Salt Effect on Ethanol-Based Aqueous Biphasic Systems Applied to

Article pubs.acs.org/jced

Cite This: J. Chem. Eng. Data XXXX, XXX, XXX−XXX

Salt Effect on Ethanol-Based Aqueous Biphasic Systems Applied to Alkaloids Partition: An Experimental and Theoretical Approach Mateus Oltramari Toledo, Fabiane Oliveira Farias, Luciana Igarashi-Mafra, and Marcos R. Mafra* Department of Chemical Engineering, Federal University of Paraná (UFPR), Polytechnic Center, Jardim das Américas, Curitiba, Paraná 81531-990, Brazil

Downloaded via MACQUARIE UNIV on February 20, 2019 at 18:27:08 (UTC). See https://pubs.acs.org/sharingguidelines for options on how to legitimately share published articles.

S Supporting Information *

ABSTRACT: Aqueous biphasic systems (ABSs) based on alcohol−salt are of significant interest because of their low cost and environmental impact, as well as their higher selectivity and fast phase segregation, when compared to a polymer− salt ABS. The salt effect was evaluated in ethanol-based aqueous biphasic systems using five different salts (NaH2PO4, K2HPO4, K3PO4, K2CO3, or K3C6H5O7) at 298.15 K and atmospheric pressure. The results suggest that both the cation and anion natures present an influence on liquid−liquid equilibrium (LLE). To describe the experimental LLE data, the nonrandom twoliquid model was used to adjust the experimental data, which showed a good fit (rmsd < 0.68%). The salt influence in ABSs and its partition ability was accounted by phase diagrams, as well as a partition study using nicotine and caffeine. Results have shown high partition yield and high selectivity. According to Aniszewski (2017),24 alkaloids are biologically significant as active stimulators, inhibitors, and terminators of growth, a part of an endogenous security and regulation mechanism. In general, alkaloids are important for different areas of the economy, industry, trade, and services and can be used in some applications as well as agricultural insecticide25 or health medicines.26,27 The nicotine detection in trace levels is crucial, considering its addictive property.28 Meanwhile, caffeine plays an important role in the medical field and sports science,29−32 and food engineering.33,34 Common methods used for extraction of these alkaloids, such as supercritical carbon dioxide,35−38 liquid−liquid39−41 and solid−liquid42 extraction with organic solvents, present low extraction yields. Besides, these methods can generate undesirable compounds, in addition to using toxic organic solvents.17 The aim of this work is to evaluate the salt influence on ethanol-based aqueous biphasic systems on the alkaloids partition. For this purpose, five different salts (monosodium phosphate, dipotassium phosphate, tripotassium phosphate, potassium carbonate, and potassium citrate) were used to obtain liquid−liquid equilibria (LLE) experimental data with ethanol and water at 298.15 K and atmospheric pressure. Furthermore, the nonrandom two-liquid model (NRTL) was applied to correlate the experimental data.

1. INTRODUCTION Albertsson, in 1956, reported for the first time an aqueous biphasic system (ABS) applied to proteins separation.1 In general, these systems are produced by the combination of two hydrophilic solutes which present incompatibility in aqueous solution above the critical concentrations resulting in two imiscible aqueous phases.1−5 Traditional ABSs were composed of an aqueous solution of two polymers or a polymer and a salt. In this case, the relative effectiveness of various salts to promote the phases separation follows the Hofmeister series, which is a classification of ions based on their salting-out ability.6 Compared to conventional extraction methods, such as the use of organic solvents7 and supercritical fluids,8 ABSs have some advantages, such as low energy consumption, fast separation, simple technology, and low cost, and they are easy to scale-up.9 Moreover, since both phases are mainly composed of water, the ABSs are a biocompatible method of extraction and purification for a large range of materials,10 e.g., proteins,11 phenolic compounds,12 enzymes,13 metallic ions,14 and other high valueadded biomolecules. Besides polymers,15 several compounds, such as ionic liquids,16,17 deep eutectic solvents (DES)18 and organic compounds (e.g., alcohols and acetone)19,20 can be used as a phase former in ABSs. The systems composed by salt solution and hydrophilic organic solvents, such as alcohol−salt, have been of great interest because of their easy recovery and low environmental impact. In addition, their higher selectivity, lower viscosity, fast phase separation, large throughput and low cost when compared to a polymer-salt ABS highlight their value.21−23 © XXXX American Chemical Society

Special Issue: Latin America Received: November 1, 2018 Accepted: February 4, 2019

A

DOI: 10.1021/acs.jced.8b01024 J. Chem. Eng. Data XXXX, XXX, XXX−XXX

Journal of Chemical & Engineering Data

Article

Table 1. Materials Purities and Suppliers chemical name

molecular formula

CASRN

purity

source

ethanol monosodium phosphate dipotassium phosphate trispotassium phosphate potassium carbonate potassium citrate monohydrate (−)nicotine caffeine

