Interaction of moxifloxacin hydrochloride with sodium dodecyl sulfate and tween 80: Conductivity & phase separation methods

Journal Pre-proof Interaction of moxifloxacin hydrochloride with sodium dodecyl sulfate and tween 80: Conductivity & phase separation methods

Sk.Md. Ali Ahsan, Nora Hamad Al-Shaalan, Md. Ruhul Amin, Mohammad Robel Molla, Shahina Akter, Md. Masud Alam, Malik Abdul Rub, Saikh Mohammad Wabaidur, Md. Anamul Hoque, Mohammed Abdullah Khan PII:

S0167-7322(19)35746-0

DOI:

https://doi.org/10.1016/j.molliq.2020.112467

Reference:

MOLLIQ 112467

To appear in:

Journal of Molecular Liquids

Received date:

20 October 2019

Revised date:

28 December 2019

Accepted date:

5 January 2020

Please cite this article as: S.M.A. Ahsan, N.H. Al-Shaalan, M.R. Amin, et al., Interaction of moxifloxacin hydrochloride with sodium dodecyl sulfate and tween 80: Conductivity & phase separation methods, Journal of Molecular Liquids(2018), https://doi.org/10.1016/ j.molliq.2020.112467

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© 2018 Published by Elsevier.

Journal Pre-proof

Interaction of moxifloxacin hydrochloride with sodium dodecyl sulfate and tween 80: Conductivity & phase separation methods

Sk. Md. Ali Ahsana, Nora Hamad Al-Shaalanb, Md. Ruhul Amina, Mohammad Robel Mollaa, Shahina Aktera, Md. Masud Alama,c, Malik Abdul Rubd, Saikh Mohammad Wabaidure, Md. Anamul Hoquea*, Mohammed Abdullah Khana a

Department of Chemistry, Jahangirnagar University, Savar, Dhaka- 1342, Bangladesh

b

Chemistry Department, P. O. Box 84428, College of Science, Princess Nourah bint

Abdulrahman University, Riyadh-11671, Saudi Arabia c

Department of Chemistry, Mawlana Bhashani Science and Technology University, Santosh,

Tangail-1902, Bangladesh Chemistry Department, Faculty of Science, King Abdulaziz University, Jeddah-21589, Saudi

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d

Arabia e

Chemistry Department, P. O. Box 2455, College of Science, King Saud University, Riyadh

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11451, Saudi Arabia

*

Address of corresponding Author: Dr. Md. Anamul Hoque Professor Department of Chemistry Jahangirnagar University Savar, Dhaka-1342, Bangladesh Email: [email protected] (M.A.Hoque) PABX: 880-2-7791045-51, extension: 1437 Fax: 880-2-7791052

1

Journal Pre-proof ABSTRACT Herein, antibiotic moxifloxacin hydrochloride (MFH) drug interaction with surfactants has been studied by the means of the conductometric as well as cloud point (TCP) measurement techniques in the absence and presence of different electrolytes. In this study sodium dodecylsulfate (SDS) and Tween-80 (Tw-80) were used as anionic and non-ionic surfactants respectively. For pure surfactant and (surfactant+MFH) mixture two clear critical micelles concentration (c*) values denoted by c*1 (first) and c*2 (second) were observed. Variation of the c* values in various systems signifies the interaction among the studied systems. The spontaneous surfactant assembly and stability of that aggregates were illustrated from the negative ∆G0m values of SDS / (SDS+MFH) in the H2O/ H2O+electrolytes medium. From ∆H0m and ∆S0m values it is clear that hydrophobic and electrostatic interactions are present between SDS as well as MFH. Various thermodynamic parameters of micellization were also determined. In the clouding phenomenon of Tw-80, the cloud pint (TCP) values were decreased with the enhancing content of Tw-80. In

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the presence of drug/ salts, the TCP values decreased dramatically. The obtaining ∆G0c values were positive which indicates the non-spontaneity of clouding. On the other hand, the values of ∆H0c and ∆S0c show the presence of electrostatic/ hydrophobic relations amongst MFH & Tw-80.

thoroughly for both studied systems.

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Various thermodynamic properties of transfer were also determined as well as explained

Keywords: Moxifloxacin hydrochloride (MFH), Critical micelle concentration (c*), Cloud point,

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Thermodynamics parameters, Hydrophobic interaction

2

Journal Pre-proof 1. Introduction Interaction of fluoroquinolone antibiotic drug with surfactant (cationic, anionic, nonionic) in an aqueous medium in addition to aqueous salts solution has been receiving increased attention in the recent year. This is due to the extensive application of the drug-surfactant system in both fundamental and applied fields [1]. Many modern drugs are amphiphilic/ hydrophobic in nature that creates some serious problems. These types of problems are observed in the case of their formulation and solubilization in body fluids. However, the drugs are struggling to exhibit their effectiveness in aqueous medium [2]. Nowadays, the surfactant has become the main focus for the researchers for new pharmaceuticals formulation as well as drug delivery systems [2]. Surfactants can form micelle in a watery environment because of their amphiphilic nature [3-7]. Sodium dodecyl sulfate (SDS) is an anionic surfactant that is extensively utilized in cleaning procedures. In pharmaceutical formulations, SDS is also used in huge quantities. SDS is also utilized as a constituent for lysing cells in the time of DNA extraction or RNA extraction. A

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micelle is a cumulative entity make up of several monomers of surface-active substances. Micelles solubilize dust as well as oils by picking from the surface of materials and scattering them into the solvent. Micelle formation facilitates emulsification, solubilization, along with the dispersion of otherwise non-compatible fabrics. The needed amphiphile concentration upon

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which micelles formation start is known as critical micelle concentration (c*) means above this concentration surfactant starts to eliminate dirt from the material surface. Critical micelle concentration (c*) is assessed of surfactant effectiveness. A lesser value of c* specifies a smaller amount of surfactant is required to saturate interfacial surface furthermore form micelles.

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Micelle can establish a unique core-shell structure [8]. These core-shell structures are capable to unite the drug molecules as well as can increase the drug solubility which is actually

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required for the drug delivery system [9-11]. From the previous statics, it is found that antimicrobial drugs are highly used drugs in the whole world [12]. MFH, a synthetic fourthgeneration fluoroquinolone antibiotic drug, is known to prescribe for treating a number of

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infections such as intra-abdominal infections, respiratory tract infections, pneumonia, endocarditis, sinusitis, anthrax, meningitis, tuberculosis, etc. Moxifloxacin helps to prevent bacterial DNA gyrase which is an important stage for DNA duplication as well as persuades bacterial lysis [13]. MFH works against bacterial pathogens which are responsible for infections in the gastrointestinal, urinary zone as well as stomach portion [14]. CP is a phenomenon that is distinct for non-ionic surfactants. Tween-80 is used as an emulsifier in cosmetics, pharmaceuticals along with food goods. In particular nutrients, the usage of the tween (equal to 1%) is permitted via the US Food and Drug Administration. The solubility of non-ionic surfactants decreases with the increasing of temperature. For this reason at a certain temperature, a solution becomes cloudy and phase separation happens as well as this heat is considered as CP [15]. If formulations are stored above CP values then phase separation can occur and can decrease the stability. For this reason, CP is important for the preparation of ointments, foam, suspension and emulsion [16]. The addition of different electrolytes can change the physical properties of surfactants as well as can increase the rate of a reaction. From the literature, it is observed that electrolytes can intensely influence the clouding properties of non-ionic surfactant mixture [17]. 3

Journal Pre-proof The relation of MFH (Scheme I) with SDS (Scheme II) (anionic surfactant) and Tween80 (Scheme III) in presence, as well as absence of electrolytes, was undertaken through conductivity and cloud point calculation techniques respectively. Various physic-chemical indicators (∆G0m, ∆H0m, as well as ∆S0m) related to the drug-SDS mixture in an aqueous environment as well as in attendance of salts have been investigated to explain the contact manners between MFH as well as a surfactant (SDS). Also the CP and connected several thermodynamic indices for MFH-Tw-80 mixtures have also been calculated as well as explained

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thoroughly.

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Scheme I. Moxifloxacin hydrochloride (MFH).

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Scheme II. Sodium dodecyl sulfate (SDS).

