Clouding and Thermodynamic Characteristics of Triton X-100 in the

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

Clouding and Thermodynamic Characteristics of Triton X‑100 in the Presence of Ciprofloxacin Hydrochloride: Influence of Polyols Shamim Mahbub,†,‡ Malik Abdul Rub,§,∥ and Md. Anamul Hoque*,‡ †

Department of Chemistry & Physics, Gono Bishwabidyalay, Savar, Dhaka, 1344, Bangladesh Department of Chemistry, Jahangirnagar University, Savar, Dhaka, 1342, Bangladesh § Chemistry Department, Faculty of Science, King Abdulaziz University, Jeddah, 21589, Saudi Arabia ∥ Center of Excellence for Advanced Materials Research, King Abdulaziz University, Jeddah, 21589, Saudi Arabia Downloaded via UNIV OF GOTHENBURG on August 27, 2019 at 08:01:20 (UTC). See https://pubs.acs.org/sharingguidelines for options on how to legitimately share published articles.

‡

S Supporting Information *

ABSTRACT: Herein, the cloud point (CP) measurement of Triton X-100 (TX100) in aqueous/polyols medium has been performed in the absence/presence of ciprofloxacin hydrochloride (CFH) antibiotic drug and demonstrated in detail. The executed CP values of TX-100 in H2O/polyols were obtained to be decreased with an increase of concentration of TX-100 up to a certain value, and then increased with the further increase of the concentration of TX-100. The CP values were reduced in the presence of CFH in all cases. The obtained CP values of TX-100 were lower in the presence of polyols as compared to that in an aqueous medium and reduced further with the subsequent rise of the polyols concentration. The Gibbs free energy of clouding (ΔG0c ) was positive in all cases. The enthalpy of clouding (ΔH0c ) and entropy of clouding (ΔS0c ) as well as transfer properties of the clouding of TX-100 were evaluated in aqueous/polyols media in the absence/attendance of CFH and discussed thoroughly. The more spontaneous clouding phenomenon in the presence of polyols is indicated by the negative value of free energy of transfer (ΔG0c,tr). The entropy−enthalpy compensation was observed in all cases studied. to permeabilize unfixed/lightly fixed eukaryotic cell membranes.11 It is used in the plating of metal and also in the lysis buffer for the extraction of DNA. The nonionic surfactants show higher solubility in an aqueous medium due to the existence of H-bonding. TX-100 is soluble in water almost in all proportion because of the presence of a great amount of Hbonding with water. With the augmentation of the temperature, these infirm H-bonds break and result in the reduction of the solubility of nonionic surfactants in the aqueous medium, and a cloudy appearance is observed at a certain temperature which is called the cloud point (CP).1,12 The CP is considered the limit of solubility for a nonionic surfactant, and solutions of nonionic surfactants occur as a single-phase at a higher and lower temperature than the CP.13 The knowledge of CP values of nonionic surfactants is important in the liquid− liquid extraction to isolate various compounds such as metal complexes depending on their comparative solubility in two immiscible liquids. The clouding phenomenon of the nonionic surfactants can be illustrated with the help of two circumstances:14,15 (i) micelles of nonionic surfactants proceed up to CP;8 and (ii) the CP implies a critical temperature at which the nonionic micelles are close together, and at temperatures

1. INTRODUCTION Surfactants are unique compounds containing both polar and nonpolar groups in their structure which provide them special solubility properties. This unique molecular structure of the surfactants helps them to reduce the surface/interfacial tension of most solvents and thus increase the solubility of feebly soluble organic compounds.1 Because of a subtle balance of the hydrophilic and hydrophobic interaction of the surfactant, a molecular aggregation is formed2 called micelles. Micelles occur beyond an assured concentration of the surfactant which is known as critical micelle concentration (cmc).3,4 Surfactants are exclusively utilized in cosmetic and detergents preparation and also in various industries as emulsifiers, solubilizers, leveling, and wetting agents. Besides these, in the separation of metal ions, organic molecules, and enzymes, etc. surfactants play a vital role. In pharmaceutical formulations, surfactants are employed as the adept substance in order to solubilize the weekly soluble organic substances, preserving them in the micelle interior.5−8 Surfactant micelles exhibit similar properties such as a biological membrane. We can obtain information about the influence of different additives on the biological membrane by means of investigating the impact of those additives on the surfactant micelles.9,10 TX-100 is extensively used in the extraction of protein/organelles. It is commonly used in the laboratory as a detergent. In the influenza vaccine, TX-100 is one of the common ingredients. It can be employed © XXXX American Chemical Society

Received: June 19, 2019 Accepted: August 5, 2019

A

DOI: 10.1021/acs.jced.9b00579 J. Chem. Eng. Data XXXX, XXX, XXX−XXX

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higher than CP the micelles tend to be insoluble in the aqueous phase. The addition of different types of additives (electrolytes/drugs/alcohols) which can be found to exist in our body can alter the physicochemical properties of surfactants. Thus, the investigation of the impact of these additives on the physiochemical properties of a surfactant is important. In the treatment of different types of bacterial infections such as skin infection,16 bone and joints infections, respiratory tract infections, and urinary tract infections as well as endocarditis, prosthetic joint infection,17 CFH is a broadly employed antibiotic drug. Alauddin et al.13 executed the CP of TX-100 in the presence of aliphatic compound/alcohols. Mudawadkar et al.14 explored phase segregation as well as thermodynamics characteristics of TX-100 in the absence/attendance of several polyvinylpyrrolidones (PVP) and found the CP values to be enhanced slightly from 336 to 340 K with the increment of TX-100 concentration from 1 to 10 wt %. The alteration of CP values of TX-100/TX-100+sodium dodecyl sulfate mixture in aqueous/electrolyte medium was studied by Panchal et al.15 The influence of different electrolytes on the phase differentiation of TX-100/TX-100+levofloxacin hemihydrate drug was investigated by Amin et al.18 Though a large number of studies has been reported in the literature, the clouding phenomenon, as well as thermodynamic properties of TX-100/ TX-100+CFH in polyols medium, has not been studied yet. Considering all facts, we devised our study to observe the clouding characteristic of TX-100 (Scheme 1) in the absence/