C2H6O NaH2PO4 K2HPO4 K3PO4 K2CO3 K3C6H5O.H2O7 C10H14N2 C8H10N4O2

64-17-5 7558-80-7 7758-11-4 7778-53-2 584-08-7 6100-05-6 54-11-5 50-08-2

99.5% 98.0% 98.0% 99.5% 99.0% ≥99.90% ≥99% 99.0%

Dinâmica Neon Alphatech Vetec Alphatech Neon Sigma Biotec

2. EXPERIMENTAL SECTION 2.1. Materials. The water used in the experiments was obtained from a reverse osmosis system purification (Vexer ́ Smart VOS 106). Ethanol was supplied by Dinâmica Quimica Contemporânea Ltd.a (Diadema, SP, Brazil). Different salts were employed during the experiments: monosodium phosphate and potassium citrate monohydrate, both from Neon Comercial (São Paulo, SP, Brazil), dipotassium phosphate and potassium carbonate, from Alphatech Ltd.a (São Bernardo do Campo, SP, Brazil), and tripotassium phosphate from Vetec ́ Quimica Fina Ltd.a (Duque de Caxias, RJ, Brazil). Nicotine was supplied by Sigma-Aldrich (St. Louis, MO, USA), and ́ caffeine was obtained from Biotec Quimica Ltd.a (Juiz de Fora, MG, Brazil). Further information can be found in Table 1. 2.2. Phase Diagrams Determination. To obtain a binodal curve the cloud point titration method10,43 was applied at 298.15 ± 0.1 K and atmospheric pressure (around 91 kPa). Ethanol and salt aqueous solutions were prepared using a gravimetric procedure (AUX320, Shimadzu). For the ethanol solutions, concentrations from 60 to 75 wt % were used. Concerning the salt solution, different salt concentrations were employed: NaH2PO4, K3PO4, K2CO3, and K3C6H5O7 at 50 wt % and K2HPO4 at 60 wt %. The ethanol dilution in water was realized to avoid loss by evaporation, which is higher using pure ethanol, meanwhile, the salt solutions concentrations correspond to the salt solubility limit. Ethanol or salt aqueous solutions were added dropwise to each other under constant stirring, until the detection of the cloud point (biphasic region). After this, water was added to the system until a clear solution was obtained (monophasic region). All compositions of the ternary solution were calculated by gravimetric analysis (AUX320, Shimadzu). Equation 1 with the capability to predict the binodal curve, and proposed by Merchuk et al.,44 was adjusted to experimental data. y = A exp( −Bx 0.5 − Cx 3)

lying in the two-phase region were chosen. The systems’ components were gravimetrically weighed (AUX320, Shimadzu) with an uncertainty of 0.0001 g, in centrifuge tubes (15 mL), vigorously stirred using a vortex mixer (Gomixer, MX-S) and allowed to reach equilibrium at 298 ± 0.1 K (Lab Companion, RW-1025G) for approximately 24 h.17 Top and bottom phases were carefully separated with a glass Pasteur pipet and weighed, and their pH was measured (pH 11 series, OaktonTM). The pH meter was previously calibrated with three buffer solutions (pH values of 4.00, 7.00, and 10.00).18 A gravimetric method, described by Merchuk et al.,44 was used in order to determine the tie-lines compositions. The following system of equations, which are based on the mass balance of the components in the ABS, is solved in this method.

∑ (yi (exp) − yi (mod))2 i=1

yt =

(4)

xt =

y i1 y − jjj − 1zzzyb α kα {

(5)

x i1 y − jjj − 1zzzxb α kα {

(6)

In the previous set of equations, α is the ratio between top and overall system weights. Subscripts t and b represent top and bottom phases, respectively. The tie-line length (TLL), which represents the final concentration of phase components in the top and bottom phases, is often used to express the effect of system composition on partitioned material.10 It can be calculated from the following expression: TLL =

(xb − xt)2 + (yb − yt )2

(7)

As far as the difference between the top and bottom phases decrease, TLL starts to approach to zero and the system tends to a critical point. The critical point of each system was calculated as previously described in the literature.23 At this point, the composition and volume of both phases are equal.45 Equation 8 was applied for the calculation of the slope of the tie-line (STL). y − yb STL = t x t − xb (8)

(1)

N

OF = 10

(3)

yb = A exp( −Bxb0.5 − Cxb3)

where y and x are the mass fraction of ethanol and salt, respectively, present in the aqueous solution (overall composition). Constants A, B, and C can be obtained by minimization of an objective function (OF), according eq 2. In the present study Gnumeric package with a nonlinear solver was used for this purpose. 10

yt = A exp( −Bxt0.5 − Cxt3)

2.3. Biomolecules Partition. To evaluate the nicotine and caffeine partition the tie-line furthest from the critical point of each system was chosen. All system compounds were adequately weighed and instead of water, aqueous solutions of nicotine and caffeine at 1 g/L were used. This concentration corresponds to a 6.16 × 10−3 mol/L for nicotine and 5.15 × 10−3 mol/L for

(2)

As described by Sampaio et al.17 a constant of optimization (1010) can be used to improve the objective function. Once the phase regions were identified, the construction of tie-lines could be achieved. Six points with overall composition B



Article

Table 3. Equilibrium Data of the ABS Composed of Ethanol (we) + salt (ws) + water at 298.15 K and 91 kPaa overall TL

Figure 1. Binodal curves for different systems composed of water, ethanol, and salt at 298.15 K and 91 kPa: (a) mass fraction and (b) molality.