Scheme III. Molecular structure of Tween-80. 2. Experimental section 2.1. Materials Chemicals employed herein were utilized without further treatment because all were of analytical grade. Moxifloxacin hydrochloride (MFH) antibiotic drug (purity: 0.97, CAS number: 151-21-3) was utilized in this work was delivered by General pharmaceuticals Ltd., Bangladesh. SDS (purity: 0.98, CAS number: 151-21-3, BDH, England), Tween-80 (Tw-80, purity: 0.99, CAS number: 9005-65-6, Merck, Germany), NaCl (purity: 0.99, CAS number: 7647-14-5, BDH, England), sodium sulfate (Na2SO4, purity:0.99, CAS number: 7757-82-6, Scharlau Chemicals, 4

Journal Pre-proof Spain), sodium phosphate (Na3PO4, purity: 0.99, CAS number: 7601-54-9, Merck, Germany) were used. Molality was utilized as the concentration unit for the surfactant, drug and drug+surfactant mixtures preparation (in the presence/ absence of a certain content of electrolytes). Solutions of drugs, as well as surfactants (attendance or non-attendance a fixed content of electrolytes), were made using distilled and de-ionized water having the specific conductivity of 2.5−3.0 μS cm-1.

2.2. Methods 2.2.1. Conductivity The specific conductivities of pure SDS/(MFH+SDS)/ (SDS+MFH+salts) in water were measured utilizing a 4510 conductivity meter (Jenway, UK) connected through a dip cell having cell constant 0.97 cm-1 (according to manufacturer report) maintaining the same guideline utilized in the previous works [18,19]. Conductivity meter used in this work was calibrated using

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freshly prepared potassium chloride solution of a certain concentration. An aqueous solution of SDS containing 50 mmol kg-1 (with and/or without a certain content of drug/ drug+salt) was gradually added to 20 mL of water/ MFH+H2O mixture of a specific content (with and/or without a certain content of salt) as well as at a fixed temperature using Lauda water-

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thermostated bath with precision of ±0.2 K. The conductivity was determined after each insertion with thoroughly stirring and allowing the resulting mixed system sometimes for thermal equilibration. The effect of the salt was observed by preparing both the MFH and MFH+surfactant mixtures in attendance of salt so that both solutions have the same content of

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electrolyte. The accuracy of the measurement of the conductivity utilizing the conductivity meter

2.2.2. TCP measurement

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is within ± 0.5%.

To get equilibrium situation, Tw-80 solution in pure or in the attendance of various

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additives was stirred for around one hour. Surfactant mixed solutions TCP were determined by image observation of the temperature, at which the studied solution becomes cloudy upon being heated up as well as vice versa on cooling [20-22]. Pure Tw-80 mixtures or Tw-80 mixtures containing different additives such as drugs, electrolytes were taken in thin test tubes and slowly heated in the temperature-restricted water bath with interior movement. The section was heated slowly as well as at the speed of up to 0.2 K min-1 after the temperature prolonged a few degrees under the fixed TCP temperature. After the temperature overtakes the TCP, the sample was cooled under the TCP temperature as well as then it was heated the mixture again to observe the reproducibility of the calculations. This method was done three times, and the usual TCP temperatures were taken from the average of these three measured values. The TCP values were reproducible within 0.2 K.

3. Results and discussion 3.1. Micellzation behavior of SDS and (SDS+MFH) mixed system Values of critical micelles concentration (c*) of the studied system were obtained from the graph of the change of specific conductivity (κ) against the content of surfactant (cSurfactant) in 5

Journal Pre-proof aqueous or (drug+SDS) mixture. Fig. 1 has shown for the specific conductivity (κ) against concentration of SDS (Csurfactant) for pure surfactant and (drug + surfactant) mixture in the watery environment at 298.15 K. The concentration from where the increase of conductivity of solution reduce compare to the previous state is called critical micelle concentration [18,23,24]. For solo surfactant and (SDS+ MFH) mixture two clear break-point was observed as well as the content of the equivalent break-points of SDS was think as (c*) as well as denoted by c*1 and c*2. The first and second break-point may be thought of as the development of MFH+surfactant complex and the SDS micellization (in presence of MFH) [18]. Two c* was also observed in the previous works [18,25,26]. From the previous study, it is found that the initial enhancement of specific conductivity because of the involvement of Na+ as well as DS− ions [1,2,19,20]. Further increasing concentration of surfactant, enhancing conductivity decrease because of the development of surfactant’s assembles and compression of

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Na+ with SDS micelles for the development of the Helmholtz layer [18,19,27,28]. 120

200

(a)

150

(S. cm-1)

80

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-1

S.cm )

(b)

100

100

50

0

5

10

15

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0 20

60 40 20 0

25

-1

0

5

10

15

20

25

-1

Csurfactant (mmol.kg )

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Csurfactant (mmol.kg )

Fig. 1. Graph of κ versus cSurfactant for (a) pure surfactant and (b) (MFH+surfactant) mixture in an

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aqueous environment at 298.15K.

The binding of the Na+ with micelles occurs due to the development of stable micelle by minimizing the outward charge repulsion as well as hence the intermolecular revulsion potential. Therefore, the association of sodium ions as well as DS− ions gives micelles extra heavier as well as eventually, the micelles exhibit minus movement in comparison to their monomeric surfactant form [19,29]. The values of degree of micelle ionization (α) were determined through the fraction of the ratio of the parallel successive lines similar to the pre and post c* [19,24]. The corresponding upper and lower region slopes are represented by S2 and S1 of c*1, whereas the respective upper and lower region slopes are expressed as S3 and S2 of c*2. Thus, the values α1 and α2 of were determined from the respective relations, for example, S2/S1 as well as S3/S1 correspondingly. Furthermore, the values of β were also determined by using the subsequent equation, β = (1 –α). 3.2. Observation of the impact of different salts on c* as well as β for (MFH+SDS) mixture Various types of salts containing cation/ anion are observed in the human body as well as their content in the cellular membranes probably will vary as well as in presence of amphiphiles 6

Journal Pre-proof mixture they may show relations on the amphiphiles mixtures. For this reason, it is required to investigate the association nature of surfactants along with drug-surfactant mixed systems through heat and in the presence of various electrolytes. Sodium salts (NaCl, Na2SO4 as well as Na3PO4) are used in this work to observe the impact on micellization of surfactant and MFH+SDS mixtures. The values of c* and β for pure surfactant as well as drug+surfactant mixture in watery environment and electrolytes mixture are shown in Table 1 at 303.15 K. The obtaining value of c* for SDS+MFH mixture in the aqueous medium increased compared to pure SDS. In attendance of NaCl salt, the c* values of SDS+MFH mixture decreased firstly in magnitude in comparison to those of SDS+MFH mixture in the watery environment as well as then increased with enhancing of electrolyte concentration [30]. In attendance of Na2SO4 and Na3PO4 salts, the c* values of the SDS+MFH mixture increased firstly in magnitude in comparison to those of SDS+MFH mixture in the watery

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environment as well as then decreased with enhancing of electrolyte concentration. The Na 2SO4 and Na3PO4 can create more influence over potassium chloride (NaCl) in decreasing c* values. The chloride ion (Cl-) is a chaotropic ion that has low charge density and has the capability to crack the H2Oarrangement as well as slightly declines hydrophobic associates of amphiphile

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monomers. Though SO4-2 and PO4-3 are strong kosmotropic ion-containing high charge density than chloride ion, it works as an H2O arrangement maker [31,32]. It stabilizes the micelles as well as salts out the hydrophobic moiety of surfactant from water as well as inclines to reduce the c*values to a greater range compared to chloride ions.

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Table 1. Values of c* as well as β for (MFH+surfactant) mixture in the presence of electrolytes

System

Medium

Isalt/ mmol.kg-1

c*1/ mmol.kg-1

c*2 / mmol.kg-1

β1

β2

0.00 0.00

3.48 5.11

8.54 11.37

0.72 0.72

0.92 0.92

0.01 0.10 0.30 0.50 1.00

4.95 4.67 4.23 4.73 4.91

11.14 10.99 10.68 10.82 10.98

0.62 0.63 0.59 0.56 0.60

0.83 0.84 0.84 0.82 0.81

SDS+MFH H2O+Na2SO4 0.01

4.43

10.49

0.61

0.83

0.10 0.30 0.50 1.00

4.85 4.04 3.88 3.67

10.88 10.27 9.92 9.73

0.62 0.54 0.52 0.47

0.83 0.82 0.81 0.77

SDS+MFH H2O+Na3PO4 0.01

4.63

10.95

0.62

0.85

0.10 0.30 0.50

4.76 4.34 4.07

11.14 10.78 10.58

0.63 0.59 0.56

0.83 0.80 0.79

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SDS H2O SDS+MFH H2O

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like NaCl, Na2SO4 and Na3PO4 at 303.15 K and pressure p = 0.1 MPaa.

