LWT - Food Science and Technology 168 (2022) 113897

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LWT
journal homepage: www.elsevier.com/locate/lwt

Functional and physicochemical properties of non-centrifugal cane sugar

obtained by three concentration technologies
Lizzet Vargas Valencia a, Maria Hernández-Carrión a, **, Fabian Velasquez b, John Espitia b,
Jader Rodriguez Cortina b, *
a
Universidad de Los Andes, Department of Chemical and Food Engineering, Grupo de Diseño de Productos y Procesos (GDPP), Carrera 1 # 18A – 12, ZP: 111711,
Bogotá, Colombia
b
Corporación Colombiana de Investigación Agropecuaria (Agrosavia), Km 14 Vía Mosquera, Bogotá, Colombia

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

Keywords: Non-centrifugal cane sugar (NCS) is characterized by its content of carbohydrates, phenolic compounds, anti­
Polyphenol profile oxidants, and minerals responsible for its functional properties. A few of these properties change during NCS
Acrylamide content production owing to thermal processing. This is particularly true when physical and chemical changes occur.
Antioxidant activity
This study investigated the effects of three concentration technologies (calandria (CAL), marmite (MAR), and
Concentration technologies
refractance window (RW)) on food safety, functionality, and physical properties. The acrylamide content,
antioxidant capacity, phenolic, sugar, and mineral content, color, moisture, glass temperature, and micro­
structure were determined. The results showed that most of the parameter changes were related to the tem­
perature degradation processes, showing an inverse relationship with phenolic content and a direct relationship
with acrylamide content. Sugar content (sucrose inversion and reactive fructose) is related to the Maillard re­
actions that occur during thermal processing. Caramel colorations were observed with high phenolic content
(14.20–18.70 mg/kg) and low acrylamide contents (up to 40 μg/kg). The best results were obtained with con­
centration technology that employed lower temperatures (marmite). These results suggest that the new con­
centration technologies used in this study could be an alternative to the traditional process, allowing better
quality, functional, and safe food products.

flowing through the open heat exchangers involved in the system

1. Introduction
Non-centrifugal cane sugar (NCS) is obtained from the solute con­
centration of sugarcane juice through evaporation process. It has
potentially useful compounds for end consumers and offers a substantial
difference from refined sugars (Velásquez, Espitia, Mendieta, Escobar, &
Rodríguez, 2019). The traditional NCS production process begins with
milling the sugarcane to extract its juice, using its subproduct (bagasse)
as a combustible material for furnaces. Heat from the furnaces is used for
juice cleansing and product concentration, whereas suspended bagasse
residues are removed, and sugarcane syrup is obtained. Finally, syrup is
crystallized at high temperatures (approximately 120 ◦ C), up to 92–95
◦
Brix, and molded into solid shapes for the final product. The production
process consists of a heat exchange process capable of evaporating
water, which includes vapor and liquid phases during boiling of the juice
(Velásquez et al., 2021).
Sugarcane juice evaporation process has been reported to affect the
nutritional and antioxidant properties of the NCS products (Asikin et al.,
2016). Different studies have focused on understanding the physical and
chemical changes during the NCS manufacturing process, as they affect
the physicochemical, nutritional, antioxidant, and safety properties of
the final product (Lee et al., 2018; Velásquez et al., 2019; Zhu et al.,
2020). Zhu et al. (2020) evaluated sugar product obtained from sugar­
cane juice clarified with 50 nm ceramic membrane and compared these
properties with commercially available NCS products. Chemical char­
acterization and a comparative assessment of the NCS samples obtained
by using traditional molding and powdering via spray-drying was re­
ported by Alarcón et al. (2021). During the process, the initial compo­
sition, and properties of the sugarcane juice change owing to thermal
processing (Rodríguez, Velásquez, Espitia, Escobar, & Mendieta, 2018).

* Corresponding author. Colombian Corporation for Agricultural Research - Agrosavia, Centro de Investigación Tibaitatá, Kilómetro 14 vía Mosquera Bogotá,
Colombia.
** Corresponding author. Chemical and Food Engineering Department, Faculty of Engineering, Universidad de los Andes, Bogotá, 111711, Colombia.
E-mail addresses: m.hernandez1@uniandes.edu.co (M. Hernández-Carrión), jrodriguezc@agrosavia.co (J. Rodriguez Cortina).

