financial support. Furthermore, the authors gratefully acknowledge the
Fourier-Transform Infrared Spectroscopy (FTIR, Cary 660, Agilent, USA). Federal University of Santa Catarina for its support, as well as to the Central
Analyses were performed in the infrared region between 4000 and Laboratory of Electronic Microscopy (LCME) and Interdisciplinary Labora-
400 cm−1 using 4 cm−1 resolution with 20 scans and KBr pellets.[26] tory for Nanostructures Development (LINDEN) for the analyses.
Thermal Properties: Thermal properties of the samples were analyzed
by differential scanning calorimetry (DSC, Jade, Perkin Elmer, USA). Ap-
proximately 3 mg (d.w.) of the samples were dispersed in distilled in a
1:2 (w/w, sample to H2 O) proportion in aluminum pans, sealed with alu-
Conflict of Interest
minum caps and kept hydrating in for 1 h.[16] Afterwards, hydrated sam- The authors declare no conflict of interest.
ples were heated from −30 to 95 °C at 10°C min−1 in two-cycle mode.
Nitrogen (N2 ) was used as flushing gas at 45 mL min−1 and an empty
aluminum pan was used as reference.
Solubility in Water and Swelling Factor: For solubility (SW, %) and SF Data Availability Statement
(dimensionless), samples of PS and PSNPs (W) were dispersed in distilled The data that support the findings of this study are available from the cor-
water (1% w/v, sample to H2 O, d.b.), heated at 25 and 90 °C for 30 min and responding author upon reasonable request.
mixed for 10 s in a vortex every 10 min. Samples were cooled down to room
temperature and centrifuged at 4000 rpm for 15 min. The supernatant was
separated and dried at 105 °C in order to obtain the dry mass (Wr ). The
slurry that remained in the tubes was weighted (Wt ) and then SP and S Keywords
were calculated using Equations (4) and (5), respectively.[22]
alternative starch sources, anti-solvent precipitation method, carbohy-
drate nanoparticles, physicochemical properties
Wt
SF = (4)
W − Wr Received: October 13, 2022
Revised: January 30, 2023
Wr Published online: April 29, 2023
S = 100 × (5)
W
Oil and Water Absorption Capacities: OAC (g of oil g−1 of sample, d.b.)
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