SDS+MFH H2O+NaCl

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2.23

7.44

0.51

0.82

Standard uncertainties (u) are u(T) = 0.2 K, u(c) = 0.01 mmol∙kg-1 and u(p) = 5 kPa (level of

confidence = 0.68). Relative standard uncertainties (ur) are ur(c*1/ c*2) = ±3%, and ur(β1/ β2) = ±4%. 3.3. Impact of temperature on c* values of SDS and MFH+SDS mixture in attendance or absence of electrolytes The c* as well as β values for pure surfactant and drug+surfactant mixture in the watery medium as well as electrolytes solutions, are tabulated in Table 2. For solo surfactant (SDS), the c* values increased continuously with the increase of temperature in aqueous solution (Table 2). Alam et al. [33] and Rub et al. [34] also observed that c* values of pure SDS in aqueous solution increased with increasing temperature. In our previous study [35], it was found that c* values of pure SDS in water deceased initially with increasing temperature and then increased with

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increasing temperature. Moreover, it was also found that the c* values of pure SDS in aqueous system decreased continuously with increasing temperature [36]. Impacts of temperature on c* values can be elucidated by the modification of types of hydration around the SDS/ MFH facilitated surfactant (SDS) micelles with changing temperatures. Jointly hydrophilic and

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hydrophobic hydrations are feasible in the case of the monomeric form of employed SDS in addition to only hydrophilic hydration that applies its influence on the micellized surfactant (SDS) as in spherical form. It is observed that both kinds of hydration are reduced with enhancing of temperature. It was found by many researchers [37,38] that micellization favors the reduction of hydrophilic hydration whereas a decrease of hydrophobic hydration disfavors

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micellization. That is why two primary issues have been counted, one is de-solvation of ionic or

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polar head groups of SDS/ MFH facilitated SDS (decline hydrophilic hydration) promotes the micelle formation that is, c* values reduce as well as disruption of the arranged water particles, as well as destruction of hydrogen bonds neighboring non-polar portions of surfactant/

rise [23,37-39].

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MFH+SDS by the enhance of temperature, reduces the aggregation that is, c* values incline to

Table 2. Values of c* as well as β for (MFH+SDS) mixtures containing 0.50 mmol.kg-1 MFH in electrolytes solution at various temperatures and pressure p = 0.1 MPaa. System

Medium

Isalt/

T/

c*1 /

mmol.kg-1

K

mmol.kg-1

c*2 /

β1

β2

mmol.kg-1

SDS

H2O

0.00

298.15 303.15 308.15 313.15 318.15

3.32 3.48 3.59 3.66 3.85

8.44 8.54 8.78 9.14 9.35

0.72 0.72 0.72 0.74 0.71

0.90 0.92 0.91 0.93 0.87

(MFH+SDS)

H2O

0.00

298.15 303.15 308.15 313.15

5.15 5.11 4.91 4.75

11.31 11.37 11.21 10.76

0.59 0.61 0.63 0.63

0.41 0.83 0.37 0.37

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4.61

10.14

0.62

0.38

(MFH+SDS)

NaCl

0.50

298.15 303.15 308.15 313.15 318.15

4.97 4.73 4.58 4.71 5.03

10.98 10.82 10.56 10.71 11.03

0.56 0.55 0.60 0.64 0.62

0.80 0.81 0.84 0.86 0.85

(MFH+SDS)

Na2SO4

0.50

298.15 303.15 308.15 313.15 318.15

4.27 3.88 4.31 4.52 4.78

10.18 9.22 10.31 10.48 10.84

0.55 0.52 0.59 0.55 0.64

0.80 0.80 0.83 0.84 0.86

(MFH+SDS)

Na3PO4

298.15 4.38 10.75 0.58 0.81 303.15 4.07 10.58 0.56 0.79 308.15 4.46 10.39 0.55 0.82 313.15 4.68 10.67 0.61 0.83 318.15 4.95 10.92 0.60 0.85 a -1 Standard uncertainties (u) are u(T) = 0.2 K, u(c) = 0.01 mmol∙kg and u(p) = 5 kPa (level of

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0.50

confidence = 0.68). Relative standard uncertainties (ur) are ur(c*1/ c*2) = ±3%, and ur(β1/ β2) =

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±4%.

For these reasons, the above two issues determine the decrease or increase of c* values at a constant series of temperatures. The second factor controls the aggregation of pure surfactant in a watery medium at all temperatures. The first factor controls the aggregation of drug+surfactant

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in the watery medium at all temperatures. On the other hand, the first factor influences the

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aggregation of drug+surfactant in electrolytes solutions at inferiors’ temperature and secondfactor controls at upper temperature.

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3.4. Investigation of thermodynamic parameters of pure SDS as well as (SDS+MFH) mixed systems

In order to achieve detail knowledge about the occurred interaction between the observed substances (in the absence/ presence of additives), four different thermodynamic parameters are studied and analyzed on the basis of calculated values which are summarized in the following tables.

Tables 3. Values of the physic-chemical parameters for (MFH+surfactant) mixtures containing 0.50 mmol.kg-1 MFH in water as well as an aqueous solution of electrolytes at various temperatures and pressure p = 0.1 MPaa. I T -1 (mmol.kg ) (K) 0.5

298.15 303.15 308.15 313.15

ΔGom,1 ΔGom,2 (kJ/mol) -36.49 -37.69 -38.88 -39.84

-38.32 -39.27 -40.24 -41.39

ΔHom,1 ΔHom,2 ΔSom,1 ΔSom,2 ΔCom,1 ΔCom,2 (kJ/mol) (J mol-1K-1) (J mol-1K-1) Aqueous Medium -0.43 -41.37 120.95 -10.24 0.77 -37.53 126.87 5.74 2.09 -33.20 132.95 22.85 0.27 0.91 3.50 -28.47 138.42 41.26 9

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0.5

298.15 303.15 308.15 313.15 318.15

0.5

298.15 303.15 308.15 313.15 318.15

-40.17

-36.17 -36.73 -38.57 -40.04 -40.11

-36.57 -36.76 -38.67 -38.22 -40.74

298.15 -37.10 303.15 -37.52 308.15 -37.60 313.15 -39.37 318.15 -39.60 a Standard uncertainties (u) are

4.94

-23.10

141.77

60.33

-38.19 -39.12 -40.44 -41.49 -41.83

(H2O+NaCl) Medium 39.75 -20.72 254.66 31.32 -27.09 224.49 23.21 -34.21 200.49 13.86 -41.79 172.12 3.23 -49.20 136.24

58.59 39.67 20.23 -0.99 -23.18

-1.81 -1.43

-38.58 -39.64 -40.47 -41.13 -42.07

(H2O+Na2SO4) Medium 9.20 -4.61 153.49 1.15 -11.67 125.06 -7.57 -19.52 100.94 -16.53 -27.71 69.24 -27.70 -36.74 40.96

113.92 92.27 67.99 42.86 16.74

-1.83 -1.61

-38.37 -38.66 -40.15 -40.90 -41.91 u(T) =

(H2O+Na3PO4) Medium 16.65 -30.66 180.27 9.82 -36.83 156.16 2.73 -44.56 130.86 -4.97 -52.26 109.86 -13.21 -60.80 82.93 0.2 K, u(c) = 0.01 mmol∙kg-1

25.84 6.04 -14.32 -1.49 -1.51 -36.28 -59.39 and u(p) = 5 kPa (level of

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0.5

-42.30

pro of

318.15

confidence = 0.68). Relative standard uncertainties (ur) limits are ur(ΔGom,1/ΔGom,2), ur(ΔHom,1 /ΔHom,2), ur(ΔSom,1/ΔSom,2), and ur(ΔCom,1/ΔCom,2), are ±3%, ±4%, ±5%, and ±5% respectively. The values of thermodynamic parameters were determined by utilizing the subsequent equations

