Influence of Different Additives on the Clouding Nature and

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

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Influence of Different Additives on the Clouding Nature and Thermodynamic Behavior of Tween 80 Solution in the Absence and Presence of the Amikacin Sulfate Drug Muhammad Akhlaqur Rahman Khan,† Md. Ruhul Amin,† Marzia Rahman,† Malik Abdul Rub,†,‡ Md. Anamul Hoque,*,† Mohammed Abdullah Khan,† and Abdullah M. Asiri†,‡ †

Department of Chemistry, Jahangirnagar University, Savar, Dhaka- 1342, Bangladesh Chemistry Department, Faculty of Science, King Abdulaziz University, Jeddah-21589, Saudi Arabia

‡

J. Chem. Eng. Data Downloaded from pubs.acs.org by IOWA STATE UNIV on 02/05/19. For personal use only.

S Supporting Information *

ABSTRACT: Herein, the cloud-point (CP) measurements of a nonionic surfaceactive agent named Tween 80 [poly(oxyethylene) (20) sorbitanmonooleate; Tw 80] were carried out in this study in the absence and attendance of an amikacin sulfate (AS) drug/(AS+ inorganic electrolyte (NaCl, NaNO3 and Na2SO4)). AS drug has been utilized to treat or prevent a wide range of bacterial infections. The measured values of CP in the aqueous phase for Tw 80 were observed in decreasing fashion with an increase in the concentration of surfactant. The obtained values of CP for Tw 80 solution were also noticed to decrease with increasing drug concentration. The determined CP values for (surfactant + drug) mixture were observed to decrease for the electrolytes’ participation with respect to their nonparticipation, and the presence of electrolytes (sodium salts) in declining CP measurement was recorded and followed the order NaCl > NaNO3 > Na2SO4. The ΔGc0 values are found to be positive that denotes the character of clouding is nonspontaneous. The ΔHc0 and ΔSc0 calculations were shown to be negative for the system studied except for the (Tw 80 + H2O) phase. The negative values of ΔHc0 and ΔSc0 decreased with the increment of electrolyte concentration. The thermodynamic parameters of transfer for the studied system were also evaluated and are illustrated in detail. why it changes the environment of the micelle.9,10 In aqueous solution, the formation of turbidity/cloudiness cause the differentiation into the two separate phases and introduces certain disadvantages into its utilization. The CP value that is known for nonionic surfactants is important because formulations at temperatures significantly higher than the CP will cause an unstable state and will lead to phase separation. This observed neutral (nonionic) surfactant is very potent below and near the CP value of that particular surface-active agent.10 For this reason, this is of essential significance to calculating the performance of several item additions to the cloud point of a nonionic surface tension reducing agent. The effects of diverse electrolytes on the clouding phenomenon of Triton X-100 with sodium lauryl sulfate (SDS) were assessed by Panchal et al.9 In their report, they claim that SDS causes an increment in the CP value for Triton X100 and upon addition of electrolytes decrease the values of the cloud point (CP). The influence of glycol oligomers and triblock polymers on the clouding nature of Tw 80 was evaluated by Mahajan et al.10 The measured outcome shows that the items

1. INTRODUCTION Poly(oxyethylene)-based surface-active agents have largely been utilized as detergents and emulsifiers for several decades.1−3 Nonionic surface-active agent solutions are notably different from ionic surfactant solutions. A distinct property of nonionic surfactant solution is acute phase separation with the application of heat to the solution. This phase division occurs at a definite temperature, and this is called the cloud point (CP).4 The equilibrium of interaction within the aquaphilic and lyophobic is a vital force for constructing the cloud point.5 The numerical value of the cloud point (CP) for nonionic surfactants is notably sensitive to the presence of any additive. Additions of any element/compounds (organic solute, dye, drug, electrolyte, salts, etc.) to the system, even at very low concentration, cause the change of CP values. Because the additives specifically change the CP of the nonionic surfactant, this is a tool for using the item according to the requirement of various conditions and purposes by a convenient increase or decrease in the number of additives. The use of nonionic surfactants in industrial and pharmaceutical formulations is notable, and in the solid medium, the extraction of a number of types of different organic compounds is accomplished using hydrated phases.6−8 The clouding properties of nonionic surfactants are highly influenced by the addition of different additives to the solution, and this is © XXXX American Chemical Society