Table 1. Provenance, Mass Fraction Purity, and CAS Number of the Compounds Utilized compounds

CAS number

TX-100 glucose fructose ciprofloxacin hydrochloride

9002-93-1 50-99-7 57-48-7 86483-48-9

source Merck (Germany) Merck (Germany) Merck (Germany) Gonoshasthaya Pharmaceuticals Ltd. (Bangladesh)

mass fraction purity 0.99 0.99 0.98 0.98

the entire solutions. Ten milliliters of each target solution (prepared in H2O/glucose/fructose with or without a certain amount of CFH) was placed in a pyrex glass tube and subsequently positioned in a moving water thermostated bath, and the temperature of the solutions was increased slowly. Then the CP of the corresponding systems was executed from visual observation. The temperature at which the cloudiness just appears is termed as CP. The CP value was estimated following the procedure mentioned in the literature.19,20 For certain solution systems, the same mode of action was repeated at least three times, and the mean temperature of six readings (three for the appearance of clouding and three for the disappearance of clouding) was taken as the CP of the corresponding solutions. The correctness of the CP value was about ±0.1 K. All of the calculations in order to estimate different parameters were performed by Microsoft Excel, and the graphical representations were done by Origin 7 software.

Scheme 1. Molecular Design of TX-100

3. RESULT AND DISCUSSION 3.1. Effect of Additives on CP of TX-100. Different physicochemical parameters such as the cmc, micellar shape and size, and micellar aggregation number as well as the clouding phenomenon of surfactants had significant results.1,21 These physicochemical properties of the surfactants can be altered with the addition of various additives such as electrolytes, drug, alcohols, polyols, etc. The CP temperature can be considered as the solubility limit temperature as at CP the solutions of nonionic surfactants separate into two different phases and cloudiness appears. The CP value of the nonionic surfactants is a function of the microenvironment; thus, it is dependent on the presence of additives as well as their concentration. The phase segregation of the nonionic surfactant is an energetically controlled phenomenon, thus the impact of different additives especially pharmaceutical ingredients need to be studied from an application viewpoint. There are two major reasons which make the researcher investigate the phase separation occurring: (i) significant pathways involved in the extraction of different substances as well as in the separation techniques; (ii) the use of these methods for a certain objective can adversely have a consequence on the action of surfactant mediated formulation, which should be avoided. With the increase of the temperature, the water molecules start to unleash, and at the CP of the corresponding surfactant phase separation appears. With the augmentation of the temperature, the aggregated surfactants (micelles) start to interact with each other and consequently develop a network structure.22 In the case of CP assessment, the concentration of the employed surfactant (TX-100) was sustained above the cmc signifying that TX-100 exists in micellar form.23 The magnitudes of CP of TX-100 varied gradually with its

Scheme 2. Molecular Design of CFH

presence of CFH (Scheme 2) in aqueous or polyols medium. Besides the CP measurement, we planned to estimate different thermodynamic parameters of clouding, for example, the Gibbs free energy of clouding (ΔG0c ), the enthalpy of clouding (ΔH0c ), and entropy of clouding (ΔS0c ).

2. EXPERIMENTAL SECTION All of the chemicals employed herein were of extra pure/ analytical grade and no further purification was performed prior to their utilization. The provenances and mass fraction purity along with the CAS registration numbers of the compounds used have been profiled in Table 1. Double distilled−deionized H2O containing specific conductivity of 0.8−2.1 × 10−6 S cm−1 (temperature-dependent, from 298.15 K to 318.15 K) was utilized in order to prepare B

DOI: 10.1021/acs.jced.9b00579 J. Chem. Eng. Data XXXX, XXX, XXX−XXX

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Table 2. Values of CP of TX-100 in Absence/Attendance of Polyols (Glucose/Fructose) at Pressure p = 0.1 MPaa 10.04 mmol·kg−1 glucose

water CTX‑100

CCFH

mmol·kg−1 1.06 5.09 10.11 15.13 24.89 35.05 50.21 1.01 4.95 9.91 15.07 25.12 35.05 50.13 14.92 14.92 14.92 14.92 14.92

CP

CTX‑100

0.00 0.00 0.00 0.00 0.00 0.00 0.00 1.03 1.03 1.03 1.03 1.03 1.03 1.03 0.54 1.04 2.89 5.06 6.92

337.51 337.02 337.12 337.76 338.21 338.83 339.45 337.11 336.87 337.05 337.3 337.7 338.13 338.69 337.41 337.28 336.94 336.57 336.15

