Experimental Free Amino Acids Selective Extraction by Supercritical Carbon Dioxide: Modelling and Optimization

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Journal of Food Measurement and Characterization

https://doi.org/10.1007/s11694-023-01977-7

ORIGINAL RESEARCH

Experimental free amino acids selective extraction by supercritical


carbon dioxide: modelling and optimization
Amin Armion1 · Ali Vaziri1 · Bizhan Honarvar2 · Reza Fazaeli3 · Nadia Esfandiari2

Received: 27 February 2023 / Accepted: 11 May 2023


© The Author(s), under exclusive licence to Springer Science+Business Media, LLC, part of Springer Nature 2023

Abstract
A supercritical fluid extraction (SFE) method has been investigated to find the optimal conditions for selectively extracting
free amino acids using carbon dioxide. This study examined three variables: temperature, pressure, and time. It was found
that the SFE can selectively extract Alanine, Glycine, Cysteine, Histidine, and glutamic acid depending on the temperature
and pressure of the extraction vessel. However, SFE showed a low extraction performance for other amino acids in the
operating range studied. A design Expert was employed to generate a statistical model using the experimental data. The
final optimization obtained the highest degree of selectivity for glutamic acid (P = 14 MPa T = 20 ºC t = 40 min), Glycine
(P = 12 MPa T = 60 ºC t = 40 min), Histidine (P = 20 MPa T = 60 ºC t = 20 min), Alanine and serine (P = 20 MPa T = 60 ºC
t = 60 min). This condition can be used to selectively extract each amino acid studied due to the striking difference between
the optimal operating conditions of each category.

Keywords Supercritical fluid · Amino acid · Extraction · LC-MS-MS · Optimization

Introduction and protein extraction. Separating amino acids from the


primary product is critical, and the separation method sig-
The human body utilizes amino acids as building blocks to nificantly affects product quality [4–8]. For example, sepa-
synthesize proteins, which can be created in various variet- ration by conventional extraction causes concerns regarding
ies by linking amino acids in different sequences. Among flammability during the process, product toxicity due to
the twenty-two types of amino acids involved in protein unwanted residual solvents, and environmental concerns
formation, nine are considered essential, nine are non- [9, 10]. A growing interest is seen in using green solvents
essential, and four are semi-essential [1–3]. Nutritional due to the difficulties associated with separating them from
value, taste, therapeutic properties, and amino acid chemi- products, recycling them entirely, and the potential hazards
cal properties are important in the pharmaceutical, food, their use can cause. It is important to note that an environ-
and agricultural industries. It is estimated that 66% of the mentally friendly chemical process should be based on
amino acids produced are used in health and food produc- green solvents; however, most processes tend to be based
tion [4, 5]. Various industrial methods are used to produce on toxic or hazardous solvents [11, 12]. The separation of
amino acids, including chemical processing, fermentation, solvents is necessary both ecologically and economically.
Both environmentally and economically, it is essential to
separate solvents and recycle them by reintroducing them
into the process. Ionic liquids, supercritical fluids, and water
Ali Vaziri are among the most commonly used green solvents for this
[email protected]
purpose. Among these, supercritical carbon dioxide is envi-
1
Department of Chemical Engineering, Science and Research ronmentally safe, economically feasible and non-flamma-
Branch, Islamic Azad University, Tehran, Iran ble. Its low critical temperature is suitable for processing
2
Department of Chemical Engineering, Marvdasht Branch, temperature-sensitive amino acids, and it is easy to recover
Islamic Azad University, Marvdasht, Iran fully without any residual remains in the product. Carbon
3
Department of Chemical Engineering, Faculty of dioxide offers numerous benefits over traditional gases,
Engineering, South Tehran Branch, Islamic Azad University, such as its chemical inertness, suitability for use in food and
Tehran, Iran

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A. Armion et al.