Received: October 6, 2018 Accepted: January 7, 2019

A

DOI: 10.1021/acs.jced.8b00897 J. Chem. Eng. Data XXXX, XXX, XXX−XXX

Journal of Chemical & Engineering Data

Article

influence the clouding nature of Tw 80. It shows an increase in the duplicating portion of polymeric glycol additives and the hydrophobic/hydrophilic proportion in the triblock polymers that lowers the cloud point of Tween-80. The result studied for the effect of PVSA (polyvinyl sulfonic acid) in the thermodynamics of phase accumulation of nonionic surfactants was determined by Jadhav et al.11 It was observed that the Tw 80 CP value decreased with the increase in the concentration of Tw 80 as well as with the increase in PVSA concentration. In our previous work, we performed a study of the effect of the addition different ions on the CP of Tw 80 and TX-100 solution and discussed the thermodynamic behavior.12,13 Though a literature evaluation provides the results of numerous studies on the phase separation of nonionic surface tension reducing agents, more studies are still essential for new system requirements.1,7,14 AS is an aminoglycoside antibiotic drug which is used for the treatment and prevention of a wide range of bacterial diseases in the form of injection (into either a vein or muscle). In particular, this is used to treat joints, the intraabdominal region, meningitis, pneumonia, sepsis, and urinary tract infections.15 Tw 80, a nonionic surfactant, is utilized as an emulsifier in cosmetics, pharmaceuticals, and food products. In selected foods, the use of Tw 80 (up to 1%) is approved by the U.S. Food and Drug Administration.16 Keeping all of these matters in mind, we performed a study on the clouding nature of Tw 80 (Scheme 1) under water-soluble

Table 1. Source and Purity of the Compounds Employed in This Worka material Tw 80 AS NaCl Na2SO4 NaNO3

source/obtained from Incepta Pharmaceuticals Ltd. Bangladesh General Pharmaceuticals Ltd. Merck, Mumbai India Merck, Mumbai, India Merck, Mumbai, India

purity

CAS number

MW (g/mol)

98%

9005-65-6

1310

98%

37517-28-5

585.60

99% 99% 99.5%

7647-14-5 7757-82-6 7631-99-4

58.44 142.04 84.9947

a Distilled deionized H2O was used to prepare all solutions, and H2O has a specific conductivity of 1−1.6 (μS/cm) (depending on the solution temperature). Tw 80 is freely soluble in water, and the Tw 80 solutions having different desired concentrations are easily prepared in water without providing any pressure/temperature.

made water bath was employed for the heating setup (continuously stirred at a velocity of ∼400 rpm to sustain the heat supply throughout, along with the steady temperature). The employed solution heated the sample gradually, and we observed that the temperature reached only a few degrees less than the approximate CP. When the temperature exceeded the cloud point, it prevented the solution from becoming cooler than the temperature of the CP and thereafter was increased once more to guarantee the reproducibility of the observation. A Teflon cap was employed to tighten the top of the pyrex glass tube to stop evaporation physically. Investigations were performed at least three times, and three average values of three consequent temperature measurements for the appearance and disappearance of clouding were taken as CP. A lamp was also employed for the evaluation of the cloud point. It was positioned close to the Pyrex glass tube for fine visualization along with confirming the accurate temperature of the cloud point. The uncertainty in the CP measurements was within ±0.1 K.

Scheme 1. Molecular Structure of Tw 80

3. RESULTS AND DISCUSSION 3.1. CP Values of Tw 80 in Water and Drug/(Drug + Salt) Solution. Measurements of the cloud point for surfaceactive agents can be used as its solubility because its boundary area is isolated at a temperature above the CP. The solvated water molecule (H2O) of the surfactant left the company of other water molecules and remained separated from the solution. Within the concentration range of 1 × 10−3 to 10 × 10−3 (mol/kg), the CP of solutions was measured in water, and the CP values in aqueous solutions are presented in Table S1 (Supporting Information). For Tw 80 aqueous (water) solution having a concentration 1.02 × 10−3 (mol/kg), the CP value is 365.07 K. Hoque et al.13 noticed the value of CP 365.35 K for 1.02 mM Tw 80 in water and the CP value of 364.25 K for 0.763 mM Tw 80 in water.14 Jadhav et al.11 found the value of CP 364.25 K for 0.763 mM Tw 80 solution in water. Mahajan et al.10 measured the CP value of 368.25 K for 0.1 mM Tw 80 in the aqueous phase (water). The CP values were found to decrease with increasing surfactant concentration in this study. Figure S1 (Supporting Information) also indicate values of Tw 80 as the reason for its content in the H2O environment. This observation is similar to the literature reports.11−13 This kind of outcome is expected because of the decreasing hydration of the oxyethylene oxygens aquaphilic group with decreasing cloud-point value. It has a high probability of a declining accumulation number and inter-