CCFH

mmol·kg−1

K 1.02 4.95 9.88 14.91 25.08 35.14 50.17 1.06 4.95 10.05 15.11 24.91 35.21 49.86 15.03 15.03 15.03 15.03 15.03

10.07 mmol·kg−1 fructose CP

CTX‑100

0.00 0.00 0.00 0.00 0.00 0.00 0.00 1.05 1.05 1.05 1.05 1.05 1.05 1.05 0.47 0.98 2.94 5.12 7.09

333.31 332.93 333.17 333.54 333.91 334.32 334.87 332.43 332.28 332.57 332.97 333.53 333.87 334.24 333.22 332.99 332.69 332.41 332.05

CCFH

CP

0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.97 0.97 0.97 0.97 0.97 0.97 0.97 0.47 0.97 2.95 5.09 7.09

332.87 332.68 332.99 333.33 333.66 334.03 334.39 332.44 332.13 332.57 332.97 333.23 333.71 334.14 333.21 332.97 332.55 332.13 331.79

mmol·kg−1

K 0.99 4.98 10.03 15.07 24.98 34.94 50.12 0.98 5.03 9.93 15.11 24.97 35.07 50.11 14.96 14.96 14.96 14.96 14.96

K

Standard uncertainties (u) are u(T) = 0.1 K and u(c) = 0.02 mmol·kg−1 (level of confidence = 0.68).

a

Figure 1. Variation of CP with the variation of concentration of TX100 in different solvents.

Figure 2. Variation of CP with the variation of concentration of polyols.

sustained concentration.15 Different additives of a diverse nature with different concentrations were employed in order to understand the influence of these additives on the phase segregation phenomenon of TX-100. Herein, we employed CFH antibiotic drug and polyols (glucose/fructose) having different concentration as additives. TX-100 solutions having a concentration range of 0.98−50.21 mmol·kg−1 were employed to study the phase separation phenomenon in the absence or attendance of CFH/polyols (glucose/fructose). The estimated CP values of TX-100 in aqueous and polyols (glucose/ fructose) media in the absence/presence of CFH are listed in Table 2. In the aqueous medium, the CP value of 10.11 mmol·kg−1 TX-100 was found to be 337.12 K which is in good agreement with the reported value by Amin et al.18 who observed a CP value of 336.99 K for 9.51 mmol·kg−1 TX-100. Herein, the observed CP values of TX-100 were found to be reduced

initially with the enhancement of the concentration of TX-100 (up to about 5 mmol·kg−1) and then increase with the subsequent rise of the TX-100 concentration (Table 2 and Figure 1). In contrast, Khan et al.24 found that CP values remain unchanged at lower concentration but increased at the higher concentration of TX-100. Again, in the attendance of polyols (glucose/fructose), the attained values of CP were lower as compared to that found in an aqueous medium (Table 2 and Figure 1). In the presence of glucose/fructose, the solubility, as well as the micellar size of TX-100, was reduced.25,26 Maclay found the variation of the CP of TX-100 as a function of polyols concentration to be reduced with the upsurge of polyols concentration.27 In our current study, we also observed a similar result; that is, the CP values of TX-100 were found to decrease with the augmentation of the glucose/fructose concentration (Figure 2). The monotonical reduction of CP values of TX-100 with C

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Table 3. Various Thermodynamic Parameters [ΔGoc (kJ mol−1), ΔHoc (kJ mol−1), and ΔSoc (J·K−1 mol−1)] of Clouding in the Absence/Presence of a Drug (CFH) in Different Solvents at Pressure p = 0.1 MPaa 10.04 mmol·kg−1 glucose medium

aqueous medium cTX‑100

cCFH

mmol·kg−1 1.06 5.09 10.11 15.13 24.89 35.05 50.21 1.01 4.95 9.91 15.07 25.12 35.05 50.13

0.00 0.00 0.00 0.00 0.00 0.00 0.00 1.03 1.03 1.03 1.03 1.03 1.03 1.03

cTX‑100 ΔGoc /ΔHoc /ΔSoc 30.49/911.85/2611.37 26.05/848.41/2440.09 24.13/861.33/2483.37 23.05/944.36/2727.72 21.68/1003.11/2901.85 20.76/1084.56/3139.63 19.78/1166.57/3378.39 30.53/22.85/-22.80 30.51/22.81/-22.87 30.53/22.84/-22.82 30.55/22.88/-22.74 30.59/22.95/-22.61 30.63/23.03/-22.48 30.68/23.13/-22.31

cCFH

cTX‑100

mmol·kg−1 1.02 4.95 9.88 14.91 25.08 35.14 50.17 1.06 4.95 10.05 15.11 24.91 35.21 49.86

0.00 0.00 0.00 0.00 0.00 0.00 0.00 1.05 1.05 1.05 1.05 1.05 1.05 1.05

10.07 mmol·kg−1 fructose medium

ΔGoc /ΔHoc /ΔSoc 30.22/1584.49/4663.14 25.81/1712.97/5067.60 23.92/1631.89/4826.30 22.80/1506.43/4448.14 21.38/1380.41/4070.02 20.47/1240.09/3648.04 19.52/1050.75/3079.51 30.03/2210.79/6560.06 25.76/2362.68/7032.99 23.83/2068.78/6148.94 22.73/1661.69/4922.26 21.38/1088.45/3199.33 20.44/738.52/2150.78 19.50/356.08/1007.02

cCFH

mmol·kg−1 0.99 4.98 10.03 15.07 24.98 34.94 50.12 0.98 5.03 9.93 15.11 24.97 35.07 50.11