Table 2. Adjusted Constants of Merchuk Equation (eq 1) for the System Salt + Water + Ethanol salt

A

B

C × 10

NaH2PO4 K2HPO4 K3PO4 K2CO3 K3C6H5O7

73.1674 89.1351 79.1915 105.8032 82.8694

0.3072 0.4245 0.3396 0.4167 0.2467

1.3258 0.8863 2.1185 2.8128 2.1705

5

r

100we

100ws

top phase 100we

1 2 3 4 5 6

20.0 20.5 20.9 21.5 22.0 22.5

20.1 20.5 21.1 21.5 21.9 22.5

31.3 32.8 35.3 37.6 39.7 41.6

1 2 3 4 5 6

17.0 17.5 18.0 18.5 19.0 19.5

16.9 17.5 18.0 18.5 19.0 19.5

23.9 25.2 27.8 29.8 31.5 34.2

1 2 3 4 5 6

20.0 20.7 21.2 21.5 21.9 22.7

19.9 20.5 21.1 21.4 21.9 22.5

38.1 40.3 42.4 44.4 46.6 48.4

1 2 3 4 5 6

18.6 19.0 19.5 20.0 20.5 21.0

18.5 19.0 19.5 20.0 20.5 21.0

40.8 44.1 48.1 50.6 53.7 56.8

1 2 3 4 5 6

22.5 23.0 23.4 24.0 24.4 25.1

22.7 23.0 23.5 24.0 24.5 25.0

47.2 51.0 54.0 57.1 59.8 61.9

100ws

bottom phase 100we

NaH2PO4 7.5 7.0 6.7 5.9 5.6 5.5 4.7 5.1 3.9 4.8 3.4 4.2 K2HPO4 9.5 9.1 8.8 7.3 7.5 6.8 6.6 6.3 6.0 5.8 5.1 5.6 K3PO4 4.6 5.9 3.9 4.8 3.4 4.1 2.9 4.1 2.4 3.7 2.1 3.1 K2CO3 5.2 9.2 4.4 8.2 3.6 7.6 3.1 6.7 2.6 6.1 2.2 5.6 K3C6H5O7 5.2 11.6 3.8 10.6 3.0 9.0 2.3 7.9 1.7 7.2 1.4 5.9

100ws

STL

TLL

34.5 36.7 37.6 38.6 39.2 40.8

−0.91 −0.90 −0.93 −0.96 −0.99 −1.00

36.39 40.28 43.75 47.04 49.65 52.96

25.4 28.9 30.1 31.4 32.6 33.1

−0.93 −0.89 −0.93 −0.95 −0.97 −1.02

21.7 27.0 30.8 34.1 37.1 40.0

31.8 34.0 35.3 35.4 36.2 37.9

−1.19 −1.18 −1.20 −1.24 −1.27 −1.27

42.2 46.6 49.8 51.8 54.6 57.8

24.1 25.3 26.2 27.3 28.2 29.1

−1.67 −1.71 −1.79 −1.81 −1.86 −1.90

36.8 41.5 46.4 50.1 54.0 57.9

30.4 31.4 33.2 34.5 35.6 37.3

−1.41 −1.47 −1.49 −1.52 −1.56 −1.56

43.6 48.9 54.2 58.8 62.5 66.5

a

Standard uncertainties u are u(w) = 0.005, u(T) = 0.2 K, and u(P) = 10 kPa.

2

0.9997 0.9985 0.9984 0.9987 0.9991

K=

[alkaloid]alcohol [alkaloid]salt

(9)

where [alkaloid]alcohol and [alkaloid]salt are the alkaloid concentration in alcohol and salt-rich phase, respectively. Moreover, the ratio between K-values of both biomolecules (at the same system) can be used to evaluate the selectivity (S) of the systems, which in this work was defined according to eq 10.

caffeine, which were chosen to achieve infinite dilution preserving the LLE behavior. All mixtures were prepared with a 0.0001 g uncertainty in the centrifuge tubes, properly stirred by a vortex mixer (MX-S, Gomixer), and maintained at 298.15 K in a thermostatic bath (Lab Companion, RW-1025G) during 24 h.46 The top and bottom phase were properly separated. In sequence alkaloid concentration (z), caffeine or nicotine, in each phase was determined using a UV−vis spectrophotometer (UV-1800, Shimadzu) at 260 and 273 nm, respectively. A calibration curve relating the absorbance of the biomolecule and its concentration in the aqueous solution was previously obtained. The partition coefficient (K) of the alkaloid (caffeine or nicotine) was determined as the ratio between its concentration in the alcohol and salt-rich phase (eq 9).

S=

K nicotine Kcaffeine

(10)

Extraction efficiency (E) was calculated as eq 11. E(%) =

[alkaloid]alcohol . malcohol [alkaloid]alcohol . malcohol + [alkaloid]salt . msalt (11)

where m represents the mass of each phase (alcohol and saltrich phases) in equilibrium. C



Article

Figure 2. Experimental phase diagrams of systems formed by water, ethanol, and salt at 298.15 K and 91 kPa: (a) monosodium phosphate, (b) dipotassium phosphate, (c) tripotassium phosphate, (d) potassium carbonate, and (e) potassium citrate.