conditions and in the presence of AS drug/(AS + electrolyte) composite systems. Thermodynamic quantities such as ΔGc0, ΔHc0, and ΔSc0 and also some thermodynamic parameters of transfer with the clouding process of Tw 80 were also determined and are discussed in detail in aqueous solution in the presence of different additives.

2. EXPERIMENTAL SECTION The samples in Table 1 were used in this study as received. Tw 80 solution was prepared in a water solution of AS or (AS + electrolyte). The prepared solution was stirred for more than 40 min to reach the proper state of saturation. The concentration of surfactant was taken depending on the cmc values of Tw 80, not on the cloud-point (CP) values of Tw 80. The concentration that was used was greater than the cmc values of Tw 80 so that there was a scope to detect the clouding phenomenon for a large concentration range. Cloud-point values of the solutions were made by visual observation of the sudden appearance/disappearance of turbidity during the heating of the Tw 80 solution.12,13 In the tube made of pyrex glass, a fixed amount (volume) of Tw 80 solutions in water/(surfactant + AS) in combination and noncombination with different ionic elements were gathered and keep in a constant-temperature heating setup. The manually B



Article

Mechanisms of two kinds are engaged in explaining the ion’s place in the Hofmeister series.16 Ordinarily, the technique involved seemed to be related to the ability of ions to change the bonding (H-bonding) arrangement of water. Ions that work as water structure makers are represented on the left of the Hofmeister series (such as a sulfate ion). Furthermore, these ions cause entropy loss, and the result is the cessation of the water molecule. The result is that the salted-out anions on the nonionic surfactant participate in the solutions. Ions located on the right side of the Hofmeister series are water molecule structure breakers, and these ions possess high polarity, which directs the interruption of self-aggregated water molecules. These ions further release particular water molecules which have the ability to create hydrogen bonds with ether groups of surface-active agent molecule, which view the salting in effects happens. 3.2. Thermodynamic Parameters of the Clouding Phenomenon. Thermodynamic quantities such as the standard free energy (ΔGc0), enthalpy (ΔHc0), and entropy (ΔSc0) changes for the process of clouding were determined, allowing for the solubility limit at the temperature of clouding by utilizing the below-mentioned equations.12,13,22−25

micellar interaction accompanied by small micellar integration in the solution at CP temperature that causes the formation of turbidity and creates two liquid phases.17 When the concentration of Tw 80 in the solution is increased up to 10 × 10−3 (mol/kg), the micelles have smaller dimensions and form transformation occurs as a sphere rather than as a disk. This transition in shape seems to cause a lowering of the surface area of the micelle, which causes a decrease in hydration and an increase in the CP of solution.18,19 In this study, the CP value of Tw 80 was also investigated along with the addition of an AS drug. The CP values for concentrations of 1.53 × 10−3 (mol/kg), 3.05 × 10−3 (mol/kg), and 6.11 × 10−3 (mol/kg) of Tw 80 mixtures having different drug contents are presented in Figure 1 as well as in Table S2

ΔGc 0 = −RT ln Xs

(1)

ΔHc 0 = RT 2(∂ ln Xs)/∂T

(2)

ΔSc 0 = (ΔHc 0 − ΔGc 0)/T

(3)

Here, Xs represents the mole fractional concentration of additive at CP, where R and T are called the universal gas constant and temperature. The cloud points rely on the fact that Xs that can be shown as a regular parabolic curve using the relation26−29

Figure 1. Graph of CP against AS content for (■) 1.53 (mmol/kg), (▲) 3.05 (mmol/kg), and (◀) 6.11 (mmol/kg) Tw 80 solutions.