(1)

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∆G0m = (1+β) RT lnXc*

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(1 − 4) [29,40-43]:

Here, lnXc* is c* in the mole fraction unit. The enthalpy change (∆H0m) for the aggregation

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process has been evaluated by operating the below-expressed relations, ∆H0m = − (1+β) RT2 (∂ln Xc*)/∂T

(2)

Here Xc*, can be expressed by using the following equation, ln Xc* = A+BT+CT2 where A, B, and C are constant, and their value was calculated by using the regression analysis. A repetitive typical graph of ln Xc* versus T is presented in Fig. 2 for the determination of enthalpy change (∆H0m). The values of A, B as well as C are shown in Table S1 (supplementary materials). The enthalpy of micellization is evaluated by using the subsequent relation 3 [43,44]: ∆H0m = − (1+β) RT2 [B+2CT]

(3)

The standard entropy changes (∆S0m) for the micellization technique have been evaluated by utilizing the below-expressed relation 4 [46,47], ∆S0m = (∆H0m−∆G0m) / T

(4)

Table 3 embraced magnitudes of different parameters such as standard change of free energy (∆G0m), standard change of enthalpy (∆H0m), standard change of entropy (∆S0m), and 10

Journal Pre-proof standard change of molar heat capacity (∆C0m) in water along with three different salts medium (NaCl, Na2SO4, and Na3PO4). -8.48 -8.50 -8.52

lnxc*

-8.54 -8.56 -8.58 -8.60 -8.62 295

300

305

310

315

320

T (K)

pro of

Fig. 2. A repetitive graph of lnXc* versus T for the determination of enthalpy change (∆H0m). In terms of standard change of free energy (∆G0m), almost all the values are negative which shows that the aggregation process is spontaneous in nature [7,48-50] and the spontaneity

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is gradually increased with rising temperatures in all cases (with/ without salts) which proves that spontaneity is enhanced due to rise of temperature. The second negative values of ∆G0m are comparatively a bit higher than the first negative values which clear from Table 3. The aggregation phenomenon of the surfactants facilitated by hydrophobic interaction and counterion binding for ionic surfactants which are responsible for the negative values of ΔG0c. In an aqueous

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medium, the values of ΔHom,1 are positive except a value at 298.15 K. Apart from this, the values

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of ΔHom,1 in the salt medium are positive at lower temperatures which indicates the endothermic process. However, an alteration from positive to negative values was observed in the higher temperatures suggesting the exothermic process. On the other hand, the values of both ΔHom,1

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and ΔHom,2 are negative in aqueous as well as salts medium signifying the exothermic process. Therefore, the exothermic condition is higher at higher temperatures than lower temperatures. The magnitudes of all ΔSom,1 are positive in salt and salt-free. In terms of second entropy values, positive values were observed in the aqueous system at almost all temperatures except at 298.15K solutions, whereas at higher temperatures these values are negative for NaCl and Na3PO4 and positive at all temperatures for Na2SO4. In the attendance of salts, both ΔSom,1 and ΔSom,2 are decreased from higher to lower values with rising temperatures, which is opposite in water medium. According to evaluated values which are shown in Table 3, the aqueous medium of (SDS+MFH) is both enthalpy and entropically controlled. Similarly, the salt mediums are mainly both enthalpy and entropy dominate with some few exceptions at lower and higher temperatures respectively. The positive and negative values of ΔSom and ΔHom respectively suggest that apart from hydrophobic interaction, electrostatic interaction applying a vital role for effective micellization [51]. According to S.M. A. Ahsan et al. [51], the negative values of ΔHom indicate the breaking of the existing water structure around the non-polar moiety which is very important for hydrophobic interaction of surfactant molecules during micellization process. In this current work, we got both negative and positive values of enthalpy and these types of values 11

Journal Pre-proof were also achieved by Hoque et al. [18,19]. Another prediction was also stated by Nusselder and Engberts that negative values of enthalpy reveal the London-dispersion forces (very weak forces) which are responsible for the aggregation of surfactant monomers [52]. Two different indications/explanations may be mentioned in terms of positive values of entropy which are line to the inner & outer environment of micelle core along with the movement of polar & non-polar portions (Table 3). Firstly, during the construction of a large structure of water network close to the organic part of monomers, enhancement of entropy values is observed due to the departure of hydrophobic parts from H2O to micelle center which facilitates the hydrophobic interaction. Secondly, when hydrocarbon portions reached the micelle’s inside, the tendency and degree of rotational movement rise which stimulates the increase of entropy [53]. 3.5. Explanation of molar heat capacity (ΔCom) An important physicochemical parameter, molar heat capacity (ΔCom) which is

pro of

responsible to structural changes in terms of binging or departure of ligands, has been studied and its values were determined by using subsequent relation (5) for pure SDS as well as (SDS+MFH) mixed systems [38, 54] and the values are viewed in Table 3. ΔCom = ((∂H)/ ∂T)p

(5)

According to Table 3, it explicit that the values of molar heat capacity ΔCom,1 and ΔCom,2

Pr e-

are

positive in water, while their values become negative in salts medium. The values of ΔCom (positive as well as negative), both in water and salts, helps to guess that there have created a positive entropic environment by increasing the temperatures due to dehydration of water

al

discharge. The positive values of drug and surfactant mixtures indicate the alteration of SDS’s structural conformation along with loss of folding capacity in terms of SDS and drug joining.

urn

The alteration of heat capacity (positive to negative respective water to salts medium) in case of SDS and MFH mixture was considered to link with motion diminution &is proportional to the

Jo

molecular surface and I. Jelesarov reported [55] that it is aligned with the alteration of the accessible exterior region in the used solvent.

3.6. Transfer properties of thermodynamic parameters of (SDS+MFH) mixed systems Different physic-chemical properties of transfer like ΔG0m.tr, ΔH0m.tr. and (ΔS0m.tr.) of the micellization process from pure SDS in an aqueous environment to (SDS+MFH) in the attendance of electrolytes can be determined by utilizing the subsequent relations [45, 56, 57]. ΔG0m.tr = ΔG0m (aq. additive) –ΔG0m (aq.)

(6)

ΔH0m.tr. = ΔH0m (aq. additive) – ΔH0m (aq.)

(7)

ΔS0m.tr. = ΔS0m (aq. additive) − ΔS0m (aq.)

(8)

The ΔG0m.tr, ΔH0m.tr.as well as ΔS0m.tr.values for (SDS+MFH) mixed system in H2O and in attendance of electrolytes is presented in Table 4. The obtained magnitudes of standard change of transfer free energy (∆G0m,tr) are randomly positive and negative in salts solutions, whereas these values are positive in an aqueous medium. The negatives values indicate the unforced aggregation process. In case of standard change of transfer enthalpy (∆H0m,tr), both positive and negative values reveal the endothermic (deportation of organic part from H2O to MFH/ 12

Journal Pre-proof (MFH+SDS) systems) and exothermic process respectively (transferring of the non-polar portion from H2O to MFH/ (MFH+SDS) systems) [51]. Table 4. Transfer of thermodynamic indicators of micellization of (SDS+MFH) mixtures (with salts) at various temperature and pressure p = 0.1 MPaa. System

Medium

(SDS+MFH)

∆G0m,tr1 ∆G0m,tr2 ∆H0m,tr1 ∆H0m,tr2 ∆S0m,tr1 ∆S0m,tr2 (kJ mol-1) (kJ mol-1) (J mol-1 K-1) 4.97 3.09 11.44 -34.87 21.68 -127.33 4.27 3.22 12.91 -29.27 28.51 -107.28 3.63 2.59 14.50 -23.20 35.26 -83.69 3.77 2.37 16.32 -16.47 40.08 -60.21 3.15 0.69 17.80 -9.52 46.04 -32.08