3. RESULTS AND DISCUSSION 3.1. Phase Diagrams and Salt Effect. The binodal experimental data in mass fractions are shown in Figure 1a. The binodal curves obtained in this work were compared with the literature ones19,47−51 showing good agreement for most of the evaluated systems (Figure S1, Supporting Information). For some systems the observed differences can be attributed to the uncertainties of the experimental measurements and to the possible ethanol evaporation during the acquisition of the binodal curves. It should be highlighted that the presence of a

volatile element, in this case ethanol, requires special care during the experiments. In this work, for example, the ethanol was diluted in water prior to titration in order to reduce ethanol losses by evaporation, as described in section 2.2 To evaluate the ability of the salts to form two-phases, the binodal curves were also presented in molality (Figure 1b). For each system was chosen the point where the molality of ethanol is equal to the molality of salt in the binodal curve. This procedure was adopted as a semiquantitative measure of the ions salting-out strength.52 Considering this, the potassium salts D



Article

presented similar behavior and the sodium salt showed the smaller biphasic region between all of them (Figure 1b). According to the position of binodal curves, it is possible to demonstrate the relative ability of these salts to induce two-phase formation, which follows the order: K3C6H5O7 ≈ K2HPO4 ≈ K3PO4 > K2CO3 > NaH2PO4. Disodium phosphate (Na2HPO4) and monopotassium phosphate (KH2PO4) salts were also evaluated. However, due to the precipitate formation, it is not possible for these systems to obtain the binodal curves, and consequently the tie-lines. The fitting parameter of eq 1 for the binodal curves in mass fraction were given in Table 2. It is possible to observe that the Merchuk adjustment44 has an excellent fit to all experimental data. Determination coefficients (r2) lie all above 0.99, with a 0.95 confidence level. Six tie-lines were obtained for each studied system. Experimental data from liquid−liquid phase equilibria, overall and phase’s compositions (in mass fraction), as well as tie-lines lengths (TLL) and the slope of tie-line (STL) can be seen at Table 3. All systems have presented an alcohol-rich top-phase and a salt-rich bottom-phase. The difference between these concentrations can be correlated with the tie-line slope (STL). It is important to highlight that water is the majority compound of both phases, characterizing an aqueous biphasic system. The most negative value of the tie-line slope is from potassium carbonate, while monosodium phosphate shows the least one (negative value). The water solubility of salts seems to influence the slope of the tie-line, since it is related with the ability of each salt to bind to ethanol for hydration complexes, which is in agreement with the Hofmeister series. The binodal curves and respective tie-line, as well as the critical point of each system, are shown in Figures 2a to 2e. Both tripotassium phosphate and potassium citrate systems showed good agreement with previous studies developed by Yun et al.19 3.2. Thermodynamic Modeling. Non-Random TwoLiquid model (NRTL), proposed by Renon and Prausnitz,53 was correlated with the experimental data. Equations for calculating NRTL activity coefficients for ABS were proposed by Sé and Aznar.54 TML-LLE 2.0 software, developed by Stragevich and D’Á vila, was used to estimate NRTL parameters (Aij and αij). The objective function (OF), given by eq 12, was minimized using a modified Simplex numeric method.55 D

OF =

Table 4. Binary Interaction Parameters of NRTL Model and Root Mean Square Deviations (δ) for Systems Composed by Ethanol (1) + Salt (2) + Water (3) at 298.15 K

M N−1 j

j

Aij (K)

1 1 2

2 3 3

1305.2 44.245 −458.83

1 1 2

2 3 3

683.47 −716.84 −1587.7

1 1 2

2 3 3

540.12 −298.17 −1326.6

1 1 2

2 3 3

610.75 663.23 6111.2

1 1 2

2 3 3

784.14 211.11 −1178.0

Aji (K) NaH2PO4 2261.0 670.44 1140.8 K2HPO4 11030 1428.8 3243.9 K3PO4 6341.3 769.60 7307.6 K2CO3 595.91 683.11 10147 K3C6H5O7 2078.0 510.90 10533

αij

δ (%)

0.2030 0.4700 0.4700

0.5351

0.2809 0.2043 0.2525

0.3686

0.2000 0.2954 0.3000

0.3935

0.3925 0.4516 0.4700

0.6802

0.2153 0.3895 0.3553

0.1845

that the NRTL model has a good fit to experimental data (δ ≤ 0.6802%), and it is shown that the model is suitable to represent the phase behavior of ethanol-based ABSs addressed in this work. 3.3. Alkaloids Partition. To evaluate the ability of ethanol-based ABSs application in the extraction processes, solutions of 1 g/L of nicotine or caffeine were used to study the partition of these biomolecules. The molecular structure of these biomolecules can be observed in Figure 4. The tie-line furthest from the critical point (TL 6) was selected to evaluate the alkaloids partition, since in this condition the top and bottom composition are quite different, which should favor the partitioning of the molecules. The overall composition of these tie-lines can be obtained in Table 3. Partition coefficients (K), selectivity (S), and extraction efficiency (E) are presented in Figure 5. Selectivity was calculated using the ratio between partition coefficients from nicotine and caffeine in each system, according to eq 10. Through the K analysis, it is possible to realize that for all systems both alkaloids were mainly partitioned to the ethanolrich phase, which was expected due to the low hydrophilicity of these biomolecules. An exception was the nicotine partition in the system containing monosodium phosphate (NaH2PO4) where K < 1, suggesting a preferential partition to the salt-rich phase. This fact can be explained through the chemical speciation of the nicotine and the pH of the systems. All ABS present basic pH (from 8.9 to 13.9, Supporting Information) with the exception of the system with NaH2PO4 (around 4.5). This way, in the greater part of the systems, nicotine has a higher affinity for the more hydrophobic phase. However, at acidic pH nicotine being present mainly as a positively charged species has a preferential partition for the most hydrophilic phase (saltrich phase).56 The caffeine, in its turn, does not suffer chemical speciation with any pH value, which agrees with the preferential partition to the ethanol rich-phase in all the cases. The highest K values were obtained to the nicotine using potassium carbonate (K2CO3) and tripotassium phosphate