(Supporting Information). With increasing drug concentration, the values of CP for Tw 80 solutions were decreased. Such suppression of the CP of the surface-active agent solution is the cause for the addition of drug, as also documented in the literature.13 The reason behind the incident may be the discharge of water (H2O) from surfactant upon addition of drug and may cause the Tw 80 micelles to approach each other more closely, which is why the CP of the surfactant decreases. The effect of sodium salts such as NaCl, NaNO3, and Na2SO4 on the cloud point of 1.05 × 10−3 (mol/kg) and 2.09 × 10−3 (mol/kg) solutions of AS solutions having 3.05 × 10−3 (mol/kg) drug was also considered, and the outcomes observed are given in Figure 2 and Table S3 (Supporting Information). The charge of the ion (co/counter) does play a significant role in the process of clouding. The CP values were found to change upon the addition of salts, and they were observed to decrease in the presence of inorganic salts compared to their values in pure aqueous media. It was noticed that the CP declines with increasing concentrations of electrolytes, and the order is NaCl < NaNO3: < Na2SO4. In the literature review, it was also noticed that the CP values of Triton X-100 decline more, in a sharp style in Na2SO4 solution in comparison to those in the solution of NaCl.13,20 This kind of decline in the CP value of Triton X-100 was also observed by Heusch.21 There is no specific reason to employ these specific salts in the current study. Because different salts such as sodium, nitrate, chloride, and sulfate might be found in the biological fluids of human beings, their presence may have an influence on the aggregation/phase separation phenomena of surfactants, which are usually used as drug carriers.

ln Xs = A + BT + CT 2

(4)

Regression analysis of the least-squares process is used for the determination of constants A, B, and C. A graph of the parabolic curve for plot ln Xs versus T (CP), which is used to calculate the enthalpy change of the method of clouding, is depicted in Figure 3. All values of A, B, and C are enlisted in Supporting Information in Table S4. The enthalpy of clouding is then determined by combining eqs 4 and 2: ΔHc 0 = RT 2[B + 2CT ]

(5)

The thermodynamic quantities for clean Tw 80 in H2O are listed in Table 2. The calculation of the standard free energy (ΔGc0) is found to be positive, which indicates that the process was nonspontaneous in nature. The positive values of ΔGc0 declined by the increment of the content of Tw 80 in the water medium. Clouding formed by liberating their solvated water molecule and separating it from the solution, and this event is called the solubility limit.30 When it reaches CP the maximum solubility at that time, the phases transform from a homogeneous to a heterogeneous phase. The ΔHc0 and ΔSc0 values are found to be negative in all cases except for the higher values of Tw 80 concentration in aqueous media. These negative values decrease with enhanced Tw 80 content in a water environment. Both positive values of enthalpies and entropies are characteristics of hydrophobic bonding, whereas negative values indicate hydrogen bonding and electrostatic interacC



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Figure 2. Plots of CP vs sodium salt (NaCl, NaNO3, and Na2SO4) concentrations of (■) 1.05 × 10−3 (mol/kg) and (▲) 2.09 × 10−3 (mol/kg) amikacin solution for (amikacin + Tw 80) systems.

Table 2. Values of the Thermodynamic Parameters of the Clouding Process for Pure Tw 80 in Watera

Figure 3. Plot of ln Xs vs Tcp of the 1.53 × 10−3 (mol/kg) Tw 80 solution in the presence of different concentrations of amikacin sulfate used to calculate ΔHc0.

cTw 80

ΔGc0

ΔHc0 × 10−2

ΔSc0 × 10−2

(mmol/kg)

(kJ/mol)

(kJ/mol)

(J/mol·K)

0.38 0.76 1.53 2.29 3.05 3.82 4.58 5.34 6.11 6.87 7.63

29.1 26.88 24.7 23.44 22.48 21.75 21.16 20.62 20.15 19.71 19.34

−5.66 −4.76 −4.11 −3.74 −2.97 −2.39 −1.96 −1.2 −0.51 0.25 0.84

−1.63 −1.38 −1.2 −1.1 −0.89 −0.73 −0.61 −0.39 −0.2 0.02 0.18

a Standard uncertainties (u) are u(T) = 0.1 K and u(c) = 0.02 (mmol/ kg). Relative standard uncertainties (ur) are ur(ΔGc0) = ±3%, u(ΔHc0) = ±3%, and ur(ΔSc0) = ±4% .