ΔGoc /ΔHoc /ΔSoc

0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.97 0.97 0.97 0.97 0.97 0.97 0.97

30.26/2428.18/7203.76 25.78/2652.76/7896.42 23.86/2286.07/6793.63 22.76/1882.31/5578.73 21.38/1488.84/4398.08 20.47/1045.81/3069.61 19.49/612.86/1774.49 30.25/1789.97/5293.34 25.71/1960.00/5823.91 23.86/1718.47/5095.51 22.73/1497.77/4429.96 21.35/1353.74/3998.40 20.44/1086.64/3194.97 19.48/846.04/2473.69

Standard uncertainties (u) are u(T) = 0.1 K, u(c) = 0.02 mmol·kg−1 and u(p) = 5 kPa (level of confidence = 0.68). Relative standard uncertainties (ur) are ur(ΔG0c ) = ±3%, u(ΔH0c ) = ±3%, and ur(ΔS0c ) = ±4%. a

Figure 3. Representative plot of enthalpy and entropy of clouding to for TX-100 in (A) water (B) 10.04 mmol·kg−1 glucose, and (C) 10.07 mmol· kg−1 fructose.

D

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value reduces. Again the penetration of the hydrophobic chain of the polyols molecules into the palisade layer of the micelle weakens the EO−water interaction which also contributes to the reduction of CP values.13 Carbohydrates such as glucose, fructose, and maltose are the structural units of the cell walls and are water structure makers29 and thus increase the hydrophobic interaction in the presence of carbohydrate molecules. Consequently hydration reduces and micelle− micelle interaction is facilitated; hence, reducing the CP values. 3.2. Thermodynamic Properties of Clouding. In the measurement of the solubility of the nonionic surfactants, the knowledge of CP values at certain conditions provides important information as nonionic surfactant solutions separate into two phases above the CP temperature. Again, the estimated CP values can be used to calculate different thermodynamic properties of clouding, such as ΔGoc , ΔHoc , and ΔSoc , by taking the solubility limit at CP by using the following equations:30,31

Figure 4. Representative plot of enthalpy−entropy compensation for TX-100+CFH in an aqueous medium.

the enhancement of concentration of glucose/fructose is due to the dehydration of the ethylene oxide (EO) group enhanced by the salting-out phenomenon. TX-100 become more hydrophobic in nature in the presence of glucose/fructose. It is reported that the polyols can be utilized as a cosolvent as they are soluble in water and are not incorporated with the micelles, thus the presence of polyols alters the nature of the water phase. As polyols have higher densities than water, the volume fraction of surfactants (TX-100) increases with the rise of polyols concentration. The enhancement of the volume fraction of surfactants causes a decrease of interlayer spacing. Again the interlayer spacing increases with the addition of polyols even when the volume fraction of the hydrophilic parts are kept constant. These two opposite effects cancel each other.28 The estimated CP values of TX-100 follow the order CPwater > CPglucose > CPfructose (Table 2). The obtained CP values of TX-100 were very similar both for glucose and fructose (Figure 2) as these two polyols have an analogous structure, and this result agrees well with the literature.24 The reduction of the CP in the presence of polyols emphasizes that the solubilization of polyols happens through a large decline in hydration of the TX-100 micelles. Actually, the polyol molecules are favorably solubilized by an adsorption phenomenon at the micelle−water interface by the hydrocarbon part in the outer shell of the hydrated polyoxyethylene chain. This adsorption of polyols molecules prohibits the hydration of TX-100 and thus enhances micelle−micelle interaction, and thus CP values are reduced. The replacement of water molecules by the polyols molecules at the micellar surface is the cause of the reduction of the dielectric constant which reduces the solubility of the micelles, and the ensuing solution become cloudy at a lower temperature; that is, the CP

ΔGco = −RT ln Xs

(1)

ΔHco = RT 2(∂ ln Xs)/∂T

(2)

ΔSco = (ΔHco − ΔGco)/T

(3)

In the above relations, XS, R, and T elicit the concentration of the additives present in mole fraction, universal gas constant, and CP of TX-100 in Kelvin accordingly. The variation of CP as a function of Xs, can be articulated as a non-asymmetrical parabolic curve through eq 432 ln Xs = A + BT + CT 2

(4)

where A, B, and C are the constants executed through the regression assessment of the least-squares. The estimated values of these constants in aqueous as well as in polyols medium are profiled in Table S1 (Supporting Information). The estimated values of the constants were then utilized for the purpose of the ΔHoc calculation from the subsequent equation: ΔHco = RT 2[B + 2CT ]

(5)

Different thermodynamic parameters calculated from the above-mentioned equations are summarized in Table 3. The estimated values of ΔGoc were positive in all cases, which illustrates the nonspontaneous phase separation phenomenon. However, as usual in the case of mixed micellization of amphiphiles systems, the Gibbs free energy was found to be negative.33,34 Mutually the values of ΔH0c and ΔS0c manage the ΔG0c at the cloud point of TX-100 in the aqueous medium, along with the presence of additives employed in the current system. The positive values of ΔGoc decreased with the upsurge of TX-100 concentration (except TX-100+CFH system in an

Table 4. Entropy−Enthalpy Compensation Parameters of the Clouding Process of TX-100 at Pressure p = 0.1 MPaa 10.04 mmol·kg−1 glucose

water −1

CCFH (mmol·kg ) ΔHo,c * (kJ mol−1) TC (K) R2

0.00 24.272 337.880 0.99946

1.03 35.652 561.566 0.99999

0.00 22.6013 333.822 0.99988

1.04 21.484 333.210 0.99999

10.07 mmol·kg−1 fructose 0.00 21.693 333.520 0.99999

1.07 22.067 333.160 0.99999

a Standard uncertainties (u) are u(T) = 0.1 K, u(c) = 0.02 mmol·kg−1 and u(p) = 5 kPa (level of confidence = 0.68). Relative standard uncertainties (ur) are ur(ΔHo,c *) = ±4%.