https://doi.org/10.1016/j.lwt.2022.113897
Received 13 June 2022; Received in revised form 27 July 2022; Accepted 22 August 2022
Available online 30 August 2022
0023-6438/© 2022 The Authors. Published by Elsevier Ltd. This is an open access article under the CC BY license (http://creativecommons.org/licenses/by/4.0/).
L. Vargas Valencia et al.
Abbreviations
NCS Non-centrifugal cane sugar
CAL Calandria
MAR Marmite
RW Refractance Window
MEE Multiple-effect evaporation
FRAP Ferric Reducing Antioxidant Power method
DPPH 2, 2 - Diphenyl - 1 - picrylhydrazyl method
In addition, some control constraints result in hot-spots on the evapo­
rator surfaces, where the product develops toxic compounds, such as
acrylamides, and the attractive components get degraded (Velásquez
et al., 2019). Therefore, it is necessary to evaluate the effects of different
evaporation technologies and their operating conditions on the prop­
erties of NCS, ensuring customer safety, composition, and better phys­
ical properties.
The current study investigated the effect of innovative concentration
technologies such as Calandria (CAL) (T > 120 ◦ C), Marmite (MAR),
vacuum concentration (54 ◦ C > T > 80 ◦ C), and refractance window
(RW) (T ~ 90 ◦ C) on NCS samples. The product obtained from each
technology was characterized by measuring properties such as food
safety, functionality, and physical properties, allowing the selection of
the best technology.
2. Materials and methods
2.1. Samples
The NCS samples were produced at Agrosavia CIMPA headquarters
in Santander, Colombia. The food safety, functionality, and physical
properties of each sugarcane-derived were characterized.
• Two sugarcane juice samples (pretreated and clarified),
• one sugarcane syrup sample,
• and NCS samples from each concentration technology (CAL, MAR,
and RW)
It is worth mentioning that the operating conditions, quantity of raw
materials, and process times at which samples were obtained were
determined using technologies established by Agrosavia in previous
studies.
2.2. The manufacturing processes
During the evaporation process, the sugarcane juice was concen­
trated to a syrup by increasing the sugar concentration from 22 ± 2 to 60
± 10 ◦ Brix. This process was performed using a multiple-effect evapo­
ration (MEE, three effects) equipment to obtain syrup (60 ± 10 ◦ Brix),
while milling, cleaning, beating, and molding stages were the same as in
the traditional process. MEE works with a parallel configuration with a
clarified juice feed flow of 3.5 L/min at 90 ◦ C. This configuration fa­
cilitates the passage of juices from one effect to the next because of the
pressure distribution, flowing from higher to lower pressures.
2.2.1. Concentration technologies
The syrup (60–70 ◦ Brix) obtained in the previous evaporation stage
was concentrated using three different concentration technologies until
reaching 94 ◦ Brix.
2.2.1.1. CAL system. The concentrator consisted of a tube heat
exchanger inside an evaporator close to the exchange zone. It included a
short and wide tube jacket located on the outside that was fed with
2
LWT 168 (2022) 113897
steam. In addition, a centered tube was installed to return the juice from
the upper tube plate to the bottom to collect the concentrated juice. In
particular, the CAL is an open concentrator operated at a vapor pressure
of 50 psi until reaching 120 ◦ C.
2.2.1.2. Vacuum concentration system (MAR). Vacuum concentrators
such as MARs are widely used in the food industry to reduce boiling
temperature and energy consumption, as they work at low temperatures
with continuous agitation and vacuum conditions. The product was
continuously recirculated in an evaporator to achieve progressive water
separation from the syrup. The kettle had a hemispherical bottom with a
stirrer to ensure efficient heat exchange and avoid incrustations on the
wall. The MAR concentrator operated at a vapor pressure of 50 psi,
vacuum conditions (− 0.735 to − 0.27 atm), and temperatures between
54 and 80 ◦ C.
2.2.1.3. RW system. This nonthermal technique was designed to dry
heat-sensitive products, characterized by maintaining a relatively low
temperature inside the food, as it requires shorter drying times. The
moisture content was removed when the samples were applied evenly
on a polyethylene film simultaneously moving over a hot water surface
at 90–95 ◦ C.
Three active heat transfer mechanisms occur during the drying
process: radiation, conduction, and convection. Hot water flows in flat,
shallow canals to transfer energy across the film, which is thin enough to
attain the water temperature almost immediately. Hence, if a product