tions.31,32 The negative ΔHc0 and ΔSc0 values define that the clouding is directed entirely by the enthalpy contribution. For (AS + surfactant) system in watery environment, the ΔGc0 value of surfactant solutions (1.53 × 10−3 to 6.11 × 10−3 (mol/kg)) having various AS concentrations are positive which indicates the processes are nonspontaneous. The positive values of ΔGc0 are decreased with increasing the concentration of amikacin sulfates in every scenarios, which indicates that the method turn to shift toward spontaneity with enhance of AS content. For 1.53 × 10−3 (mol/kg), 3.05 × 10−3 (mol/kg), and 6.11 × 10−3 (mol/kg) Tw 80 solutions possessing various

concentration of amikacin sulfate, all of the calculated values of ΔHc0 and ΔSc0 are found to be negative. These negative values decrease with the incresing concentration of AS. Rub et al. found negative values of ΔHc0 and ΔSc0 for some amphilic drugs in the presence of Tw 80 and also in the presence of other additive mixed systems.30,33−36 Negative ΔHc0 and ΔSc0 were also noticed earlier with respect to the phase-separation characteristics of many nonionic surfactant systems in water and in the presence of sodium chloride.35 The negative ΔHc0 values D



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Table 3. Values of the Thermodynamic Parameters of Clouding of 1.53 (mmol/kg), 3.05 (mmol/kg), and 6.11 (mmol/kg) Tw 80 and the Changing Content of Amikacin Sulfate (mmol/kg) in an Aqueous Mediuma cTW‑80

camikacin

ΔGc0

ΔHc0 × 10−2

ΔSc0 × 10−3

ΔGc,t0

ΔHc,t0 × 10−2

(mmol/kg)

(mmol/kg)

(kJ/mol)

(kJ/mol)

(J/mol·K)

(kJ/mol)

(kJ/mol)

1.53 1.53 1.53 1.53 1.53 1.53 1.53 1.53 3.05 3.05 3.05 3.05 3.05 3.05 3.05 3.05 6.11 6.11 6.11 6.11 6.11 6.11 6.11 6.11

0 0.99 1.99 3.1 4.05 5.01 5.97 7.04 0 1.1 2.02 2.99 3.95 4.98 6.07 7.09 0 1.12 1.98 3.01 4.02 4.97 6.03 7.02

24.7 31.88 29.77 28.38 27.53 26.81 26.27 25.73 22.48 31.12 29.28 28.08 27.21 26.47 25.82 25.32 20.15 30.75 29.07 27.81 26.9 26.22 25.63 25.13

−4.11 −5.47 −4.68 −3.52 −2.64 −1.43 −1.07 −0.26 −2.97 −4.94 −4.02 −3.33 −2.68 −1.9 −1.12 −0.51 −0.51 −5.65 −4.91 −4.13 −2.93 −1.94 −1.37 −0.53

−1.2 −1.65 −1.42 −1.09 −0.84 −0.49 −0.38 −0.15 −0.89 −1.52 −1.25 −1.05 −0.86 −0.63 −0.4 −0.22 −0.2 −1.74 −1.52 −1.29 −0.94 −0.65 −0.48 −0.23

7.18 5.07 3.68 2.83 2.11 1.57 1.03

−1.36 −0.57 0.59 1.47 2.68 3.04 3.86

8.64 6.79 5.59 4.72 3.98 3.33 2.83

−1.97 −1.05 −0.36 0.29 1.07 1.85 2.46

10.61 8.92 7.67 6.75 6.07 5.48 4.99

−5.14 −4.4 −3.61 −2.42 −1.42 −0.86 −0.02

Standard uncertainties (u) are u(T) = 0.1 K and u(c) = 0.02 (mmol/kg). Relative standard uncertainties (ur) are ur(ΔGc0) = ±3%, u(ΔHc0) = ±3%, ur(ΔSc0) = ±4%, ur(ΔGc,t0) = ±4%, and ur(ΔHc,t0) = ±4% a