E

DOI: 10.1021/acs.jced.9b00579 J. Chem. Eng. Data XXXX, XXX, XXX−XXX

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aqueous medium where the reverse trend was observed), which indicates that nonspontaneity is reduced at a greater concentration of TX-100, and this result is in good agreement with literature results.18 The exhibition of phase separation reveals the augmented desolvation of the polar parts of the surfactant. The phase separation phenomenon draws out the H2O molecules from the micelles, and insolubility appears at a higher temperature, and therefore the clouding phenomenon is observed. It is believed that the system has a maximum solubility of solutes at that certain temperature;35 therefore, ΔG co associated with clouding emphasizes that phase separations happen, going from a single to two different phases. The estimated magnitudes of the ΔHoc and ΔSoc of clouding for TX-100 in the absence/attendance of polyols were obtained to be positive in all cases. In the case of pure TX-100, these magnitudes of ΔHoc and ΔSoc decreased first with the development of TX-100 concentration and then increased with the succeeding rise of the TX-100 concentration in aqueous medium, but the reverse result was observed in the presence of glucose/fructose. The positive magnitudes of both ΔHoc and ΔSoc reveal that the clouding phenomenon is a totally entropy controlled process (Table 3). Again, in the presence of CFH, the magnitudes of ΔHoc and ΔSoc were positive, and negative respectively in an aqueous medium (Table 3). The positive magnitudes of ΔHoc in the presence of CFH dwindles first with the concentration of TX100 and then augments with a further rise of the content of TX-100, whereas the negative values of ΔSoc show the opposite trend. The positive values of ΔHoc along with the negative values of ΔSoc emphasize that the clouding of TX-100+CFH in the aqueous medium is both an enthalpy and entropy controlled phenomenon. On the other hand the magnitudes of ΔHoc and ΔSoc were positive for the TX-100+CFH system in the presence of glucose/fructose, and these values increase first with the rise of concentration of TX-100 and then decrease with the subsequent rise of the concentration of TX-100. The positive values of ΔHoc and ΔSoc jointly imply that the clouding of the TX-100+CFH system in the presence of glucose/ fructose is a totally entropy controlled process. In an aqueous medium, the involvement of ΔHoc to ΔGoc was found to increase with the increase of CP temperature, which was the opposite in the case of the entropy contribution. In the presence of polyols (glucose/fructose), the trend of the contribution of ΔHoc and ΔSoc to ΔGoc with CP temperature was found to be opposite that of the aqueous medium. The involvement of ΔHoc and ΔSoc to ΔGoc in diverse media is profiled in Figure 3. The positive value of ΔHoc is the outcome of the disruption of the H2O structure near the nonpolar parts of the surfactant,36−40 whereas the negative ΔHoc value implies the presence of an attractive force such as London dispersion forces during surfactant association.41,42 3.3. Thermodynamic Properties of Transfer. The different thermodynamic indices of transfers such as free energy transfer (ΔGoc,tr) and enthalpy of transfer (ΔHoc,tr) as well as the entropy of transfer (ΔSoc,tr) during the phase separation phenomenon for TX-100+CFH in a different medium can be calculated through the following equations:43−47 o ΔGc,tr = ΔGco(aq additive) − ΔGco(aq) o ΔHc,tr = ΔHco(aq additive) − ΔHco(aq)

(8)

The calculated values of ΔGoc,tr, ΔHoc,tr, and ΔSoc,tr for the phase separation phenomenon of TX-100+CFH in polyols medium are provided in Table S2. o The magnitudes of ΔGc,tr for the phase separation phenomenon of the TX-100+CFH system were found to be negative both in glucose and fructose media which indicates that the clouding phenomenon is more spontaneous in the presence of glucose/fructose. This result is supported by lower CP values in the polyols medium (Table 2). The values of ΔHoc,tr for the phase separation phenomenon of TX-100+CFH in polyols media were positive at an lower concentration of TX-100 and negative at a higher concentration of TX-100 in all cases. Again the values of ΔSoc,tr were negative at a lower concentration of TX-100 and positive at higher concentration of TX-100 in the absence of CFH in glucose medium but the opposite result was found in fructose medium. Again, in the presence of CFH, the magnitudes of ΔSoc,tr were positive at a lower concentration of TX-100 but negative at a higher concentration both in glucose and fructose medium (Table S2). 3.4. Enthalpy−Entropy Compensation. The graphical representation of ΔHoc versus ΔSoc for TX-100/TX-100+CFH were linear in all cases with an R2 value of 0.99946−0.99999, and this type of result is called the enthalpy−entropy compensation (Figure 4) which is obtained through the subsequent equation20,44,48,49 ΔHco = ΔHco, * + TcΔSco

(9)