with considerable humidity, such as sugarcane syrup, is extended on the
film, refraction at the interface decreases, and radiant thermal energy
passes to the product. In the last stage, when the product is almost dry,
heat transfer by conduction dominates and the heat transfer rate di­
minishes as the product dries (Nindo & Tang, 2007). The RW concen­
trator operated using water at a temperature of 90 ◦ C.
2.3. Preparation of extracts for phenolic and acrylamide quantification
The samples were freeze-dried for the subsequent dissolution of 30 g
of the dried sample and methanol (1:1 w/v). The mixture was homog­
enized at 10,000 rpm for 1 min in an ice-water bath. The extracts ob­
tained were filtered under reduced pressure through filter paper
(Whatman No.1) and then concentrated in a rotatory evaporator at 37 ◦ C
and 100 rpm for 30 min. Finally, concentrated extracts were diluted in
60 mL of methanol and stored at 4 ◦ C until their analysis (Cifuentes
et al., 2021).
2.4. Acrylamide quantification
The acrylamide content of the extracts was analyzed using a Dionex
Ultimate 3000 ultra-high-performance liquid chromatograph (UHPLC)
(Thermo Scientific, Sunnyvale, CA, United States) with a binary gradient
pump (HP G3400RS), an automatic injector of samples (WPS 300TRS),
and a thermostated unit for the column (TCC 3000). The LC-MS interface
was electrospray ionization (ESI), and the mass spectrometer was of high
resolution with an Orbitrap ion current detection system. Chromato­
graphic separation was performed on a Hypersil GOLD Aq column 100
× 2.1 mm with a 1.9 μm particle size at 30 ◦ C. The mobile phase con­
sisted of an aqueous solution of 0.2% ammonium formate and acetoni­
trile with 0.2% ammonium formate. The initial gradient condition was
100% ammonium formate–acetonitrile, changing linearly to 100%
ammonium formate (8 min), held for 4 min, then returned to initial
conditions in 1 min. The total running time was 13 min, with a 3 min
post-run. An Orbitrap mass spectrometer (Exactive Plus) connected by
an electrospray interface (HESI) was operated positively with a capillary
voltage of 4.5 kV. Nitrogen was used as a drying gas. Mass spectra were
acquired in the mass range m/z 60–900. The Orbitrap mass detector was
calibrated, and identification of the compounds was carried out using
L. Vargas Valencia et al.
the full scan acquisition mode and ion extraction corresponding to the
[M+H]+ of compounds of interest, mass measurement with accuracy and
precision of Δppm <0.001, and using a standard solution of the com­
pounds (Mastovska & Lehotay, 2006).
2.5. Antioxidant activities assay
2.5.1. Ferric reducing antioxidant power (FRAP) method
A working FRAP solution (0.25 M acetate buffer with pH 3.6, 0.01 M
2,4,6-Tripyridiltrazine (TPTZ, ≥99%, Sigma-Aldrich), and 0.02 M ferric
chloride (Iron (III) chloride hexahydrate (99%), Merck)) was added to
dissolve the samples (1 g of sample in 10% (w/v) water). The mixtures
were incubated in the dark for 30 min, and the absorbance readings
were recorded at 593 nm using a PG Instruments T80+ UV/VIS spec­
trophotometer (United Kingdom). A calibration curve was obtained
using a 6-hydroxy-2.5.7.8-tetramethylchroman-2-carboxylic acid (Tro­
lox, Sigma-Aldrich) solution (Nielsen, 2019). All tests were conducted in
triplicates.
2.5.2. 2, 2 - diphenyl - 1 - picrylhydrazyl (DPPH) method
Sample diluted to 12% (w/v) were centrifuged at 6000 rpm for 15
min. DPPH free radical (ChemCruz) 0.002 M in ethanol (Roda Quimicos)
was added to 0.1 mL of the diluted samples supernatant to different
concentrations (0–10 mg/mL). The mixture was agitated and allowed to
stand at room temperature in the dark for 30 min. The absorbance was
recorded at 520 nm using a PG Instruments T80+ UV/VIS spectropho­
tometer (United Kingdom). The scavenging capability of DPPH radical
was calculated using Equation (1), where Actl is the absorbance of the
control sample (ethanol and DPPH solution) and ASam is the absorbance
of the evaluated sample (Harish Nayaka, Sathisha, Manohar, Chandra­
shekar, & Dharmesh, 2009). All tests were conducted in triplicates.
Actl − ASam
% Scavenging effect = x100 (1)
Actl
2.6. Phenolic content and polyphenol profile
2.6.1. Phenolic content
The phenolic content of NCS and juice samples was determined by
the Folin-Ciocalteu method using gallic acid as the standard. Folin-
Ciocalteu reagent 1N and sodium carbonate 20% (w/v) were added to
dissolve the samples (1 g of samples in 10% (w/v) water). A calibration
curve was constructed using different concentrations of gallic acid
standard solutions (0–5 mg/L). The mixtures were incubated in the dark