in the presence of electrolyte in the current study. It can be described as the disorderness of water molecule structure in the area of hydrophobic alkyl tails of amphiphilic molecules for positive values of ΔHc0.39 The negative sign integer for ΔHc0 also indicates the significance of London dispersion forces as an attractive energy of accumulation for (AS + Tw 80) mixed systems.40,41 However, the positive sign of ΔHc0 implies the rupturing of arranged water molecule in the hydrophobic region of the molecules.42,43 The negative along with positive ΔHc0 values were also achieved in the case of phase separation of surfactant systems.44,45 In parallel to this, negative as well as positive ΔHc0 values were also attained in case of mixed micellization of the drug−additives mixture.46−49 The calculations of ΔGc,t0 and ΔHc,t0 for the clouding process from the water medium to the medium with salts are gathered using the below mentioned equations.50−52

indicate an exothermic process. The CP values of solutions in a nonionic surfactant system remained in a disordered state. The thermodynamic indices of Tw 80 solution in an aqueous medium and in the presence of (amikacin sulfate + electrolytes) were measured, and the values achieved for the thermodynamic characteristics are presented in Tables 3 and 4. In all of these cases, the ln Xs versus T plots are depicted in Figures S2−S5 (Supporting Information) and are shown to be nonlinear. The values of ΔGc0 for both 1.05 × 10−3 (mol/kg) and 2.09 × 10−3 (mol/kg) solutions of amikacin sulfate having a concentration 3.05 × 10−3 (mol/kg) Tw 80 and various sodium salt concentrations are observed to be positive, meaning that the process is still nonspontaneous. The positive values of ΔGc0 decline with the increasing concentration of all salts used for both 1.05 × 10−3 (mol/kg) and 2.09 × 10−3 (mol/kg) solutions of amikacin sulfate, which describes that the method moves toward spontaneity with increasing electrolyte concentration. The positive ΔGc0 values are noticed to be higher in the range of lower electrolyte concentration than in the water environment. The calculated values of ΔHc0 and ΔSc0 obtained are negative in all cases for both 1.05 × 10−3 (mol/kg) and 2.09 × 10−3 (mol/ kg) solutions of amikacin sulfate having a concentration of 3.05 (mmol/kg) Tw 80 and for different sodium salts except the higher percentage of sodium chloride salt. It reduces the negative values of ΔHc0 and ΔSc0 with enhanced electrolyte content, and at higher content, the sign changes from negative to positive (Table 4). A negative value for ΔHc0 indicates the hydration of water molecules of the hydrophilic headgroup compared to the alteration of the water molecules’ arrangement of the hydrophobic alkyl chains of amphilic monomers.13,37−39 Both ΔHc0 and ΔSc0 values control the ΔGc0 at the CP of Tw 80

ΔGc, t 0 = ΔGc 0(aq of additive) − ΔGc 0(aq)

(6)

ΔHc, t 0 = ΔHc 0(aq of additive) − ΔHc 0(aq)

(7)

ΔG0c,t

The values of (free energy of transfer) decrease with enhanced concentrations of AS and electrolytes. For all drug contents, calculated ΔG0c,t (free energy of transfer) values (presented in Table 3) are positive in sign. However, ΔH0c,t (transfer of enthalpy) changes from negative to positive except in the case of a (surfactant + amikacin sulfate) mixture having 6.11 × 10−3 (mol/kg) Tw 80 in the absence of salt, and their values increases with increases in drug and salt concentrations. Negative transfers of enthalpies of micellization were defined by the migration of sodium chloride and amino acids from water solution to urea solution.53,54 E



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Table 4. Values of the Thermodynamic Parameters of Clouding for (AS+Tw 80) Mixtures having 3.05 (mmol/kg) Tw 80 and Different Concentrations of AS (Drug) in a (Water + Salt) Mediuma cdrug

csalts

ΔGc0

(mmol/kg)

(mmol/kg)

(kJ/mol)