T (K) 298.15 303.15 308.15 313.15 318.15

H2O

298.15 303.15 308.15 313.15 318.15

0.32 0.95 0.30 -0.20 0.06

0.13 0.16 -0.20 -0.09 0.47

40.19 30.55 21.12 10.35 -1.70

20.65 10.44 -1.01 -13.32 -26.10

133.71 97.62 67.53 33.70 -5.53

(SDS+MFH) H2O+Na2SO4

298.15 303.15 308.15 313.15 318.15

-0.07 0.93 0.21 1.63 -0.57

-0.26 -0.37 -0.23 0.26 0.23

9.63 0.38 -9.66 -20.04 -32.64

36.76 25.87 13.68 0.76 -13.64

32.54 124.16 -1.81 86.53 -32.02 45.13 -69.18 1.60 -100.81 -43.59

Pr e-

298.15 -0.61 -0.05 17.08 10.71 59.32 303.15 0.16 0.61 9.05 0.70 29.30 308.15 1.28 0.09 0.64 -11.36 -2.10 313.15 0.47 0.49 -8.47 -23.79 -28.56 318.15 0.57 0.39 -18.15 -37.70 -58.84 a Standard uncertainties (u) are u(T) = 0.2 K, u(c) = 0.01 mmol∙kg-1 and u(p) = 5 kPa

urn

al

(SDS+MFH) H2O+Na3PO4

pro of

(SDS+MFH) H2O+NaCl

68.83 33.93 -2.62 -42.25 -83.51

36.08 0.30 -37.17 -77.54 -119.7 (level of

confidence = 0.68). Relative standard uncertainties (ur) limits are ur(∆G0m,tr1/∆G0m,tr2), ur(∆H0m,tr1

Jo

/∆H0m,tr1), and ur(∆S0m,tr1 /∆S0m,tr2), are ±3%, ±4%, and ±5% respectively. The magnitudes of ∆S0m,tr demonstrate a similar pattern of ∆H0m,tr positive values (positive at inferior and negative at upper temperature) in salts medium. A. Rakshit and others accounted that negative ∆H0m,tr values in the case of amino acids are possible [53,58]. All values of ∆H0m,tr, and ∆S0m,tr indicate that water medium is merely entropically dominated and salts medium is mutually entropically and enthalpy dominated at all studied temperatures. 3.7. Enthalpy – entropy compensation phenomena Enthalpy-entropy compensation study of this (SDS+MFH) mixture in water/ salts has been by utilizing the following relation (Eq. (9)) [24] and the evaluated values are summarized in Table 5. ∆H0m = ∆H0,*m + Tc ∆S0m

(9)

From the plotted plots of ∆H0m versus ∆S0m in all cases it is clear that all the lines are linear having R2 magnitudes in the range of 0.98 – 0.99 (Fig. 3).

13

Journal Pre-proof Table 5. Enthalpy-entropy compensation indicators for SDS and (SDS+MFH) mixtures in salts solutions and pressure p = 0.1 MPaa. System

Medium

I

∆Ho,*m,1 ∆Ho,*m,2

cdrug

(mmol.kg-1) 0.0 0.5

(kJ mol-1) -30.86 -38.93

R2,1

R2,2

(K) 249.88 258.35

0.98

0.99

Tc,1

Tc,2

(SDS+MFH)

H2O

(SDS+MFH)

H2O+NaCl

0.5

0.5

-39.49

-41.22

312.58

350.94

0.99 0.99

(SDS+MFH)

H2O+Na2SO4

0.5

0.5

-40.18

-42.05

325.58

329.57

0.99 0.99

(SDS+MFH)

H2O+Na3PO4

0.5

0.5

-38.58

-39.46

308.93

356.07

0.99 0.99

a

Standard uncertainties (u) are u(T) = 0.2 K, u(c) = 0.01 mmol∙kg-1 and u(p) = 5 kPa (level of

confidence = 0.68). Relative standard uncertainties (ur) limits is ur(∆Ho,*m,1/∆Ho,*m,2) = ±4%.

70

pro of

60

40 30 20 10 0 -10 -20 -45

-40

Pr e-

-1 -1 0 Hm,2 /(kJ.mol K )

50

-35

-30

-1

0

-25

-20

-1

al

Sm,2 /(kJ.mol .K )

urn

Fig 3. A plot of enthalpy-entropy compensation for (SDS+MFH) in water with R2 = 0.99.

In the aforementioned relation, Tc (slope) denotes the compensation temperature as well as

Jo

∆Ho,*m (intercept) signifies the intrinsic enthalpy gain correspondingly. The evaluated magnitudes of slope refer to the solvation event, solute-solvent interaction and intercept demonstrate chemical event, solute-solute interaction. As reported that the aggregation process of a surface-active agent is related to both solvation and chemical parts [18]. The values of intrinsic enthalpy gain are negative revealing the non-suitable environment of micellization even at ∆S0m = 0. The existing values Tc in the range of 270 – 300K is an important tool by which augmentation of water entity can be analyzed [59]. In our study, the Tc values are present in the group of 249.88 – 356.07 K which is almost close to the expected range. The Tc values of our (SDS+MFH) systems are indicative of the consideration of biological fluids with consisting little exceptions. Similar phenomenon of compensation in terms of aggregation systems was illustrated by Sugihara and Hisatomi [60].

3.5. Clouding phenomenon of Tween-80 (Tw-80) in H20/ (H2O + electrolytes) Usually, surfactants which are nonionic show clouding behavior and gives cloud point (TCP) values. TCP values were determined within a content series of 1.02×10-3 - 10.08×10-3 mol. kg as well as shown in Table S2 (supplementary materials). We got TCP value 365.35 K for 14

Journal Pre-proof 1.02×10-3 mol/ kg Tw-80 in the water medium, which shows good similarity with Rahman et al [61]. For 0.763 mmol.kg-1 Tween-80 in water medium TCP value got 364.25K by Hoque et al. [62]. For 0.763 mmol.kg-1 Tween-80 in water medium TCP value got 364.25K by Mahajan et al [63]. He found that the TCP values were decreasing with the increasing concentration of Tween 80. This type of success is spontaneously accepted by others [64,65]. It may possible that with the decreasing of temperature hydration of oxyethylene oxygen decreases of polyoxyethylene hydrophilic part of Tw-80. With the increasing concentration of surfactant (Tween-80) equipped a definite level (10.08×10-3 mol/ kg) of surfactant (Tw-80), the spherical micelle turns to lesser in size and phase separation takes place. Mandal et al. [66], as well as Silva et al. [67], indicated that phase transition from one to another reduces the outer surface region of the produced micelle and insist to reduce hydration [53]. In this work, the TCP values were determined for various contents of Tw-80 to investigate the impact of MFH on the clouding nature of the surfactant. The observed results of (drug + surfactant) mixture in H2O are shown in Fig. 4 along with Table S3

pro of

(supplementary materials).

357 356

Pr e-

355

Tcp (K)

354 353 352

al

351

urn

350 0.0

0.5

1.0

1.5

2.0

2.5

3.0

3.5

4.0

4.5

-1

cMFH (mmol kg )

Jo

Fig. 4. Plot of TCP vs. concentrations (c) of MFH for (■) 2.01×10-3 mol.kg-1, (●) 6.03×10-3 mol.kg-1, and (▲) 10.0×10-3 mol.kg-1 Tw-80 solution.

Fig. 4 shows that TCP values decreased with increasing concentration of drug which is also calculated by others [64,68]. In some cases, it is found that Tw-80 (surfactant) produce mixed micelle with drug [33,69,70]. In this case, drug molecules reduce the water molecules from the head groups of the aggregates as well as reduce repulsion among the surfactant molecules. In this way, drug molecules reduce the TCP [71,72]. For the investigation of the effect of salts like NaCl, Na2SO4, and Na3PO4 on the TCP nature of Tw-80 in the (drug+surfactant) mixture has been investigated at several contents of electrolytes as well as the observed outcomes are exposed in Fig. 5 along with Table S4 (supplementary materials). The TCP values of (drug+Tw-80) mixture decreased in presence of various electrolytes compared to those in an aqueous environment as well as follow the following series: TCP (NaCl) < TCP (Na2SO4) < TCP (Na3PO4). Shinoda et al [72] observed that the TCP values of TX-100 were decreased in the presence of various salts. This type of reduction of (TCP) values was also 15

Journal Pre-proof observed in the presence of salts in earlier [73,74]. The reduction of values of TCP of the tween in the presence of drug/ electrolytes is also found by other researchers [61].

352

350

Tcp (K)

Tcp (K)

348

346

344

342 0

2

4

6 -1

8

10

pro of

csalt (mmol kg )

Fig. 5. Graph of TCP against contents of NaCl (■), Na2SO4 (●) & Na3PO4 (▲) salts for (MFH+surfactant) mixture having 6.008×10-3 mol.kg Tw-80, and 2.05×10-3 mol.kg-1 MFH drug.