for 2 h, and the absorbance readings were recorded at 760 nm using a PG
Instruments T80+ UV/VIS spectrophotometer (United Kingdom). All
tests were conducted in triplicates.
2.6.2. Polyphenol profile
The samples for polyphenol profile analysis were prepared by dis­
solving the extracts obtained earlier (Section 2.3) in a methanol:water
(0.2%) in formic acid (1:1) solution, followed by vortexing for 5 min and
ultrasonication for 5 min. The analysis was performed using UHPLC
(Thermo Scientific, Sunnyvale, CA, United States), as described in Sec­
tion 2.4. The mobile phases used were A: aqueous solution containing
0.2% formic acid and B: acetonitrile with 0.2% ammonium formate,
with the following gradient program: 100% A (4 min), changing linearly
to 100% B (8 min), returning to the starting conditions in 1 min, and a
total running time of 13 min with 3 min of post-running. Nitrogen was
used as the sheath and auxiliary gas. Mass spectra were recorded at a
resolution of 30,000 in full scan mode in a mass range of m/z 60–900.
Identification of polyphenolic compounds were determined by
comparing retention time and mass measurements (Δppm <0.001) with
reference standards. Results are presented as concentration of respective
polyphenol per kg of dry sample and the corresponding error propaga­
tion analysis as estimated from the instruments precision (%).
3
LWT 168 (2022) 113897
2.7. Sugar content
Following the NREL/TP-510-42618 protocol with slight modifica­
tions, the samples were diluted in HPLC-type water to a concentration of
5% (w/v). A nine-point standard curve was prepared for all saccharides
(0.1–50 mg/L) (D (− ) fructose (98%), PanReac AppliChem. D (+)
glucose (97.5%), Scharlau. Sucrose (97.5%), Sigma-Aldrich). A Rezex™
RCM-Monosaccharide Ca+2 (8%) column was necessary for the run, 7.8
× 100 mm, at a temperature of 80 ◦ C, injection volume of 20 μL, and a
flow of 0.4 mL/min, using an ultrapure water mobile phase (Snow,
Trass, Rivera, Klein, & Misa, 2015). All tests were conducted in
triplicate.
2.8. Color measurement
Color was determined using a Konica Minolta CR-20 colorimeter
(Japan). The results were expressed in accordance with the CIELAB
system, with reference to illuminant D65 and a visual angle of 10◦ . The
parameters determined were L∗ (lightness), a∗ (green-red hue), and b∗
(blue-yellow hue). All measurements were conducted in triplicate.
2.9. Mineral and moisture content
The mineral content was determined according to the EPA 3015A
protocol using an aqueous sample extracted using microwave heating.
Both the sample and acids (nitric and hydrochloric) were placed in a
fluorocarbon polymer, sealed, and heated for the time determined by the
protocol. After cooling, the contents were filtered, centrifuged or
allowed to settle, and diluted to determine the metal content according
to the appropriate determinative method. All measurements were con­
ducted in triplicate.
Moisture content was determined using gravimetry with a Precisa
XM 60 moisture analyzer (Switzerland), using 3 g of homogenized
samples weighted in porcelain crucibles (Mauer & Bradley, 2017). The
results are expressed as the wet base (%). This test was conducted in
duplicate.
2.10. Glass transition temperature analysis
Glass temperature analysis was conducted using a differential scan­
ning calorimeter (DSC; TA Instruments DSC Q2000, United States). The
samples (10 mg) were weighed into TA Tzero capsules and hermetically
encapsulated using a Tzero press. An equal empty capsule was used as a
reference. A scanning rate of 5 ◦ C⋅min− 1 was used to analyze the sam­
ples, after cooling them to − 50 ◦ C at a 5 ◦ C⋅min− 1 rate and holding for 1
min. The samples were scanned after heating them from − 50 to 200 ◦ C
(Jagannadha Rao, Das, & Das, 2009).
2.11. SEM analysis
High-resolution images were obtained by scanning electron micro­
scopy (SEM) (up to 3 nm) using a beam of electrons. Three vacuum-dried
samples (70 ◦ C and − 0.040 MPa) were analyzed using a TESCAN FE-
MEB LYRA3 SEM (Czech Republic) with integrated EDS (Energy
Dispersive X-ray spectroscopy). Owing to the risk of having volatile NCS
crystals in the instrument related to the focused beam of electrons,
different magnifications were used: 60x, 200x, 600x, and 1000x for all
samples, and an additional 2000x and 5000x for MAR samples.
2.12. Statistical analysis
Atypicality, normality, variance, and one-way ANOVA with Tukey’s
test (95% confidence level) were applied to determine whether signifi­
cant differences existed among samples. Statistical analyses were per­
formed using Minitab® 18.1 software.
L. Vargas Valencia et al. LWT 168 (2022) 113897