pharmaceutical processes, and its non-flammability, non- extracting free amino acids have been investigated. This
toxicity, non-explosion, and non-corrosion properties in dry study examined three variables: temperature, pressure, and
environments [13–15]. Extracting polar compounds from time in supercritical and subcritical conditions.
natural materials can be challenging with carbon dioxide
due to its low polarity. However, this limitation can be over-
come by incorporating polarity modifiers as co-solvents. Materials and methods
The primary purpose of modifiers is to increase the criti-
cal fluid’s polarity, increase extraction efficiency and speed Chemicals
up the extraction procedure [16, 17]. In a study, Varaee et
al. utilized supercritical fluid extraction (SFE) to separate Abu Ghadara company supplied 99.99% pure carbon
sugar beet molasses and sugar cane sugar. They optimized dioxide as a solvent (Shiraz, Iran). Dichloromethane with
pressure, temperature, and extraction time, finding that a purity of 99.5%, ethanol and methanol with a purity of
the most efficient extraction of beet molasses occurred at 99.8% were provided by Merck, Germany. A zero-TDS dis-
P = 18.4 MPa, T = 43 ºC, and 76 min. Under these condi- tilled water of the Zolal brand had used (Tehran, Iran).
tions, aspartic acid, along with glutamic acid, alanine, and
lysine, were extracted with yields of 42%, 63%, 46%, and Samples
31%, respectively [18]. In an earlier study, Radfer et al.
utilized ethanol and carbon dioxide as solvents for isolat- Amino acid tablets were obtained from Cystic Nutrition
ing L-cartenin from oyster mushrooms via SFE. The study Company (Dunakeszi, Hungary). This company produces
identified four operating parameters that were optimized to amino acids by hydrolysis of protein. These tablets are used
achieve a 55% extraction efficiency [19]. The free amino as a control sample rich in free amino acids.
acids in broccoli leaves were extracted with supercritical
solvents by Arnaiz et al. Results showed that the method Equipment
exhibited greater efficiency and selectivity than other
extraction methods [20]. Bernal et al. conducted a study to Azad Marvdasht University’s chemical engineering depart-
evaluate the nutritional value of genetically modified barley ment designed and assembled a device to perform the
and soybeans. The study analyzed biological and synthetic extraction. This laboratory setup, schematically shown in
amino acids using SFE [21]. Shen et al. conducted a use- Fig. 1, comprises of a capsule containing 20 kg of liquid
ful analysis in which amino acids were extracted from sea CO2, which is equipped with a cooling chiller that reduces
turtle egg powder. Soaking the sample in water can increase the temperature of the CO2 entering the pump to -20. The
extraction efficiency, which is a notable benefit of this pro- extraction cell was supplied with high-pressure fluid from
cedure [21]. A study by Kong et al. scrutinized the impacts a piston pump of the Haskell American brand MSHP-71
of removing tuna waste by extraction and found that amino that can produce up to 60 MPa of pressure via high-pres-
acids such as leucine, glutamic acid, lysine, L-proline, and sure pipes. The extraction tube was constructed of stainless
taurine were found along with fatty acids from the tuna [22]. steel cylinders and could be accessed through two screws at
In addition, Vedarman et al. employed SFE to extract amino both ends. To prevent solids from exiting, a mesh net covers
acids, utilizing a method that involved derivatizing with the both entry and exit channels on each side of the piston. The
benzyloxy carbonyl group in the N-terminal. This method entire chamber contains a heater that maintains a constant
effectively made amino acids less polar and enhanced their temperature during extraction. Several valves are provided
dissolution into non-polar carbon dioxide by covering both in the extraction chamber, including control valves, pres-
ends of the amino acid (acidic and amino groups) [23]. Jian- sure relief valves, and safety valves. A U-shaped tube filled
lou Mu et al. make study to whole compare between soxhlet with dichloromethane follows the pressure relief valve at
and SFE technique for fatty acids extraction they found the output of the extraction chamber, which is intended to
higher yield extraction with soxhlent while upper quality for provide better performance for trapping the extracted ana-
extract has rich by SFE-CO2 [24]. Melgosa et al. study show lytes. The sensitivity of pressure and temperature gauges are
that bio refining strategies using supercritical carbon diox- ± 0.1 MPa and ± 1 ºC, respectively.
ide and subcritical water point out a suitable alternative for
the valuation of waste streams such as sardine heads, viscera Analyses of extracted analytes by LC-MS-MS
and spines. While extracts have good antioxidant activity
and anti proliferative effect against HT-29 adenocarcinoma The extracted analyte was subjected to high-performance
cells have been detected in the bioactivity assays [25]. In liquid chromatography, which involved using two mass
this work, the optimal operating conditions for selectively detectors for analysis. Separation was carried out using