1.05 1.05 1.05 1.05 1.05 2.09 2.09 2.09 2.09 2.09

0.99 1.98 3.02 3.97 5.05 1.04 1.99 3.01 3.99 5.02

31.03 28.99 27.74 26.88 26.08 30.82 28.88 27.66 26.8 26.05

1.01 1.01 1.01 1.01 1.01 2.03 2.03 2.03 2.03 2.03

0.99 1.99 3.02 3.98 5.02 1.04 1.98 3.02 4.02 5.02

31.03 28.92 27.64 26.79 26.02 30.83 28.87 27.56 26.61 25.87

1.03 1.03 1.03 1.03 1.03 2.05 2.05 2.05 2.05 2.05

0.98 1.99 3.01 3.99 5.04 1.03 1.98 3.01 3.97 5.01

30.72 28.64 27.41 26.56 25.81 30.51 28.56 27.34 26.46 25.76

ΔHc0 × 10−2

ΔSc0 × 10−3

ΔG0c,t

ΔH0c,t × 10−2

(kJ/mol)

(J/mol ·K)

(kJ/mol)

(kJ/mol)

−2.47 −1.92 −1.52 −0.85 0.01 −1.98 −1.46 −1.16 −0.82 −0.23

8.55 6.51 5.26 4.4 3.6 8.34 6.4 5.18 4.32 3.57

−5.14 −3.29 −1.91 0.35 3.26 −3.47 −1.71 −0.68 0.47 2.46

−1.53 −1.18 −0.86 −0.65 −0.27 −1.38 −1.11 −0.86 −0.57 −0.31

8.55 6.44 5.16 4.31 3.54 8.35 6.39 5.08 4.13 3.39

−1.94 −0.74 0.33 1.04 2.31 −1.43 −0.51 0.33 1.33 2.21

−1.99 −1.5 −1.12 −0.75 −0.24 −1.65 −1.28 −1.13 −0.79 −0.64

8.24 6.16 4.93 4.08 3.33 8.03 6.08 4.86 3.98 3.28

−3.43 −1.8 −0.52 0.72 2.42 −2.28 −1.03 −0.55 0.59 1.1

Tween-80-Amikacin-NaCl-H2O −8.11 −6.26 −4.88 −2.62 0.29 −6.44 −4.68 −3.65 −2.5 −0.51 Tween-80-Amikacin-NaNO3-H2O −4.91 −3.71 −2.64 −1.93 −0.66 −4.4 −3.48 −2.64 −1.64 −0.76 Tween-80-Amikacin-Na2SO4-H2O −6.4 −4.77 −3.49 −2.25 −0.55 −5.25 −4 −3.52 −2.38 −1.87

a Standard uncertainties (u) are u(T) = 0.1 K and u(c) = 0.02 (mmol/kg). Relative standard uncertainties (ur) are ur(ΔGc0) = ±3%, u(ΔHc0) = ±3%, ur(ΔSc0) = ±4%, ur(ΔG0c,t) = ±4%, and ur(ΔH0c,t) = ±4%.

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4. CONCLUSIONS

ASSOCIATED CONTENT

S Supporting Information *

This experiment depicts the role of the CP (cloud point) of Tw 80, the nonionic surface active agent, that was estimated in water (aqueous) solution along with different ionic elements (electrolytes) and drugs. Measurements of the CP were made in the aqueous phase and in the presence of additives (Drug/ (electrolytes+drug)). CP values decrease with the addition of electrolytes, and SO42− is the most proficient suppressor of all of the ions used, including monovalent Cl− and NO−3. The thermodynamic indices are also calculated at the cloud point. The ΔHc0 (enthalpy) and ΔSc0 (entropy) calculated values are found to bear a minus sign (negative), which indicates exothermic interactions during clouding among the components. The negative values of ΔHc0and ΔSc0 are observed to decrease with increasing concentration of electrolytes. The result exhibited the presence of exothermic interactions among Tw 80 molecules as well as between Tw 80 and drugs. The free energy of transfer properties of the studied clouding processes were found to be positive in sign.

The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acs.jced.8b00897. Data for the cloud point and thermodynamic parameters of some studied systems (PDF)

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AUTHOR INFORMATION

Corresponding Author

*E-mail: [email protected]. Tel: 880-2-7791045-51, ext 1437. Fax: 880-2-7791052. ORCID

Malik Abdul Rub: 0000-0002-4798-5308 Md. Anamul Hoque: 0000-0002-2609-1815 Abdullah M. Asiri: 0000-0001-7905-3209 Notes

The authors declare no competing financial interest. F



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ACKNOWLEDGMENTS The authors acknowledge General Pharmaceuticals Ltd., Bangladesh, for supplying the standard sample of amikacin sulfate as a gift item to carry out this research.

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