3. Results and discussion 3.2. Antioxidant capacity and phenolic content

3.1. Acrylamide content
As shown in Table 1, UHPLC detected acrylamide content regardless
of the stage in the process, reaching values of up to 40 ± 2.40 μg/kg and
corresponding confidence intervals. Acrylamide formation showed a
relationship with thermal processes, as maximum concentrations were
reached in NCS products, confirming the Maillard reaction effect due to
its precursors (asparagine and sugar reducers). Also, juices and syrup
presented minimal amounts of the compound, which were lower than
the ‘limit of quantification (<LOQ)’ (Mesias, Delgado-Andrade,
Gómez-Narváez, Contreras-Calderón, & Morales, 2020). As expected,
CAL had the highest acrylamide content (40 ± 2.40 μg/kg), which could
be attributed to the fructose content present in this product together
with the thermal conditions applied. This is expected given the tem­
perature at which the technology operates, providing the conditions for
stimulating Maillard reactions. In addition, this content was lower than
the amounts previously reported: 60–3058 μg/kg(Gómez Narváez et al.,
2019), 35–2325 μg/kg, (Kawahara, Imaizumi, Kuroda, Aoki, & Suzuki,
2018), and 29–2762.8 μg/kg (Instituto Nacional de Vigilancia de Med­
icamentos y Alimentos (INVIMA), 2018), the latter being the Colombian
regulation for its content in NCS.
A significant difference (p < 0.05) was observed between the sam­
ples, where MAR and RW had superior characteristics given their
acrylamide content of less than 1 ± 0.06 μg/kg, which is innocuous for
the consumer. This result supports the positive impact of the evaluated
technologies on the product. The relationship between the operating
conditions of these technologies allows control over unwanted reactions
by reducing the caramelization temperature, ensuring a low thermal
impact on the product.
Acrylamides are potentially carcinogenic in humans (Virk-Baker,
Nagy, Barnes, & Groopman, 2014). They are found in carbohydrate-rich
foods, where asparagine and reducing sugars react during drying pro­
cesses at temperatures between 65 and 130 ◦ C. The Maillard reaction,
the mechanism that explains acrylamide in food, is the main route with
the amino acid asparagine as the primary precursor for NCS products.
This production happens through the direct process linked to the reac­
tion temperature, and shows significant acrylamide concentrations near
120 ◦ C.
As shown in Table 1, the antioxidant content ranged from 679.53 ±
116.80 to 1213.32 ± 32.90 mg GAE/g for the FRAP method and from
91.63 ± 30.43 to 135.80 ± 3.76 mg GAE/g for the DPPH method. All
samples displayed contrasting but consistent grades of radical scav­
enging ability, as demonstrated by both testing methods. The phenolic
content of the samples ranged from 1.78 ± 0.02 to 4.51 ± 0.06 mg GAE/
g (Table 1).
The juice samples showed minimum activity using both methods
(FRAP and DPPH) because of their low phenolic compound content.
Syrup had a higher antioxidant capacity than juice samples. As sup­
ported by phenolic compound results, large amounts of phenols are
directly related to their antioxidant capacity, color, and bioactivity role
(Alarcón et al., 2021). The statistical results showed that CAL samples
obtained the significantly lowest values of antioxidant capacity by the
FRAP method (p = 0.001), while the MAR samples obtained the
significantly highest values by the DPPH method (p < 0.001). The RW
samples did not present a significant difference with MAR and CAL
samples in its phenol content. The results showed that MAR samples
showed promising results in terms of antioxidant capacity and phenolic
content (Table 1).
The polyphenol profile was estimated using UHPLC, which identified
the polyphenolic compounds present in the NCS samples. Table 2 lists 12
phenolic acids: apigenin, catechin, cyanidin, epicatechin, epi­
gallocatechin, kaempferol, kaempferol-3-glucoside, luteolin, pelargoni­
dine, quercetin, rosmarinic acid, and theobromine. For NCS samples,
given the importance of phenols for the quality, stability, and potential
antioxidant capacity, five of the polyphenols presented the highest
concentration: Kaempferol-3- glucoside (9.3 ± 0.00–6.1 ± 0.00 mg/kg),
rosmarinic acid (3.8 ± 0.04–2.2 ± 0.02 mg/kg), pelargonidine (2.4 ±
0.07–1.1 ± 0.03 mg/kg), catechin (1.3 ± 0.01–0.6 ± 0.01 mg/kg), and
cyanidin (1.2 ± 0.01–0.5 ± 0.01 mg/kg), along with traces of other
phenolic compounds. Results showed (Table 2) that MAR samples
showed promising results due to its significantly higher content in
Kaempferol-3- glucoside (p < 0.05), rosmarinic acid (p < 0.001),
pelargonidine (p < 0.001), catechin (p < 0.001) and cyanidin (p <
0.001) compared to CAL and RW samples. In addition to the antioxidant
effect, the richness of Kaempferol-3-glucoside also gives NCS its anti-
inflammatory properties, responding to the body’s biological pro­
cesses, where the immune system acutely or chronically affects different
organs or tissues of the body (Cifuentes et al., 2021). Temperature was

Table 1
NCS characterization results: Acrylamide content, antioxidant capacity, phenolic content, sugar content, color, and moisture content.a
Sample Acrylamide Antioxidant capacity (mg/g) Phenolic Sugar content (g/100 g NCS) CIE L* a* b* Moisture
b
content (µg/kg) content (mg content (%)
GAE/g)

FRAP DPPH Sucrose Glucose Fructose L* a* b*

PJ <LOQ 679.53 ± 91.63 ± 1.78 ± 0.02 24.11 ± <LOQ <LOQ N. A. N. A. N. A. N. A.