In the above equation, ΔHo,c * and Tc denote intrinsic enthalpy and compensation temperature, respectively. The ΔHo,c * values can be utilized to understand the solute− solute interaction, whereas Tc values provide an idea about the solute−solvent interaction.50−52 The magnitudes of ΔHo,c * and Tc for TX-100/TX-100+CFH are profiled in Table 4. In an aqueous medium, the Tc value for pure TX-100 was found to be 337.880 K, and in the presence of CFH, it was 561.566 K. Again, in the presence of polyols, the T c magnitudes for distinct TX-100/TX-100+CFH lie between 333.160 K and 333.822 K. The attained values of ΔHo,c * were positive in all media studied (Table 4). The Tc values around 270−300 K can be utilized for the estimation of the presence of water in the protein solution.53

4. CONCLUSION In this study, the clouding phenomenon of TX-100/TX100+CFH in the absence/presence of polyols (glucose/ fructose) has been studied, and the outcome of the study can be summarized as follows: • The CP magnitudes of TX-100 obtained decreased initially with the enhancement of the concentration of TX-100 and then increased with the subsequent rise of the TX-100 concentration. • The CP value decreases in the presence of polyols and follows the order CPwater > CPglucose > CPfructose.

(6)

• The CP value decreases with the enhancement of polyols concentration.

(7)

• The estimated values of ΔGoc and ΔHoc were positive in all cases. F

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• The estimated values of ΔSoc were negative in an aqueous medium and in the presence of CFH, but positive in all other cases. o • The values of ΔG c,tr for the phase separation phenomenon of the TX-100+CFH system were found to be negative both in glucose and fructose media. • The values of ΔHoc,tr in polyols media were positive at an lower concentration of TX-100 and negative at the higher concentration of TX-100 in all cases. • Enthalpy−entropy compensation was observed in all cases.

chemical microscopy (SECM). Proc. Natl. Acad. Sci. U. S. A. 2010, 107, 16783−16787. (12) Schott, H. Effect of inorganic additives on solutions of nonionic surfactants-XVI. Limiting cloud points of highly polyoxyethylated surfactants. Colloids Surf., A 2001, 186, 129−136. (13) Alauddin, M.; Parvin, T.; Begum, T. Effect of organic additives on the cloud point of Triton X-100 micelles. J. Appl. Sci. 2009, 9, 2301−2306. (14) Mudawadkar, A. D.; Sonawane, G. H.; Patil, T. J. Thermodynamics of micellization of nonionic surfactant Triton X100 in presence of additive Poly-N-vinyl-pyrrolidone using clouding phenomenon. Orient. J. Chem. 2013, 29, 227−233. (15) Panchal, K.; Desai, A.; Nagar, T. Physicochemical behavior of mixed nonionic-ionic surfactants in water and aqueous salt solutions. J. Dispersion Sci. Technol. 2006, 27, 33−38. (16) Stevens, D. L.; Bisno, A. L.; Chambers, H. F.; Everett, E. D.; Dellinger, P.; Goldstein, E. J.; Gorbach, S. L.; Hirschmann, J. V.; Kaplan, E. L.; Montoya, J. G.; Wade, J. C. Practice guidelines for the diagnosis and management of skin and soft-tissue infections. Clin. Infect. Dis. 2005, 41, 1373−1406. (17) Osmon, D. R.; Berbari, E. F.; Berendt, A. R.; Lew, D.; Zimmerli, W.; Steckelberg, J. M.; Rao, N.; Hanssen, A.; Wilson, W. R. Diagnosis and management of prosthetic joint infection: clinical practice guidelines by the Infectious Diseases Society of America. Clin. Infect. Dis. 2013, 56, e1−e25. (18) Amin, M. R.; Mahbub, S.; Molla, M. R.; Alam, M. M.; Hossain, M. F.; Rana, S.; Abdul Rub, M.; Hoque, M. A.; Kumar, D. Phase separation and thermodynamic behavior of triton X-100 in occurrence of levofloxacin hemihydrates: Influence of additives. J. Chem. Eng. Data 2019, 64, 2750−2758. (19) Rahman, M.; Khan, M. A.; Abdul Rub, M.; Hoque, M. A.; Asiri, A. M. Investigation of the effect of various additives on the clouding behavior and thermodynamics of polyoxyethylene (20) sorbitan monooleate in absence and presence of ceftriaxone sodium trihydrate drug. J. Chem. Eng. Data 2017, 62, 1464−1474. (20) Aktar, S.; Molla, M. R.; Mahbub, S.; Abdul Rub, M.; Hoque, M. A.; Islam, D. M. S. Effect of temperature and salt/alcohol on the interaction of tetradecyltrimethylammonium bromide/ Triton X-100 with moxifloxacin hydrochloride: A multitechnique approach. J. Dispersion Sci. Technol. 2019, 40, 574−586. (21) Kumar, D.; Hidayathulla, S.; Rub, M. A. Association behavior of a mixed system of the antidepressant drug imipramine hydrochloride and dioctyl sulfosuccinate sodium salt: Effect of temperature and salt. J. Mol. Liq. 2018, 271, 254−264. (22) Ferguson, M. A.; Alderson, N. L.; Trost, S. G.; Essig, D. A.; Burke, J. R.; Durstine, J. L. Effects of four different single exercise sessions on lipids, lipoproteins, and lipoprotein lipase. J. Appl. Physiol. 1998, 85, 1169−1174. (23) Rub, M. A.; Azum, N.; Asiri, A. M. Interaction of cationic amphiphilic drug nortriptyline hydrochloride with TX-100 in aqueous and urea solutions and the studies of physicochemical parameters of the mixed micelles. J. Mol. Liq. 2016, 218, 595−603. (24) Khan, M. B.; Hoque, M. A.; Islam, D. M. S. Physicochemical investigation of the clouding behavior and thermodynamics of p-tertalkylphenoxy poly (oxyethylene) ether micelles in aqueous environment and in the presence of diols. J. Chem. Thermodyn. 2015, 89, 177−182. (25) Al-Ghamdi, A. M.; Nasr-El-Din, H. A. Effect of oilfield chemicals on the cloud point of nonionic surfactants. Colloids Surf., A 1997, 125, 5−18. (26) Kim, E. J.; Kim, S. W.; Yoo, I.-K.; Chung, J. S.; Kim, J. S.; Shah, D. O. Cloud Point and Dye Solubilization Studies of Amphiphilic Drug Solutions: The Effect of Electrolytes and Nonelectrolytes. Chem. Eng. Commun. 2006, 193, 1065−1074. (27) Maclay, W. N. Factors affecting the solubility of nonionic emulsifiers. J. Colloid Sci. 1956, 11, 272−285. (28) Iwanaga, T.; Suzuki, M.; Kunieda, H. Effect of added salts or polyols on the liquid crystalline structures of polyoxyethylene-type nonionic surfactants. Langmuir 1998, 14, 5775−5781.