∑ ∑ ∑ (wijkI,exp − wijkI,calc)2 + (wijkII,exp − wijkII,calc)2 k

i

i

(12)

where mass fraction is represented by w, and superscripts I and II refer to the two liquid phases in thermodynamic equilibrium, D is the number of data sets, M and N are the tie-lines and number of components, respectively. The mass fraction was used only in the objective function in order to facilitate the convergence process. Root mean-square deviation (δ) was used to compare experimental and predicted data (eq 13). Table 4 shows all binary parameters of the NRTL model obtained, as well as the δ values. ÄÅ M N I,exp ÉÑ1/2 ÅÅ ∑ ∑ (w − wijI,calc)2 + (wijII,exp − wijII,calc)2 ÑÑÑÑ ÅÅ j i ij ÑÑ δ = ÅÅÅ ÑÑ ÅÅ 2 MN ÑÑ ÅÅÇ ÑÖ (13)

Figure 3 presents the experimental and predicted tie-lines (by NRTL model) for all five systems studied. It can be seen E



Article

Figure 3. Experimental and predicted tie-lines of systems formed by water, ethanol, and salt at 298.15 K and 91 kPa: (a) monosodium phosphate, (b) dipotassium phosphate, (c) tripotassium phosphate, (d) potassium carbonate, and (e) potassium citrate.

(K3PO4), which are the most alkaline systems. The selectivity parameter (S) was calculated to evaluate the capacity of these systems to separate nicotine from caffeine in a single step. Higher values of S were obtained in the systems composed by the salts tripotassium phosphate (K3PO4) and potassion carbonate (K2CO3). It indicates that in these systems nicotine can be selectively separated from caffeine, which is concentrated in the ethanol-rich phase. The same is observed for caffeine in relation to nicotine in systems composed of the salts monosodium phosphate (NaH2PO4) and dipotassium phosphate

Figure 4. Molecular structures of the biomolecules: (a) nicotine and (b) caffeine. F



Article

viscosity, fast phase separation, and consequently short time of separation process, as previously observed by Sanglard et al.23

4. CONCLUSION Ethanol-based aqueous biphasic systems (ABS) using five different salts (monosodium phosphate, dipotassium phosphate, tripotassium phosphate, potassium carbonate, and potassium citrate) were evaluated in this work at 298.15 K and atmospheric pressure. Phase diagrams were obtained and, based on binodal and tie-line data, it was possible to observe the high impact of salt nature on phase behavior. Experimental data were correlated using the NRTL activity coefficient model, which provides a good representation of data and a low root mean-square deviation (δ ≤ 0.68%). The evaluated systems efficiently separated alkaloids (nicotine and caffeine), and in most cases, these biomolecules were partitioned preferentially to the ethanol rich-phase. Besides, it was observed that the systems present suitable selectivity to promote the separation of both alkaloids in a single step, which demonstrates their potential for biomolecules extraction.

■

ASSOCIATED CONTENT

S Supporting Information *

The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acs.jced.8b01024. Detailed experimental data of binodal curves, pH of tielines, biomolecules extraction efficiencies and partition coefficients values (PDF)

■

AUTHOR INFORMATION

Corresponding Author

*E-mail: [email protected]. Tel.: +55 41 3361 3586. ORCID

Marcos R. Mafra: 0000-0002-0018-6867 Funding

This work was supported by the Graduation Program of Food Engineering (PPGEAL-UFPR) and CAPES−Coordenaçaõ de ́ Superior, a Brazilian Aperfeiçoamento de Pessoal de Nivel government agency. Prof. M. Mafra is grateful for a Brazilian National Council for Scientific and Technological Development (CNPq) grant (310905/2015-0). Notes

The authors declare no competing financial interest.

■

REFERENCES

(1) Albertsson, P.-Å. Chromatography and partition of cells and cell fragments. Nature 1956, 177, 771−774. (2) Albertsson, P.-Å. Partition of proteins in liquid polymer− polymer two-phase systems. Nature 1958, 182, 709−711. (3) Albertsson, P.-Å. Particle fractionation in liquid two-phase systems; the composition of some phase systems and the behaviour of some model particles in them; application to the isolation of cell walls from microorganisms. Biochim. Biophys. Acta 1958, 27, 378−395. (4) Albertsson, P.-Å.; Nyns, E. J. Counter-current distribution of proteins in aqueous polymer phase systems. Nature 1959, 184, 1465− 1468. (5) Rito-Palomares, M. Practical application of aqueous two-phase partition to process development for the recovery of biological products. J. Chromatogr. B: Anal. Technol. Biomed. Life Sci. 2004, 807, 3−11. (6) Ananthapadmanabhan, K. P.; Goddard, E. D. Aqueous biphase formation in polyethylene oxide-inorganic salt systems. Langmuir 1987, 3, 25−31.