116.80 30.43 9.45
CJ <LOQ 1008.70 ± 93.53 ± 3.27 ± 0.01 29.33 ± <LOQ <LOQ N. A. N. A. N. A. N. A.
129.40 17.90 1.63
Syrup <LOQ 1192.80 ± 128.94 ± 4.16 ± 0.14 71.60 ± 0.36 ± 4.86 ± N. A. N. A. N. A. N. A.
44.00 6.02 3.54 0.02 0.26
c
CAL 40 ± 2.4 1005.70 ± 116.59 ± 4.10 ± 0.10 c 59.61 ± 0.39 ± 4.67 ± 38.20 11.03 ± 18.37 ± 6.98 ± 0.01 d
176.20 c 8.26 c 6.28 d 0.02 d 0.70 d ± 0.87 d 0.12 c
0.70 c
MAR <1 ± 0.06 d 1213.32 ± 135.8 ± 4.51 ± 0.06 d 83.83 ± 0.42 ± 4.40 ± 45.67 8.47 ± 22.57 ± 9.24 ± 0.01 c
32.90 d 3.76 d 5.37 c d 0.00 e 0.38 d ± 0.25 c 0.67 d
1.22 d
RW <1 ± 0.06 d 1208.20 ± 131.37 ± 4.31 ± 0.10 c d 76.14 ± 0.17 ± 2.45 ± 46.27 7.70 ± 27.37 ± 6.67 ± 0.03 d
36.70 d 4.90 c 14.47 c 0.00 c 0.49 c ± 0.35 c 2.65 e
0.60 d
c-e
Different superscripts in the same column indicate significant differences (p < 0.05).
a
All data were the mean of three measurements ± standard deviation.
b
PJ: Precleaned juice, CJ: Clarified juice, CAL: Calandria, MAR: Marmite, RW: Refractance window.

4
L. Vargas Valencia et al. LWT 168 (2022) 113897

Table 2 the final product to avoid affecting its texture or stability during storage.
Polyphenol profile of the NCS extracts a. The results were favorable for MAR-processed samples because of their
Analyte RT, Concentration per sample (mg/kg) b high amounts of sucrose and moderate amounts of reducing sugars,
min making it the best option. These results demonstrate the advantages of
CAL MAR RW
working under vacuum conditions, minimizing the formation of
Apigenin 4.8 0.20 ± 0.01 c 0.20 ± 0.01 c 0.20 ± 0.01 c reducing sugars (Zhu et al., 2020) and acrylamide.
Catechin 3.1 1.30 ± 0.01 c 0.80 ± 0.01 d 0.60 ± 0.01 e
Cyanidin 3.4 1.00 ± 0.01 c 1.20 ± 0.01 d 0.50 ± 0.01 e
Epicatechin 2.3 0.30 ± 0.00 c 0.30 ± 0.00 c 0.20 ± 0.00 d 3.4. Color measurement
Epigallocatechin 2.9 <0.50* ± <0.50* ± <0.50* ±
0.00 c 0.01 c 0.01 c
Kaempferol 5 0.40 ± 0.00 c 0.40 ± 0.00 c 0.10 ± 0.00 d The colors of the samples were measured according to the CIE L∗ a∗ b∗
Kaempferol 3- 3.8 6.10 ± 0.00 c 9.30 ± 0.00 d 6.60 ± 0.00 c color space. In the L* a* b* color space (Table 1), RW and MAR displayed
glucoside significant higher values of lightness (L*) (p < 0.001) and b* parameter
Luteolin 4.5 0.70 ± 0.01 c 0.40 ± 0.00 d 0.40 ± 0.00 d
(p = 0.001), and lower values of a* (p = 0.039) compared to CAL. All
Pelargonidine 3.6 1.10 ± 0.03 c 1.60 ± 0.05 d 2.40 ± 0.07 e
Quercetin 4.5 0.30 ± 0.01 c 0.30 ± 0.01 c 0.30 ± 0.01 c samples’ a* and b* parameters were in the first quadrant of the plane,
Rosmarinic acid 4.1 3.20 ± 0.03 c 3.80 ± 0.04 d 2.20 ± 0.02 e presenting positive values, but tending to brownish orange on the color
Theobromine 2.7 0.30 ± 0.00 c 0.40 ± 0.00 d 0.70 ± 0.01 e scale. The RW and MAR samples presented high values of L* and b*,
c-e
Different superscripts in the same row indicate significant differences (p < with a light-yellow color, whereas the CAL samples had a browner and
0.05). darker color. The color parameters (L* , a* , b* ) could be related to the
a
All data are the mean of three measurements. acrylamide and phenolic contents. Therefore, a low phenolic content
b
CAL: Calandria, MAR: Marmite, RW: Refractance window. translates into darker colors related to oxidation, while high acrylamide
and reducing sugar contents tend to result in darker colors and lower
found to be crucial in the NCS production processes for preserving lightness values, related to Maillard reactions. (Mesias et al., 2020).
functional compounds such as phenols or antioxidants and their food
safety (Gómez Narváez et al., 2019).
3.5. Mineral and moisture content