ASSOCIATED CONTENT

S Supporting Information *

The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acs.jced.9b00579. Values of different constants A, B, and C for the determination of thermodynamic parameters and transfer properties of different thermodynamic parameters (PDF)

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AUTHOR INFORMATION

Corresponding Author

*Fax: 880-2-7791052. E-mail: [email protected]. ORCID

Malik Abdul Rub: 0000-0002-4798-5308 Md. Anamul Hoque: 0000-0002-2609-1815 Notes

The authors declare no competing financial interest.

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REFERENCES

(1) Rosen, M. J. Surfactants and Interfacial Phenomenon, 3rd ed.; Wiley: New York, 2004. (2) Rub, M. A.; Azum, N.; Khan, F.; Asiri, A. M. Aggregation of sodium salt of ibuprofen and sodium taurocholate mixture in different media: A tensiometry and fluorometry study. J. Chem. Thermodyn. 2018, 121, 199−210. (3) Kumar, D.; Rub, M. A. Catalytic role of 16-s-16 micelles on condensation reaction of ninhydrin and metal-dipeptide complex. J. Phys. Org. Chem. 2019, 32, e3918. (4) Kumar, D.; Rub, M. A. Studies of interaction between ninhydrin and Gly-Leu dipeptide: Influence of cationic surfactants (m-s-m type Gemini). J. Mol. Liq. 2018, 269, 1−7. (5) Attwood, D.; Florence, A. T. Surfactant Systems; Their Chemistry, Pharmacy and Biology; Chapman & Hall: New York, 1983. (6) Rub, M. A.; Azum, N.; Asiri, A. M. Binary Mixtures of sodium salt of ibuprofen and selected bile salts: interface, micellar, thermodynamic, and spectroscopic study. J. Chem. Eng. Data 2017, 62, 3216−3228. (7) Kumar, D.; Rub, M. A. Effect of anionic surfactant and temperature on micellization behavior of promethazine hydrochloride drug in absence and presence of urea. J. Mol. Liq. 2017, 238, 389− 396. (8) Kumar, D.; Rub, M. A.; Azum, N.; Asiri, A. M. Mixed micellization study of ibuprofen (sodium salt) and cationic surfactant (conventional as well as gemini). J. Phys. Org. Chem. 2018, 31, e3730. (9) Fresta, M.; Guccione, S.; Beccari, A. R.; Furneri, P. M.; Puglisi, G. Combining molecular modeling with experimental methodologies: mechanism of membrane permeation and accumulation of ofloxacin. Bioorg. Med. Chem. 2002, 10, 3871−3889. (10) Israelachvili, J. N. Intermolecular and Surface Forces, 2nd ed.; Wiley: New York, 1995. (11) Koley, D.; Bard, A. J. Triton X-100 concentration effects on membrane permeability of a single HeLa cell by scanning electroG