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Experimental free amino acids selective extraction by supercritical carbon dioxide: modelling and optimization

Fig. 1 The experimental set up (A) CO2 Cylinder (B) Refrigerator (C) Reciprocating Pump (D) CO2 loading tank (E) Barometer (F) Extraction
cell (G) Heater (H) Joule-Thomson Valve (I) U-Shape trapping Tube

AB Sciex Corporation’s API 3000 columns, which had a Prototype analysis


255 mm height, 4.8 mm inner diameter, 6-micrometre par-
ticle size, and 360 m2/g 99.99% Sika ultra-pure porosity. A The company’s claims were proved by analyzing com-
carrier phase containing 50% acetonitrile and 50% deion- mercial food supplement tablets containing amino acids by
ized water was used at a flow rate of 0.8 ml/min, and the high-performance liquid chromatography [19]. Taking into
analysis was carried out at room temperature. The mass account the permissible error limits in testing, the manufac-
detectors were calibrated with pure amino acids, and the turer’s specifications were used to calculate the values in
peaks corresponding to each amino acid were defined in the most cases since the test values were, in most cases, more
device’s library for both qualitative and quantitative identi- than 95% of the labelled values on the product. Figure 2;
fication [26]. Table 1 present the tablet data and analysis results.
Each serving consists of four tablets.
Sample treatment and loading
Design of experiments
Tablets were crushed in a mortar and passed through a sieve
with a mesh size of 70. In order to prevent channelling in Classical methods, such as one variable at a time (OVAT),
the extraction vessel, 10 g of glass beads with a diameter of have been discarded due to their significant disadvantages,
0.5 mm were added to the powder before pouring into the including high material expenses, safety concerns, the lack
extraction vessel. This prevents the powder’s agglomera- of interaction between variables, and long experiment times
tion and the solvent flow’s channelling and creates an extra [27–29]. Employing the standard design of an experiment
solvent-powder contact surface. In each loading process, (DOE) is advantageous for a researcher, as it allows them
5 gr of the sample was loaded into the extraction chamber to determine the optimal experiment number required to
depending on the chamber’s capacity. To ensure that no identify a trend. Several methods of response surface meth-
solid particles were removed from the sample, a 100 mesh odology (RSM), such as D-optimal, Taguchi, Box-Bencken
net was placed over it again. It was then possible to add (BBD), and Central Composite Design (CCD) can be uti-
an additional solvent after the sample was soaked in some lized to perform the DOE [30, 31]. A D-optimal procedure
water, and the extraction chamber lid was screwed tight to provides maximum efficacy, as it uses intermittent zones
prevent leaks when under operating pressure. and mixing rules to minimize the number of tests [32]. Mod-
ifying the obtained models is among the highly significant
aspects of the D-optimal approach. Therefore, it is possible
to identify and remove the insignificant terms. Modifying
the model without significantly affecting the model results

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A. Armion et al.

Fig. 2 HPLC result for commercial food supplement tablets containing free amino acids