Figure 5. Extraction parameters of nicotine and caffeine at systems composed of water, ethanol, and salt at 298.15 K and 91 kPa. (a) Partition coefficients, K; (b) extraction efficiency, E; and (c) selectivity, S.

(K2HPO4). However, NaH2PO4 was more selective for caffeine than K2HPO4. All the systems, with exception of nicotine extraction applying ethanol−NaH2PO4, present high extraction efficiency values (E%), up to 98.98%, indicating a high ability of the ethanol-based systems to be applied in the extraction process. It should be highlighted that alcohol-based ABSs present low G



Article

(7) Shi, C.; Jing, Y.; Xiao, J.; Wang, X.; Yao, Y.; Jia, Y. Solvent extraction of lithium from aqueous solution using non-fluorinated functionalized ionic liquids as extraction agents. Sep. Purif. Technol. 2017, 172, 473−479. (8) Scopel, R.; da Silva, C. F.; Lucas, A. M.; Garcez, J. J.; do Espirito Santo, A. T.; Almeida, R. N.; Cassel, E.; Vargas, R. M. Fluid phase equilibria and mass transfer studies applied to supercritical fluid extraction of Illicium verum volatile oil. Fluid Phase Equilib. 2016, 417, 203−211. (9) Raghavarao, K. S. M. S.; Ranganathan, T. V.; Srinivas, N. D.; Barhate, R. S. Aqueous two phase extraction−an environmentally benign technique. Clean Technol. Environ. Policy 2003, 5, 136−141. (10) Hatti-Kaul, R. Aqueous Two-Phase Systems: Methods and Protocols (Methods in Biotechnology), 1st ed.; Humana Press: Totowa, NJ, 2000. (11) Huddleston, J.; Abelaira, J. C.; Wang, R.; Lyddiatt, A. Protein partition between the different phases comprising poly (ethylene glycol)-salt aqueous two-phase systems, hydrophobic interaction chromatography and precipitation: a generic description in terms of salting-out effects. J. Chromatogr., Biomed. Appl. 1996, 680, 31−41. (12) Xavier, L.; Freire, M. S.; Vidal-Tato, I.; Gonzalez-Alvarez, J. Aqueous two-phase systems for the extraction of phenolic compounds from eucalyptus (Eucalyptus globulus) wood industrial wastes. J. Chem. Technol. Biotechnol. 2014, 89, 1772−1778. (13) Maciel, M. d. H. C.; Ottoni, C. A.; Herculano, P. N.; Porto, T. S.; Porto, A. L.; Santos, C.; Lima, N.; Moreira, K. A.; Souza-Motta, C. Purification of polygalacturonases produced by Aspergillus niger using an aqueous two-phase system. Fluid Phase Equilib. 2014, 371, 125− 130. (14) Zvarova, T. I.; Shkinev, V. M.; Vorob’eva, G. A.; Spivakov, B. Y.; Zolotov, Y. A. Liquid-liquid extraction in the absence of usual organic solvents: Application of two-phase aqueous systems based on a water-soluble polymer. Microchim. Acta 1984, 84, 449−458. (15) Sosa, F. H. B.; de Araujo Sampaio, D.; Farias, F. O.; Bonassoli, A. B. G.; Igarashi-Mafra, L.; Mafra, M. R. Measurement and correlation of phase equilibria in aqueous two-phase systems containing polyethyleneglycol (2 000, 4 000, and 6 000) and sulfate salts (manganese sulfate and copper sulfate) at different temperatures (298.15, 318.15, and 338.15 K). Fluid Phase Equilib. 2017, 449, 68− 75. (16) Freire, M. G.; Claudio, A. F. M.; Araujo, J. M. M.; Coutinho, J. A. P.; Marrucho, I. M.; Lopes, J. C.; Rebelo, L. P. N. Aqueous biphasic systems: a boost brought about by using ionic liquids. Chem. Soc. Rev. 2012, 41, 4966−4995. (17) de Araujo Sampaio, D.; Sosa, F. H. B.; Martins, A. D.; Mafra, L. I.; Yamamoto, C. I.; de Souza, M. O.; de Castilhos, F.; Mafra, M. R. Assessment of Sodium Salt Anions (SO2−4 and NO3−) Influence on Caffeine Partitioning in Polyethylene Glycol and 1-Butyl-3-Methylimidazolium Tetrafluoroborate Based ATPS. J. Solution Chem. 2016, 45, 1857−1878. (18) Farias, F. O.; Sosa, F. H. B.; Igarashi-Mafra, L.; Coutinho, J. A. P.; Mafra, M. R. Study of the pseudo-ternary aqueous two-phase systems of deep eutectic solvent (choline chloride:sugars) + KH2PO 4w+ater. Fluid Phase Equilib. 2017, 448, 143−151. (19) Wang, Y.; Mao, Y.; Han, J.; Liu, Y.; Yan, Y. Liquid-Liquid Equilibrium of Potassium Phosphate/Potassium Citrate/Sodium Citrate + Ethanol Aqueous Two-Phase Systems at (298.15 and 313.15) K and Correlation. J. Chem. Eng. Data 2010, 55, 5621−5626. (20) Lu, Y.; Hao, T.; Hu, S.; Han, J.; Tan, Z.; Yan, Y. Measurement and correlation of phase diagram data for acetone and sulfate aqueous two-phase systems at different temperatures. Thermochim. Acta 2013, 568, 209−217. (21) Wang, Y.; Yan, Y.; Hu, S.; Han, J.; Xu, X. Phase Diagrams of Ammonium Sulfate + Ethanol/1-Propanol/2-Propanol W+ater Aqueous Two-Phase Systems at 298.15 K and Correlation. J. Chem. Eng. Data 2010, 55, 876−881. (22) Fu, H.; Yang, S.-T.; Xiu, Z. Phase separation in a salting-out extraction system of ethanol−ammonium sulfate. Sep. Purif. Technol. 2015, 148, 32−37.