3.3. Sugar content
Table 1 lists the compositions of the samples evaluated. As expected,
sucrose content was high in all samples, varying between 24.11 ± 9.45
and 83.83 ± 5.37 g/100 g NCS. On the other hand, reducing sugars
showed lower contents, ranging between 0.17 ± 0.00 to 0.42 ± 0.00 g/
100 g NCS for glucose and 2.45 ± 0.49 to 4.86 ± 0.26 g/100 g NCS for
fructose. These results were consistent with our expectations, corre­
sponding to the typical sugar profiles observed in the NCS process. This
agrees with previous studies, which indicate that the chemical integrity
of saccharides in syrups is maintained during most of the evaporation
process, and only the solid content changes due to water removal
(Alarcón, Orjuela, Narváez, & Camacho, 2020). When operating at high
temperatures, it is essential to minimize the inversion of sucrose so as
not to affect the NCS parameters (solidification, hardness, and color).
Table 1 shows the increase in sucrose concentration from the juice to the
NCS samples as the process was executed. The NCS samples exhibited
higher sucrose concentrations, and syrup samples responded to their
operating temperatures. The hydrolysis of the disaccharide resulted in
the formation of two short-chain monosaccharides. Its magnitude de­
pends on the nature of the catalyst and exposure time to the thermal
process (Peña Holguín, 2017). As shown in Table 1, there was a differ­
ence in glucose content between juices and syrup samples owing to their
first heating. The amounts of glucose were in accordance with the
concentration system and process temperatures used. The syrup samples
showed glucose contents comparable to those of NCS samples, but with
low stability compared to fructose. Regarding NCS, CAL behavior was
expected, as high temperatures accelerated the hydrolysis reaction
obtaining lower contents of sucrose (p < 0.001) and higher contents of
glucose (p = 0.007) and fructose (p = 0.001). RW samples operated at
low temperatures reducing the selectivity of hydrolysis reactions to
invert the sucrose molecules and producing significantly lower amounts
of glucose and fructose. These results suggest that reducing sugars may
help differentiate NCS from brown sugar, a similar natural sweetener
obtained by crystallizing concentrated sugarcane molasses with a much
lower fructose and glucose content (Alarcón et al., 2021). This analysis is
noteworthy for evaluating the characteristics of the final product given
the hygroscopic capacity of the NCS. As NCS absorbs humidity from the
environment, it is prone to alteration when it concentrates high contents
of reducing sugars and low contents of sucrose, which is undesirable in
As shown in Table 3, potassium levels (2174–2354 mg/100 g) were
the highest among all minerals (Qu, Li, Hang, Li, & Xie, 2018), with a
significant presence in the CAL and MAR samples (p < 0.001). Potassium
is an essential mineral necessary to balance fluids and other minerals in
the body and to ensure normal blood pressure. This mineral had the
highest concentration, followed by calcium (1065–944 mg/100 g),
magnesium (151–132 mg/100 g), and iron (16.7–8.87 mg/100 g), all of
them fundamental for most of the biological processes (Gharibzahedi &
Jafari, 2017). RW samples obtained the lowest significant calcium
contents (p < 0.001) while CAL obtained the lowest iron contents (p <
0.001). No significant differences were obtained between the NCS
samples for the rest of the minerals evaluated.
Moisture content is used for quality control and is related to micro­
biological safety of food. MAR samples obtained the highest significant
values (p = 0.002). However, the moisture content of all NCS samples
was within the recommended range (Gómez Narváez et al., 2019).
3.5.1. Glass transition temperature
The DSC thermograms obtained for NCS samples helped determine
the glass transition and melting temperatures, resulting in TgCAL =
71.84◦ C, TgMAR = 78.01◦ C, and TgRW = 71.42◦ C and TmCAL = 180.42◦ C,
TmMAR = 173.85◦ C, and TmRW = 174.41◦ C for CAL, MAR, and RW samples,
respectively.
An inverse relationship was observed between Tg and the reducing
sugar content of each sample: the higher the reducing sugar content, the
lower the glass temperature. However, this difference was not due to
sugar content alone. The size and shape factor of the solids obtained
from sucrose inversion play a fundamental role in this phenomena, as
reported by Jeong-Ah et al. (2006), who stated that Tg is a response to
the physical stability of amorphous solids. This is supported by studies
conducted by Verma, Shah, and Mahajani (2020), who observed that the
amorphous solids formed around the sugar crystals influenced the
thermodynamic equilibrium of the samples, where the higher the su­
crose content, the greater the energy requirement.
3.5.2. SEM
The sugar crystals in all three NCS samples were amorphous, without
any distinction between them (Fig. 1). Based on SEM analysis, a common
characteristic of NCS samples was the initial structure presented at 60x
and 200x, where the formation of organized solids with sugar crystals