Pr e-

Hofmeister sequence is a significant implement for extraction the information of the positional consequences of anions [75]. The mechanism relies on the change of present Hbonding manner among the H2O particles by the comparative ability of the ions. Some ions are water structure breakers (such as Cl-, which are usually located at the right side) as well as maker

al

(such as SO42-, which are usually stayed at the left side). The ions which are located at the left side show their salting-out consequence on the amphiphiles particles. On the other hand, the right

urn

located ions show salting in effect by creating a convenient environment for hydrogen bonding.

3.6. Thermodynamics of tween-80 in H2O/ (H2O+electrolytes) mixtures

Jo

Due to the minimum solubility of non-ionic surfactants, it gives CP values at that point and separates into two clear states after overcoming that TCP. Various physico-chemical indices were determined from cloud point (TCP) investigation like standard free energy alters (∆G0c), standard enthalpy changes (∆H0c), & standard entropy changes (∆S0c) using the subsequent equations [76-78]: ∆G0c = −RT lnXs

(10)

∆H0c = RT2 (∂lnXs) / ∂T

(11)

∆S0c = (∆H0c− ∆G0c)/ T

(12)

Here, Xs is known as the mole fraction. On the other hand, R is considered as universal gas constant & T is considered as TCP. The values of Xs can be determined from the equation below (13) [79]: lnXs= A + BT +CT2

(13)

16

Journal Pre-proof Here A, B, as well as C are constant. ∆H0c values were determined from the graph lnXs versus T and Fig. 6 is the representative plot in this study. The values of A, B, and C have been tabulated in Table S5 (supplementary materials). Values of ∆H0c for clouding were calculated by utilizing the subsequent equation which is found by substituting equation (13) into equation (11) ∆H0c = RT2 [B + 2CT]

(14)

-8.5 -9.0

-10.0 -10.5 -11.0 -11.5 -12.0 343

344

345

346

347

pro of

lnXs

-9.5

348

349

350

351

352

Pr e-

T (K)

Fig. 6. Plot of lnXs vs. TCP to calculate ∆H0c for 6.03×10-3 mol.kg-1 Tw-80 as well as 2.05×10-3

al

mol.kg-1 MFH in the presence of salt (NaCl) having different concentrations. Table 6. The values of different physico-chemical indices of clouding for pure Tw-80 in a

(mmol.kg-1) 1.02 2.01 3.02 3.99 5.02 6.01 7.02 8.01 9.01 10.8 a

ΔG0c

(kJ mol-1)

Jo

cTw-80

urn

watery environment at pressure p = 0.1 MPaa.

33.12 31.04 29.74 28.84 28.07 27.46 26.92 26.44 26.03 25.42

ΔH0c x10-2

ΔS0c x10-2

(kJ mol-1)

(J K-1 mol-1)

-6.52 -6.24 -5.49 -4.94 -4.02 -3.20 -2.35 -1.33 -0.54 0.33

-18.75 -17.94 -15.90 -14.37 -11.86 -9.62 -7.26 -4.43 -2.22 0.22

Standard uncertainties (u) are u(T) = 0.1 K, u(c) = 0.01 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%. With the increase of concentration of Tw-80, the values of ∆G0c, ∆H0c, and ∆S0c were observed to be decreased. Values of ∆G0c for our studied system are positive which shows that the level isolation manner is non-spontaneous in behavior. TCP of Tw-80 is the consequence of the cleavage of H-bonds between water and Tw-80 which is the outcome of a positive value of ∆G0c. 17

Journal Pre-proof At the time of clouding, the TCP elements release as well as push their solvated H2O particles for remaining separate from the solution that causes the maximum solubility [80]. Obtaining values (Table 6) for ∆H0c and ∆S0c were achieved negative with the exception at 10.08 mmol.kg-1 of tween which indicates that the reaction is exothermic and enthalpy dominated. From other studies [81,82], it has been found that the negative enthalpies & entropies indicate the presence of hydrogen bonding or London-dispersion force as well as electrostatic forces. The ∆H0c, as well as ∆S0c values, were found negative which indicates that the process is purely enthalpy dominated [61]. The values of different physico-chemical indices of clouding (MFH+Tw-80) in a watery environment are exposed in Table 7. The observed values of ∆G0c for pure Tw-80 as well as (drug+Tw-80) mixture are positive in value that shows the system is non-spontaneous in behavior. For all concentrations of Tw-80 (2.01×10-3, 6.03×10-3, and 10.00×10-3) the obtaining ∆G0c values were positive and declined with increasing concentration of MFH, which shows that

pro of

the non-spontaneity tends to decline with increasing concentrations of MFH and this shows similarity with Rahman et al [61]. For (MFH+Tw-80) mixture the values of ∆H0c and ∆S0c are negative at lower content of MFH and gradually decreased with the increasing of MFH concentration which is with the previous studies [82,83].

Pr e-

The standard enthalpy change ∆H0c changes because of electrostatic interaction, hydrophobic relation, hydration of polar head portions, as well as counter-ion binding to the micelles [84]. The ∆H0c values were achieved negative which shows the presence of dispersion forces between drug and surfactant components. Values of ∆S0c were negative which show the taking away of hydrophobic chains from water medium to the micellar interior [85]. For all

al

content of MFH (except at 10 mmol.kg-1 Tw-80 and 3.51 mmol.kg-1 MFH) the (MFH+Tw-80)

urn

mixture in aqueous solution is enthalpy dominated.

Table 7. Different physico-chemical indices of clouding of (MFH+Tw-80) mixed systems

cTw-80 (mmol.kg-1)

2.01

6.03

Jo

having different content of drug at a certain content of Tw-80 at pressure p = 0.1 MPaa. cMFH

∆G0c

∆H0c x10-2 (kJ mol-1)

∆S0c x10-2

∆G0c,t

(mmol.kg-1)

(kJ mol-1)

0.00 0.49 1.00 1.51 1.99 2.50 3.00 3.14 3.99

31.04 34.47 32.30 31.02 30.15 29.43 28.86 28.67 27.92

-6.24 -9.22 -7.99 -6.47 -5.16 -4.16 -3.17 -1.98 -0.61

-17.94 -26.85 -23.38 -19.11 -15.42 -12.60 -9.79 -6.44 -2.53

3.43 1.27 -0.02 -0.89 -1.60 -2.18 -2.36 -3.12

-2.98 -1.76 -0.23 1.07 2.07 3.07 4.25 5.63

0.00 0.48 1.01 1.49 1.98 2.48 3.00

31.04 34.41 32.17 30.96 30.04 29.33 28.74

-6.24 -7.89 -7.12 -5.89 -4.52 -3.47 -2.87

-17.94 -23.20 -20.99 -17.53 -13.67 -10.68 -8.97

6.95 4.71 3.49 2.58 1.86 1.27

-4.69 -3.92 -2.69 -1.32 -0.26 0.34

18

(J mol-1 K-1) (kJ mol-1)

∆H0c,t x10-2 (kJ mol-1)

Journal Pre-proof

10

a

3.51 4.03

28.24 27.79

-2.12 -1.38

-6.84 -4.72

0.77 0.33

1.08 1.82

0.00 0.49 1.00 1.52 2.02 2.48 3.02 3.51 4.01

31.04 34.28 32.12 30.85 29.93 29.30 28.68 4.09 27.75

-6.24 -5.27 -5.24 -5.20 -5.15 -5.13 -5.09 0.10 -5.01

-17.94 -15.85 -15.71 -15.61 -15.46 -15.40 -15.31 1.16 -15.11

8.86 6.71 5.43 4.52 3.89 3.27 -21.33 2.34

-5.60 -5.57 -5.53 -5.48 -5.46 -5.42 -0.23 -5.34

Standard uncertainties (u) are u(T) = 0.1 K, u(c) = 0.01 mmol∙kg-1 and u(p) = 5 kPa (level of

confidence = 0.68). Relative standard uncertainties (ur) are ur(ΔG0c) = ±3%, u(ΔH0c) = ±4%, ur(ΔS0c) = ±5%, u(∆G0c,t) = ±3%, and u(∆H0c,t) = ±4%.

pro of

In the presence of various electrolytes like NaCl, Na2SO4, and Na2PO4 the values of various physico-chemical indices (∆G0c, ∆H0c, and ∆S0c) are shown in Table 8. The obtaining values for ∆G0c were positive and reduced with increasing content of salts as well as the values were lesser in magnitudes compared to electrolytes free mixtures. This situation indicates the rising of spontaneity because of the presence of electrolytes (Tables 7-8). Finding ∆G0c values

Pr e-

was positive which indicates the whole process was non-spontaneous. The ∆H0c and ∆S0c values for all salts (NaCl, Na2SO4, and Na2PO4) were negative. From the studies [86,87], the negative values of ∆H0c indicate the quick amalgamation of polar head groups via water particles declare more prominent contrast to interruption of water composition in the hydrocarbon part of the

al

considered amphiphilic individuals. Positive ∆H0c magnitudes also show that the H2O particles in disarray environment [61].

urn

the region of the hydrophobic alkyl chains are always under disrupting as well as producing a The values of ΔG0c.t and ΔH0c.t of CP study from watery medium to (Tw-80+MFH)/ (Tw-

Jo

80+MFH+electrolytes) mixtures were additionally calculated by using the subsequent equations [47] as well as shown in Tables 7 & 8. ∆G0c,t = ∆G0c,t (aq. of additive) − ∆G0c,t (aq.)