(23) Sanglard, M. G.; Farias, F. O.; Sosa, F. H. B.; dos Santos, T. P. M.; Mafra, L. I.; Mafra, M. R. Measurement and correlation of aqueous biphasic systems composed of alcohol (1-propanol/2propanol/tert-butanol) + (NH)4S2O + 4HO2 at 298 K and a textile dye partition. Fluid Phase Equilib. 2018, 466, 7−13. (24) Aniszewski, T. Alkaloids. Secrets of Life, 1st ed.; Alkaloids: Chemical and Biological Perspectives; Elsevier Science, 2007. (25) Yang, Y.; Cheng, J.; Garamus, V. M.; Li, N.; Zou, A. Preparation of an Environmentally Friendly Formulation of the Insecticide Nicotine Hydrochloride through Encapsulation in Chitosan/Tripolyphosphate Nanoparticles. J. Agric. Food Chem. 2018, 66, 1067−1074. (26) Flood, P.; Damaj, M. I. Nicotine is out: nicotinic agonists may have utility as analgesics. Anesth. Analg. 2014, 119, 232. (27) Kyte, S. L.; Toma, W.; Bagdas, D.; Meade, J. A.; Schurman, L. D.; Lichtman, A. H.; Chen, Z.-J.; Fabbro, E. D.; Fang, X.; Bigbee, J. W.; Damaj, M. I.; Gewirtz, D. A. Nicotine Prevents and Reverses Paclitaxel-Induced Mechanical Allodynia in a Mouse Model of CIPN. J. Pharmacol. Exp. Ther. 2018, 364, 110−119. (28) Dobrowska, J. S.; Erarpat, S.; Chormey, D. S.; Pyrzynska, K.; Bakirdere, S. A Novel Liquid-Liquid Extraction for the Determination of Nicotine in Tap Water, Wastewater, and Saliva at Trace Levels by GC-MS. J. AOAC Int. 2016, 99, 806−812. (29) Burke, T. M.; Markwald, R. R.; McHill, A. W.; Chinoy, E. D.; Snider, J. A.; Bessman, S. C.; Jung, C. M.; O’Neill, J. S.; Wright, K. P. Effects of caffeine on the human circadian clock in vivo and in vitro. Sci. Transl. Med. 2015, 7, 1−9. (30) Rath, P.; Nardiello, C.; Morty, R. E. A new target for caffeine in the developing lung: endoplasmic reticulum stress? American Journal of Physiology-Lung Cellular and Molecular Physiology 2017, 313, L659− L663. (31) Harvanko, A. M.; Derbyshire, K. L.; Schreiber, L. R. N.; Grant, J. E. The effect of self-regulated caffeine use on cognition in young adults. Hum. Psychopharmacol. 2015, 30, 123−130. (32) Souza, D. B.; Coso, J. D.; Casonatto, J.; Polito, M. D. Acute effects of caffeine-containing energy drinks on physical performance: a systematic review and meta-analysis. Eur. J. Nutr. 2017, 56, 13−27. (33) Lane, S.; Palmer, J.; Christie, B.; Ehlting, J.; Le, C. Can Cold Brew Coffee Be Convenient? A Pilot Study For Caffeine Content in Cold Brew Coffee Concentrate Using High Performance Liquid Chromatography. Arbutus Review 2017, 8, 15−23. (34) Hernández-Marín, N. Y.; Lobato-Calleros, C.; RománGuerrero, A.; Alvarez-Ramirez, J.; Vernon-Carter, E. J. Physical properties and release behaviour of caffeine multiple emulsions stabilised by binary or ternary biopolymer soluble complexes under acid, bile and yogurt storage conditions. Food Hydrocolloids 2016, 58, 42−48. (35) Fischer, M.; Jefferies, T. M. Optimization of Nicotine Extraction from Tobacco Using Supercritical Fluid Technology with Dynamic Extraction Modeling. J. Agric. Food Chem. 1996, 44, 1258− 1264. (36) Rincón, J.; Lucas, A. D.; García, M. A.; García, A.; Alvarez, A.; Carnicer, A. Preliminary Study on the Supercritical Carbon Dioxide Extraction of Nicotine from Tobacco Wastes. Sep. Sci. Technol. 1998, 33, 411−423. (37) Bahar, B.; Pelvan, E.; Hasbay, I.;̇ Alasalvar, C. Decaffeinated black tea: Process optimization and phenolic profiles. J. Supercrit. Fluids 2013, 82, 116−121. (38) Tello, J.; Viguera, M.; Calvo, L. Extraction of caffeine from Robusta coffee (Coffea canephora var. Robusta) husks using supercritical carbon dioxide. J. Supercrit. Fluids 2011, 59, 53−60. (39) Millen, D. L. C.; Murphy, W. R. Countercurrent extraction of nicotine from tobacco juice. Ind. Eng. Chem. Res. 1993, 32, 3056− 3060. (40) Mulyadi, A. F.; Wijana, S.; Wahyudi, A. S. Optimization of Nicotine Extraction In Tobacco Leaf (Nicotiana tabacum L.): (Study: Comparison of Ether and Petroleum Ether). The International Conference on Chemical Engineering UNPAR 2013. H