Table 1 Comparative data for commercial tablets HPLC result via Table 2  A D-optimal design considers factors at low and high levels
company data Factors Symbol Unit Low High
Samples Company Data (mg/4 HPLC Pressure X2 (MPa) 12 20
tablets) Result (mg/ Temperature X1 (º C ) 20 60
tablets)
Time X3 (Min) 20 60
Alanine 160 151
Arginine 77 79
Aspartic acid 352 337 Here σr represents the value of the error’s system, βij, βii,
Cystine 66 - and βi represent the effect of interaction, re, linear, Y stands
Glutamic acid 907 880 for the anticipated response, and β0 represents the constant
Glycine 48 58
coefficient. Using Design Expert 11, we can solve Eq. 6 to
Histidine 63 52
assess how individual factors respond to the conditions.
Iso lieucine 210 195
Leucine 352 329
Table 2 provides information about the factors affecting
Lysine 316 288 quality assurance (time, temperature, and pressure) at low
methionine 70 57 and high levels.
Phenylalanine 110 111 A quadratic model is used for optimal design. Selectivi-
Proline 209 - ties of the Alanine, Glutamic acid, Glycine, Histidine and
Serine 162 156 serine as aimed amino acids (AAAS) in this research are
Threonine 214 215 chosen as responses. We performed 20 experiments by put-
Tryptophane 46 - ting three variables at two levels (e.g. low and high).
Tyrosine 102 102 Here selectivity is defined as AAAS mass composition
Valine 204.00 185 percent in the extracted solution (ME) ratio to that of amino
3676 3202
acid mass composition percent in the original sample (MP).

can reduce the number of required experiments. In the cal- AAASMASS


M% = × 100  (2)
culation of the D-optimal strategy, we use Eq. (1) as the W HOLEAMINOACIDSMASS
governing Eqs. [33, 34]
S = ME /MP  (3)
k
 k 
 k k

Y =β0 + β i xi + βijxi xj+ β11x21+σγ  (1)
i=1 i=1 j=1 i=1

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Experimental free amino acids selective extraction by supercritical carbon dioxide: modelling and optimization

Table 3 ANOVA results using the D-optimal procedure in favor of AAAS selectivity
model Lack of Fit p-value F-value Mean Square Sum of Squares
Response 1 Alanine significant not significant < 0.0001 81.22 0.4353 3.92
Response 2 significant not significant < 0.0001 98.05 0.4237 3.81
Glutamic acid
Response 3 significant not significant < 0.0001 85.89 2.21 19.90
glycine
Response 4 significant not significant < 0.0001 282.50 3.05 27.48
histidine
Response 5 significant not significant < 0.0001 79.69 0.7611 6.85
serine

Table 4 Fit statistics


Analysis diagrams of the contour plot
Alanine glutamic Glycine Histi- Serine
Selectivity acid Selectivity dine Selec-
Selectivity Selec- tivity An analysis of contour plot maps was performed to deter-
tivity mine the effects of temperature, pressure, and time on the
Std. 0.0732 0.0657 0.1604 0.1040 0.0977 selectivity of AAAS.
Dev.
Mean 0.8565 3.08 2.63 0.9235 1.05
Alanine’s selectivity concerning temperature, pressure, and
CV % 8.55 2.14 6.09 11.26 9.34
time
R² 0.9865 0.9888 0.9872 0.9961 0.9862
Adjusted 0.9744 0.9787 0.9757 0.9926 0.9739
R² The contour plot in Fig. 3(a-c) is a representation of the
Pre- 0.9450 0.9552 0.9487 0.9851 0.9255 mixed effects of temperature(20 ºC ≤ T ≤ 60 ºC), pres-
dicted sure(12 MPa ≤ p ≤ 20 MPa), and time( a) t = 20 min, b)
R² t = 40 min, c) t = 60) min on the selectivity of alanine. Fig-
Adeq 25.7290 38.1377 27.9136 50.1467 32.1012
ure 3, shows that high temperatures and pressure can influ-
Preci-
sion ence alanine’s selectivity. Additionally, the temperature has
a more significant impact on Alanine selectivity over time
than pressure, and extreme temperatures at higher times
Result and discussion lead to a further increase in selectivity. This behavior can
be explained by Gidding’s relationship, which shows a rela-
Verification of the experimental design tionship between the solubility power of supercritical fluids
and critical pressures [35]. It has been shown in Gidding’s
As results show in ANOVA analysis, the F-value results relationship that as the critical pressure (Pc) or density (ρ)
of the models for the AAAS are significant. It should be increases, the amount of fluid solubility (∂) increases; this
noted that statistical significance is expressed by a P-value can result in the extraction of compounds with higher polar-
less than 0.0500. Based on ANOVA analysis (Table 3), all ity. According to the contour plot (Fig. 3), the temperature
p-values of the selectivity for the AAAS are less than 0.05, increase causes the density to decrease, which leads to a
which proves that the models are significant. Moreover, decrease in solubility. The optimal intersection point for
there is no significant difference between the lack of fit and the extraction of alanine is created at high temperature and
the pure error if the number of terms is less than 4. Accord- pressure, owing to the inverse impact of pressure and tem-
ing to ANOVA results (Table 3), the AAAS models’ lack of perature on the degree of dissolution power and due to the
fit terms is insignificant (Table 4). low molecular mass and non-polar nature of alanine, which
The R2-Predicted of the AAAS selectivity models aligns and strengthens the dissolution power by supercriti-
indicate that it is reasonable to conclude that they are in cal carbon dioxide.
agreement with the R-adjusted results; this means that the
differences are a smaller amount than 0.2. Furthermore, it is Glutamic acid’s selectivity concerning temperature,
desirable to have a signal-to-noise ratio of greater than four pressure, and time
when using Adeq Precision. Our model’s ratio of AAAS
denotes an adequate signal. Navigating the design space can Figure 4(a-c) are a graphic representation of the contour
be done with the help of these models. maps for the mixed impact of pressure and temperature on
the glutamic acid’s selectivity at 20, 40 and 60 min intervals,
respectively. According to Fig. 4, temperature and pressure