(15)

∆H0c,t = ∆H0c,t (aq. of additive) − ∆H0c,t (aq.)

(16)

For (Tw-80+MFH) solution in H2O, the ∆G0c,t values at 2.01 mmol.kg Tw-80 were achieved positive inferior content of MFH and negative at upper content of MFH whereas the entire the ∆G0c,t values were obtained positive at 6.01 and 10.08 mmol.kg-1 of Tw-80 (except at 10 mmol.kg-1 Tw-80 and 3.51 mmol.kg-1 MFH). These obtaining positive values were slowly reduced with the increasing MFH content (Tables 7). The obtained ∆G0c,t values are positive at a lower concentration of salts while negative at higher concentration and magnitudes increased with enhancing contents of electrolytes (Table 8). Mutually negative as well as positive values of ∆G0c,t indicates the spontaneity and non-spontaneity of the present work. For 2.01 as well as 6.01 mmol.kg-1 Tw-80 in (Tw-80+MFH) mixture the values of ∆H0c,t was negative initially and became positive at higher drug contents and for 10 mmol.kg-1 of Tw-80, all ∆H0c,t values were negative at all concentration of the drug (Table 7) 19

Journal Pre-proof Table 8. Values of physico-chemical values of phase separation of (MFH+Tw-80) system having 6.01 mmol.kg-1 Tw-80 and 2.01 mmol.kg-1 MFH in H2O at pressure p = 0.1 MPaa. ∆S0c x10-2

(kJ mol-1) (kJ mol-1) (J mol-1 K-1) NaCl-water system

0 0.5 1 3 5 7 10

30.04 33.94 31.78 28.46 26.87 25.78 24.65

0 0.5 1 3 5 7 10

30.04 33.89 31.72 28.42 26.80 25.71 24.60

0 0.5 1 3 5 7 10

30.04 33.84 31.68 28.37 26.78 25.68 24.58

-4.52 -7.38 -6.16 -4.97 -3.79 -2.63 -1.46 Na2SO4-water system -4.52 -6.92 -5.74 -4.76 -3.52 -2.37 -1.58 Na3PO4-water system -4.52 -6.37 -5.22 -4.19 -3.17 -2.04 -1.26

∆G0c,t

∆H0c,t x10-2

(kJ mol-1)

(kJ mol-1)

-13.67 -21.97 -18.52 -15.07 -11.69 -8.36 -4.95

3.90 1.74 -1.58 -3.18 -4.26 -5.40

-2.86 -1.64 -0.44 0.73 1.89 3.06

-13.67 -20.68 -17.34 -14.50 -10.95 -7.64 -5.31

30.04 3.85 1.68 -1.63 -3.24 -4.34 -5.45

-4.52 -2.40 -1.22 -0.24 1.00 2.15 2.94

-13.67 -19.15 -15.87 -12.87 -9.95 -6.69 -4.39

30.04 3.80 1.63 -1.68 -3.27 -4.36 -5.47

-4.52 -1.85 -0.70 0.34 1.35 2.48 3.26

Standard uncertainties (u) are u(T) = 0.1 K, u(c) = 0.01 mmol∙kg-1 and u(p) = 5 kPa (level of

al

a

∆H0c x10-2

pro of

(mmol.kg-1)

∆G0c

Pr e-

csalt

confidence = 0.68). Relative standard uncertainties (ur) are ur(ΔG0c) = ±3%, u(ΔH0c) = ±4%,

urn

ur(ΔS0c) = ±5%, u(∆G0c,t) = ±3%, and u(∆H0c,t) = ±4%. The values of (∆H0c,t) were negative initially and followed by positive at higher concentration of

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electrolytes (NaCl, Na2SO4, and Na2PO4) as well as these values increased with increasing electrolytes content (Table 8). This type of result also observed in the previous report [58,88]. The negative values of ∆H0c,t show the relocating of the hydrophilic part of the surfactant from H2O to MFH/ (MFH+electrolytes) mixtures and it also indicates that it is exothermic in nature. On the other hand, the positive values of ∆H0c,t show the relocating of the hydrophilic part of Tw80 from H2O to MFH/ (MFH+electrolytes) mixed systems indicates it is endothermic in the environment.

4. Conclusion In this present work, we have executed the conductivity and TCP measurement process to observe the effect of temperature and additives as well as their content on the solution properties of anopnic surfactant SDS and nonionic surfactant Tw-80. Conductivity measurement technique shows that MFH increased the c* values at various concentrations and in the presence of electrolytes c* values decreased gradually. The obtained ∆G0m values are negative that shows the spontaneity of the association process of SDS in electrolytes or in absence of electrolytes. The values of ∆H0m were achieved negative and positive along with the values of ∆S0m were obtained 20

Journal Pre-proof almost positive in the entire studied system showing the presence of electrostatic as well as hydrophobic interactions. The values of ∆H0,*m are negative which indicates the stable micelle formation while Tc values are close to the biological fluid (protein solution). In the case of pure water, TCP values changed with the variation of concentrations of Tw-80. In attendance of MFH or salt, CP values decreased with increasing concentrations of drug/salt as well as which showed the style: TCP (NaCl) < TCP (Na2SO4) < TCP (Na3PO4). The ∆G0c values of clouding were positive for pure and mixed systems, which signify the non-spontaneity clouding. Values of ∆H0c and ∆S0c indicate the attendance of both hydrophobic and electrostatic relations. In the attendance/ non-attendance of salts, the magnitudes of various transfer energy of phase separation behavior were positive as well as negative. All the results in this present work (TCP and conductivity measurement) show the attractive interaction among the worked substances.

Supplementary materials

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Supplementary data to this article can be found online at science direct.

Declaration of competing interest

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The authors have declared that no competing interests exist.

Acknowledgment

This research was funded by the Deanship of Scientific Research at Princess Nourah bint Abdulrahman University, Riyadh, Saudi Arabia through the Fast-track Research Funding

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Program.

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Journal Pre-proof References [1]

V. Bhardwaj, T. Bhardwaj, K. Sharma, A. Gupta, S. Chauhan, S.S. Cameotra, S. Sharma, R. Gupta, P. Sharma, Drug–surfactant interaction: thermo-acoustic investigation of sodium dodecyl sulfate and antimicrobial drug (levofloxacin) for potential pharmaceutical application, RSC Adv. 4 (2014) 24935-24943.

[2]

S. Schreier, S.V. Malheiros, E. de Paula, Surface active drugs: self-association and interaction with membranes and surfactants. Physicochemical and biological aspects, Biochimica Biophysica Acta (BBA) - Biomembranes 1508 (2000) 210-234.

[3]

D. Kumar, M.A. Rub, Role of cetyltrimethylammonium bromide (CTAB) surfactant micelles on kinetics of [Zn(II)-Gly-Leu]+ and ninhydrin, J. Mol. Liquids 274 (2019) 639645.

[4]

D. Kumar, M.A. Rub, Interaction of ninhydrin with chromium-glycylglycine complex in the presence of dimeric gemini surfactants, J. Mol. Liq. 250 (2018) 329–334. D. Kumar, M.A. Rub, Studies of interaction between ninhydrin and Gly-Leu dipeptide:

pro of

[5]

Influence of cationic surfactants (m-s-m type Gemini), J. Mol. Liq. 269 (2018) 1–7. [6]

H.