Article

(41) Gadkari, P. V.; Kadimi, U. S.; Balaraman, M. Catechin concentrates of garden tea leaves (Camellia sinensis L.): extraction/ isolation and evaluation of chemical composition. J. Sci. Food Agric. 2014, 94, 2921−2928. (42) Bi, W.; Zhou, J.; Row, K. H. Decaffeination of coffee bean waste by solid-liquid extraction. Korean J. Chem. Eng. 2011, 28, 221−224. (43) Rito-Palomares, M.; Benavides, J. Aqueous Two-Phase Systems for Bioprocess Development for the Recovery of Biological Products, 1st ed.; Food Engineering Series; Springer International Publishing: Gewerbestrasse: Cham, Switzerland, 2017; Vol. 11, p 6330. (44) Merchuk, J. C.; Andrews, B. A.; Asenjo, J. A. Aqueous twophase systems for protein separation: Studies on phase inversion. J. Chromatogr., Biomed. Appl. 1998, 711, 285−293. (45) Zaslavsky, B. Y. Aqueous two-phase partitioning: physical chemistry and bioanalytical applications; M. Dekker: New York, Basel, Oxford, 1995. (46) Reis, I. A. O.; Campos, A. F.; Santos, P. H. S.; Santos, S. B.; Soares, C. M. F.; Lima, Á . S. Potassium Phosphate Salts-Based Aqueous Two-Phase Systems Applied in the Extraction of Gallic Acid from Guava. Sep. Sci. Technol. 2015, 50, 520−528. (47) Katayama, H.; Miyahara, M. Liquid-Liquid Phase Equilibria of (Ethanol or Methanol + Water) Containing either Dipotassium Hydrogen Phosphate or Sodium Dihydrogen Phosphate. J. Chem. Eng. Data 2006, 51, 914−918. (48) Liu, Y.; qi Feng, Y.; Zhao, Y. Liquid-Liquid Equilibrium of Various Aqueous Two-Phase Systems: Experiment and Correlation. J. Chem. Eng. Data 2013, 58, 2775−2784. (49) Gerlach, T.; Smirnova, I. Liquid-Liquid Equilibria of Quaternary Systems Composed of 1,3-Propanediol, Short-Chain Alcohol, Water, and Salt. J. Chem. Eng. Data 2016, 61, 3548−3558. (50) Zafarani-Moattar, M. T.; Banisaeid, S.; Beirami, M. A. S. Phase Diagrams of Some Aliphatic Alcohols + Potassium or Sodium Citrate W+ater at 25 °C. J. Chem. Eng. Data 2005, 50, 1409−1413. (51) Salabat, A.; Hashemi, M. Temperature Effect on the LiquidLiquid Equilibria for Some Aliphatic Alcohols + Water K+CO2 S3ystems. J. Chem. Eng. Data 2006, 51, 1194−1197. (52) Shahriari, S.; Neves, C. M. S. S.; Freire, M. G.; Coutinho, J. A. P. Role of the Hofmeister Series in the Formation of Ionic-LiquidBased Aqueous Biphasic Systems. J. Phys. Chem. B 2012, 116, 7252− 7258. (53) Renon, H.; Prausnitz, J. M. Local compositions in thermodynamic excess functions for liquid mixtures. AIChE J. 1968, 14, 135−144. (54) Sé, R.; Aznar, M. Thermodynamic modelling of phase equilibrium for water + poly(Ethylene glycol) s+alt aqueous twophase systems. Braz. J. Chem. Eng. 2002, 19, 255−266. (55) Nelder, J. A.; Mead, R. A simplex method for function minimization. computer journal 1965, 7, 308−313. (56) Pereira, J. F. B.; Ventura, S. P. M.; e Silva, F. A.; Shahriari, S.; Freire, M. G.; Coutinho, J. A. P. Aqueous biphasic systems composed of ionic liquids and polymers: A platform for the purification of biomolecules. Sep. Purif. Technol. 2013, 113, 83−89.

I


Salt Effect on Ethanol-Based Aqueous Biphasic Systems Applied to

Recommend Documents