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A. Armion et al.

Fig. 3 The Alanine’s selectivity in accordance with temperature (20 ºC ≤ T ≤ 60 ºC) and pressure (12 MPa ≤ p ≤ 20 MPa) (a) t = 20 min, (b) t = 40 min,
(c) t = 60 min

at 20 min have little impact on glutamic acid selectivity. at 20, 40, and 60-minute time intervals, respectively. Fig-
Nonetheless, the selectivity of the extraction of glutamic ure 5 shows how glycine selectivity increased dramati-
acid is enhanced to even greater extents at times when the cally between 20 and 40 min under high temperature and
reaction time is greater than 20 min at low temperatures with pressure. An optimal overlap point for extraction at high
a pressure range of 15 MPa to 17 MPa. Glutamic acid’s high temperatures and pressure is created for glycine due to its
molecular mass, as well as its polar-ionic nature, demand a non-polar nature and low molecular mass, making it more
more robust solvation and surrounding by the solvent for soluble in supercritical carbon dioxide. However, selectiv-
effective extraction. This can be accomplished by utilizing ity at high temperatures and pressures diminishes somewhat
a higher solvent density, enhancing the extraction efficiency with increasing duration from 40 to 60 min.
at lower temperatures.
Histidine’s selectivity concerning temperature, pressure,
Glycine’s selectivity concerning temperature, pressure, and and time
time
Temperature and pressure effects on the selectivity of histi-
The contour maps for the mixed effects of pressure and dine are plotted in Fig. 6(a-c) over intervals of 20, 40, and
temperature on the selectivity of Glycine plot in Fig. 5(a-c) 60 min. Figure 6 shows the highest selectivity observed at

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Experimental free amino acids selective extraction by supercritical carbon dioxide: modelling and optimization

Fig. 4 The Glutamic acid’s selectivity in accordance with temperature (20 ºC ≤ T ≤ 60 ºC) and pressure (12 MPa ≤ p ≤ 20 MPa) (a) t = 20 min, (b)
t = 40 min, (c) t = 60 min