5
L. Vargas Valencia et al. LWT 168 (2022) 113897

Table 3
NCS characterization results: Mineral content a.
Sample b Mineral content (P - %DB, Others - mg/kg-DB)
f
Calcium Copper Iron Magnesium Phosphorus Potassium Sodium Zinc
d c d c c c
CAL 1065.00 <0.66 8.87 137.00 0.70 2332.00 <1.41 1.01 c
MAR 1036.00 c <0.66 c
16.70 c
132.00 c
0.72 2354.00 c
<1.41 c
1.47 c
RW 944.00 e <0.66 c
16.10 c
151.00 c
0.73 2174.00 d
<1.41 c
1.76 c
c-e
Different superscripts in the same column indicate significant differences (p < 0.05).
a
All data are the mean of three measurements.
b
CAL: Calandria, MAR: Marmite, RW: Refractance window.
f
For this element, no replica was carried out, reason why it was not statistically analyzed.

Fig. 1. Scanning Electron Microscopy (SEM). 200 μm (600x) and 100 μm (100x) particles detected for NCS samples obtained by CAL (A, D), MAR (B, E) and RW(C, F)
respectively.

was not observed, but rather a predominant amorphology of the solids
formed. Melted amorphous solid structures were observed in the CAL
samples (Fig. 1A and D). The structure observed in the RW samples
(Fig. 1C and F) was similar to that observed in the MAR samples (Fig. 1B
and E) with fused solids, which hindered morphological identification.
The differences in the structure formed for each sample were observed as
the magnification increased. At 1000x, rectangular-shaped crystals were
observed, which were no longer evident at higher magnifications. The
rectangular structures observed in the MAR and RW samples could be
related to the sucrose crystals, which had excellent definition and did
not merge with the rest of the solids. These results could be related to the
reducing sugar content of the samples and the inflection in the ther­
mogram at which the NSC changed between the gummy and vitreous
states.
4. Conclusions
suggest that the new concentration technologies used in this study to
produce NCS could be an alternative to the traditional process, allowing
the production of high-quality, functional, and safe food products.
Future research, can be focused on the evaluation of the bioavailability
of the functional components of the product obtained and the determi­
nation of the impact on biomarkers of intake in vitro and in vivo.
CRediT authorship contribution statement
Lizzet Vargas Valencia: Conceptualization, Methodology, Valida­
tion, Formal analysis, Investigation, Writing – original draft, Visualiza­
tion. Maria Hernández-Carrión: Conceptualization, Resources,
Writing – review & editing, Supervision. Fabian Velasquez: Method­
ology, Validation, Writing. John Espitia: Methodology, Validation,
Writing. Jader Rodríguez Cortina: Conceptualization, Methodology,
Resources, Writing – review & editing, Supervision.

NCS samples obtained using three different technologies were Declaration of competing interest
characterized. According to the results, there were differences in the
evaluation properties attributed to the evaluated techniques (CAL, MAR, The authors declare that no known competing financial interests or
and RW). Most of the changes observed in parameters such as food safety personal relationships could have influenced the work reported in this
(acrylamide content), functionality (antioxidant capacity, phenolic paper.
compound content, and sugar content), and physical properties (color,
glass transition temperature, mineral content, moisture, and micro­ Data availability
structure) are related to temperature-dependent degradation processes.
The results showed that the higher the temperature, the lower the Data will be made available on request.
phenolic content and the higher the acrylamide content, with MAR
yielding the best functional and physical properties. Our findings

6
L. Vargas Valencia et al.
Acknowledgments
The authors want to acknowledge the financial support of Corpora­
tion Colombiana de Investigación Agropecuaria (AGROSAVIA),
Colombia and to the research team of the project entitled: “Development
of industrial processes that allows obtaining NCS added value products
from sugar cane.” Additionally, we thank the Universidad de los Andes,
Colombia, Chemical and Food Engineering Department for financing
and allowing the development of this study. Moreover, the authors wish
to thank “Elsevier” for assistance with the English manuscript.
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