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(29) Gref, R.; Domb, A.; Quellec, P.; Blunk, T.; Muller, R. H.; Verbavatz, J. M.; Langer, R. The controlled intravenous delivery of drugs using PEG-coated sterically stabilized nanospheres. Adv. Drug Delivery Rev. 1995, 16, 215−233. (30) Mahajan, S.; Shaheen, A.; Banipal, T. S.; Mahajan, R. K. Cloud point and surface tension studies of triblock copolymer-ionic surfactant mixed systems in the presence of amino acids or dipeptides and electrolytes. J. Chem. Eng. Data 2010, 55, 3995−4001. (31) Batigöc, C.; Akbas, H.; Boz, M. Thermodynamics of non-ionic surfactant Triton X-100-cationic surfactant mixtures at the cloud point. J. Chem. Thermodyn. 2011, 43, 1800−1803. (32) Blankschtein, D.; Thurston, G. M.; Benedek, G. B. Phenomenological theory of equilibrium thermodynamic properties and phase separation of micellar solutions. J. Chem. Phys. 1986, 85, 7268−7288. (33) Khan, F.; Rub, M. A.; Azum, N.; Kumar, D.; Asiri, A. M. Interaction of an amphiphilic drug and sodium bis(2-ethylhexyl)sulfosuccinate at low concentrations in the absence and presence of sodium chloride. J. Solution Chem. 2015, 44, 1937−1961. (34) Azum, N.; Rub, M. A.; Asiri, A. M. Interaction of triblockcopolymer with cationic gemini and conventional surfactants: A physicochemical study. J. Dispersion Sci. Technol. 2017, 38, 1785− 1791. (35) Da Silva, R. C.; Loh, W. Effect of additives on the cloud points of aqueous solutions ofethylene oxide-propylene oxide-ethylene oxide block copolymers. J. Colloid Interface Sci. 1998, 202, 385−390. (36) Alam, M. S.; Kabir-ud-Din; Mandal, A. B. Evaluation of thermodynamic parameters of some amphiphilic drugs in presence of sugars at the cloud point. Colloids Surf., B 2013, 105, 236−245. (37) Clint, J. H. Surfactant Aggregation; Chapman and Hall: New York, 1992. (38) Rub, M. A.; Khan, F.; Kumar, D.; Asiri, A. M. Study of mixed micelles of promethazine hydrochloride (PMT) and nonionic surfactant (TX-100) mixtures at different temperatures and compositions. Tenside, Surfactants, Deterg. 2015, 52, 236−244. (39) Kumar, D.; Rub, M. A. Aggregation behavior of amphiphilic drug promazine hydrochloride and sodium dodecylbenzenesulfonate mixtures under the influence of NaCl/urea at various concentration and temperatures. J. Phys. Org. Chem. 2016, 29, 394−405. (40) Khan, F.; Rub, M. A.; Azum, N.; Asiri, A. M. Mixtures of antidepressant amphiphilic drug imipramine hydrochloride and anionic surfactant: Micellar and thermodynamic investigation. J. Phys. Org. Chem. 2018, 31, e3812. (41) Hierrezuelo, J. M.; Molina-Bolívar, J. A.; Ruiz, C. C. An energetic analysis of the phase separation in non-ionic surfactant mixtures: The role of the headgroup structure. Entropy 2014, 16, 4375−4391. (42) Kumar, D.; Rub, M. A. Effect of sodium turocholate on aggregation behavior of amphiphilic drug solution. Tenside, Surfactants, Deterg. 2015, 52, 464−472. (43) Kresheck, G. C. In Water: A Comprehensive Treatise; Franks, F., Ed.; Plenum: New York, 1995. (44) Rahman, M.; Khan, M. A.; Rub, M. A.; Hoque, M. A. Effect of temperature and salts on the interaction of cetyltrimethylammonium bromide with ceftriaxone sodium trihydrate drug. J. Mol. Liq. 2016, 223, 716−724. (45) Hoque, M. A.; Ahmed, M. F.; Halim, M. A.; Molla, M. R.; Rana, S.; Rahman, M. A.; Rub, M. A. Influence of salt and temperature on the interaction of bovine serum albumin with cetylpyridinium chloride: Insights from experimental and molecular dynamics simulation. J. Mol. Liq. 2018, 260, 121−130. (46) Hoque, M. A.; Alam, M. M.; Molla, M. R.; Rana, S.; Rub, M. A.; Halim, M. A.; Khan, M. A.; Akhtar, F. Interaction of cetyltrimethylammonium bromide with drug in aqueous/ electrolyte solution: A combined conductometric and molecular dynamics method study. Chin. J. Chem. Eng. 2018, 26, 159−167. (47) Mishu, A. A.; Amin, M. R.; Rub, M. A.; Hoque, M. A.; Kabir, S. E.; Asiri, A. M. Impact of different diols/polyols on the phase

separation behavior as well as thermodynamic properties of tween 80. J. Phys. Org. Chem. 2019, e4001. (48) Chen, L. J.; Lin, S. Y.; Huang, C. C. Effect of hydrophobic chain length of surfactants on enthalpy-entropy compensation of micellization. J. Phys. Chem. B 1998, 102, 4350−4356. (49) Amin, M. R.; Mahbub, S.; Hidayathulla, S.; Alam, M. M.; Hoque, M. A.; Rub, M. A. An estimation of the effect of mono/polyhydroxy organic compounds on the interaction of tetradecyltrimethylammonium bromide with levofloxacin hemihydrate antibiotic drug: A conductometric study. J. Mol. Liq. 2018, 269, 417−425. (50) Gantiva, M.; Yurquina, A.; Martínez, F. Solution thermodynamics of ketoprofen in ethanol + water cosolvent mixtures. J. Chem. Eng. Data 2010, 55, 113−118. (51) Łudzik, K.; Kustrzepa, K.; Piekarski, H. Thermodynamics of micelle formation of gemini surfactants hexylene-1,6-bis(dimethyloctylammonium bromide) and dodecylene-1,12-bis(dimethyloctylammonium bromide) by electric conductance mesurements. J. Chem. Eng. Data 2014, 59, 4165−4172. (52) Łudzik, K.; Kustrzepa, K.; Piekarski, H.; Jozwiak, M. Application of conductance study to analyze micellization behavior of cationic gemini surfactants in water and water−ethanol solvent mixed media. J. Chem. Eng. Data 2016, 61, 1047−1053. (53) Lumry, R.; Rajender, S. Enthalpy-entropy compensation phenomena in water solutions of proteins and small molecules: A ubiquitous properly of water. Biopolymers 1970, 9, 1125−1127.

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DOI: 10.1021/acs.jced.9b00579 J. Chem. Eng. Data XXXX, XXX, XXX−XXX