20 min at high temperature and pressure. It can be observed extraction and that the equilibrium between solvent and ser-
that the selectivity decreases with time, from 20 to 60 min, ine happened later than others.
indicating that the equilibrium between solvent and histi-
dine is reached earlier than for other AAAS, allowing for Optimization
more selective extraction of histidine in a shorter amount
of time. Design Expert 11 was employed to adjust the temperature,
pressure, and time conditions in order to acquire the lowest
Serine’s selectivity concerning temperature, pressure, and possible energy, material response, and maximum AAAS
time selectivities. The recommended points from the software
compared to the experimental results for the implied “Opti-
Figure 7 (a-c) displays the impacts of pressure and tempera- mum Condition”, which was analyzed in the laboratory. The
ture on serine’s selectivity over time intervals of 20, 40, and software’s optimal conditions were experimentally tested
60 min. As seen in Fig. 7, with increasing time from 20 to using the random condition in order to verify its accuracy
60 min at high temperatures and pressures, the selectivity in predicting optimal conditions (Table 5). According to
of serine increases. It shows that time plays a vital role in

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A. Armion et al.

Fig. 5 The Glycine’s selectivity in accordance with temperature (20 ºC ≤ T ≤ 60 ºC) and pressure (12 MPa ≤ p ≤ 20 MPa) (a) t = 20 min, (b) t = 40 min,
(c) t = 60 min

Table 5, the optimal terms recommended by the software ºC and a pressure of 20 MPa during the static extraction
proved to yield the highest selectivity of AAAS. time of 60 min. (Maximum pressure, temperature and time).
The glutamic acid can be selectively extracted by choos-
ing a 40-minute extraction step, a 20 ºC temperature and a
low pressure of 14 MPa in the first step. In this case, it is Conclusion
evident that none of the other amino acids is self-selective
at low temperatures or pressures in 40 min. In the second This research measured the impact of operational param-
stage, keeping the time constant and considering the low eters on the SFE of amino acids with carbon dioxide sol-
pressure of 12 MPa, increasing the temperature to the upper vent. Extraction was performed on the pretreated mixture
limit of the test, we see the selective extraction of Glycine. of free amino acids. The initial mix was again analyzed
In this range (low pressure and high temperature in 40 min). with an LC-MASS Technique in order to verify its compo-
In the third step, by simultaneously increasing the tempera- sition, and 95% conformity was found. Our choice of the
ture and pressure to the highest limit of the test, i.e. 20 MPa same operating conditions enabled us to compare the direct
pressure and 60 ºC, and taking into account the static extrac- effects of the additives more accurately. Our experiments
tion time of 20 min, we can see the selective extraction of have shown that, from the initial mixture of 20 amino acids,
histidine in this range (high pressure and temperature in we have successfully extracted only Alanine, Glycine, Ser-
20 min). In the fourth step, we can see the selective extrac- ine, Histidine, and glutamic acid and that the remaining 15
tion of alanine and serine by choosing a temperature of 60 amino acids were not effectively extracted. The potential of

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Experimental free amino acids selective extraction by supercritical carbon dioxide: modelling and optimization

Fig. 6 The Histidine’s selectivity in accordance with temperature (20 ºC ≤ T ≤ 60 ºC) and pressure (12 MPa ≤ p ≤ 20 MPa) (a) t = 20 min, (b)
t = 40 min, (c) t = 60 min

the SFE technique in selectively extracting the five amino


acids was found to be significant, while the extraction of
the other 15 amino acids under the conditions used in this
research was not successful. A statistical model was created
in Design Expert software using the experimental data, and
the highest selectivity was achieved through final optimiza-
tion, as shown in Table 10. These conditions can selectively
extract each of the studied amino acids.

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A. Armion et al.

Fig. 7 The serine’s selectivity in accordance with temperature (20 ºC ≤ T ≤ 60 ºC) and pressure (12 MPa ≤ p ≤ 20 MPa) (a) t = 20 min, (b) t = 40vmin,
(c) t = 60 min

Table 5 Analyzes the difference between the factors values obtained under optimal conditions
Factors Unit Optimum conditions Optimum conditions Optimum conditions Optimum conditions Optimum conditions
For serine selectivity For alanine selectivity For glutamic acid For glycine selectivity For Histidine
selectivity selectivity
(Time) ( Min ) 60 60 40 40 20
(Temperature) (℃) 60 60 20 60 60
(Pressure) ( MPa 20 20 14 12 20
)
Fit Selectivity 2.31 1.69 3.68 3.60 3.66

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