Kumar,

N.

Sharma,

A.

Katal,

Aggregation

behaviour

of

cationic

(cetyltrimethylammonium bromide) and anionic (sodiumdodecylsulphate) surfactants in

Pr e-

aqueous solution of synthesized ionic liquid [1-pentyl-3-methylimidazolium bromide]Conductivity and FT-IR spectroscopic studies, J. Mol. Liq. 258 (2018) 285–294. [7]

A. Srivastava, H. Uchiyama, Y. Wada, Y. Hatanaka, Y. Shirakawa, K. Kadota, Y. Tozuka, Mixed micelles of the antihistaminic cationic drug diphenhydramine

al

hydrochloride with anionic and non-ionic surfactants show improved solubility, drug release and cytotoxicity of ethenzamide, J. Mol. Liq. 277 (2019) 349–359. H. Wennerström, B. Lindman, Micelles: Physical chemistry of surfactant association,

urn

[8]

Physics Reports 52 (1979) 1-86 [9]

C.J. Drummond, C. Fong, Surfactant self-assembly objects as novel drug delivery

[10]

Jo

vehicles, Current Opinion Colloid Interface Sci. 46 (1999) 449-456. P.A. Bhat, G.M. Rather, A.A. Dar, Effect of surfactant mixing on partitioning of model hydrophobic drug, naproxen, between aqueous and micellar phases, J. Phys. Chem. B 113 (2009) 997-1006 [11]

C. Tanford, The hydrophobic effect: formation of micelles and biological membranes, 2d ed. John Wiley, 1980.

[12]

S.L. Barriere. Cost-containment of antimicrobial therapy, Drug intelligence & clinical pharmacy 19 (1985) 278-281.

[13]

A. William, J. Petri, Antimicrobial agents. In Goodman and Gilman’s The Pharmacological bases of therapeutics. 10th ed. J. Hardman, L. Limbird, A. Gilman, Eds., McGraw Hill, New York, 2001, 1273-1295.

[14]

J.S. Solomkin, J.E. Mazuski, J.S. Bradley, K.A. Rodvold, E.J. Goldstein, E.J. Baron , P.J. O'Neill, A.W. Chow, E.P. Dellinger, S.R. Eachempati, S. Gorbach, M. Hilfiker, A.K. May, A.B. Nathens, R.G. Sawyer, J.G. Bartlett, Diagnosis and management of complicated intra-abdominal infection in adults and children: guidelines by the Surgical

22

Journal Pre-proof Infection Society and the Infectious Diseases Society of America, Clinical Infectious Diseases 50 (2010) 133-164. [15]

K. Shinoda, T. Nakagawa, B.I. Tamamushi, Colloidal surfactants: some physicochemical properties, 2nd ed. New York, 1969.

[16]

P.D. Huibers, D.O. Shah, A.R. Katritzky, Predicting surfactant cloud point from molecular structure, J. Colloid Interf. Sci. 193 (1997) 132-136.

[17]

J. Parikh, J. Rathore, D. Bhatt, M. Desai, Clouding behavior and thermodynamic study of nonionic surfactants in presence of additives, J. Dispersion Sci. Technol. 34 (2013) 13921398.

[18]

M.A. Hoque, M.M. Alam, M.R. Molla, S. Rana, M.A. Rub, M.A. Halim, M.A. Khan, F. Akhtar, Interaction of cetyltrimethylammonium bromide with drug in aqueous /electrolyte solution: A combined conductometric and molecular dynamics method study, Chinese J. Chem. Eng. 26 (2018) 159-167. M.A. Hoque, M.F. Ahmed, M.A. Halim, M.R. Molla, S. Rana, M.A. Rahman, M.A. Rub.

pro of

[19]

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. 260 (2018) 121-130.

Z. Wang, J.-H., Xu, W. Zhang, B. Zhuang, H. Qi. Cloud point of nonionic surfactant

Pr e-

[20]

Triton X-45 in aqueous solution, Colloids and Surfaces B: Biointerfaces 61 (2008) 118122. [21]

M.S. Ali, D. Kumar, H.A. Al-Lohedan, Effect of amphiphilic drugs on the cloud point of

al

hydroxypropylmethyl cellulose: Modulation with salt excipients, J. Mol. Liquids 194 (2014) 1-7.

Ç. Batıgöç, H. Akbaş, Thermodynamic parameters of clouding phenomenon in nonionic

urn

[22]

surfactants: The effect of the electrolytes, J. Mol. Liquids 231 (2017) 509-513. [23]

F. Akhtar, M.A. Hoque, M.A. Khan, Interaction of cefadroxyl monohydrate with

Jo

hexadecyltrimethyl ammonium bromide and sodium dodecyl sulfate, J. Chem. Thermodyn. 40 (2008) 1082-1086. [24]

M.A. Hoque, M.M. Alam, M.R. Molla, S. Rana, M.A. Rub, M.A. Halim, M.A. Khan, A. Ahmed, Effect of salts and temperature on the interaction of levofloxacin hemihydrate drug with cetyltrimethylammonium bromide: Conductometric and molecular dynamics investigations, J. Mol. Liq. 244 (2017) 512-520.

[25]

M.A. Hoque, M.D. Hossain, M. A Khan. Interaction of cephalosporin drugs with dodecyltrimethylammonium bromide, J. Chem. Thermodyn. 63 (2013) 135-141.

[26]

M. Rahman, M.A. Khan, M.A. Rub, M.A. Hoque, Effect of temperature and salts on the interaction of cetyltrimethylammonium bromide with ceftriaxone sodium trihydrate drug, J. Mol. Liq. 223 (2016) 716-724.

[27]

K.M. Sachin, S.A. Karpe, M.

Singh, A.

Bhattarai,

Self-assembly of sodium

dodecylsulfate and dodecyltrimethylammonium bromide mixed surfactants with dyes in aqueous mixtures, Royal Soc. Open. Sci. 6 (2019) 181979. [28]

J. Fendler, Catalysis in micellar and macromoleular systems, Academic Press, Elsevier, U.S., 1975. 23

Journal Pre-proof [29]

F.M. Jalali, Shamsipur, N. Alizadeh, Conductivity study of the thermodynamics of micellization of 1-hexadecylpyridinium bromide in (water+cosolvent), J. Chem. Thermodyn. 32 (2000) 755-765.

[30]

M.A. Hoque, M.R. Molla, M.R. Amin, M.M.

Alam, M.F. Hossain, M.A.

Rub, investigation of the effect of temperature, salt and solvent composition on the micellization behavior of tetradecyltrimethylammonium bromide in the presence of the antibiotic drug levofloxacin hemihydrate, J. Sol. Chem. 48 (2019) 105-124. [31]

M.J. Rosen, Surfactat and Interfacial phenomena, 3rd edn Willy, New York, 2004.

[32]

M.A. Ahsan, M.R. Amin, S. Mahbub, M.R. Molla, S. Aktar, M.A. Rub, M.A. Huque, M.N. Arshad, M.A. Khan, Interaction of ciprofloxacin hydrochloride with sodium dodecyl sulfate in aqueous/electrolytes solution at different temperatures and compositions, Chinese J. Chem. Eng. (2019) doi:10.1016/j.cjche.2019.03.019. M.S. Alam, R. Ragupathy, A.B. Mandal, The self-association and mixed micellization of an

anionic

surfactant,

sodium

dodecyl

sulfate,

and

a

pro of

[33]

cationic

surfactant,

cetyltrimethylammonium bromide: conductometric, dye solubilization, and surface tension studies, J. Dispersion Sci. Technol. 37 (2015) 1645–1654. [34]

M.A. Rub, N. Azum, S.B. Khan, H.M. Marwani, A.M. Asiri, Micellization behavior of

Pr e-

amphiphilic drug promazine hydrochloride and sodium dodecyl sulfate mixtures at various temperatures: Effect of electrolyte and urea, J. Mol. Liq. 212 (2015) 532–543. [35]

M.A. Hoque, S. Mahbub, M.A. Rub, S. Rana, M.A. Khan, Experimental and theoretical investigation

of

micellization

behavior

of

sodium

dodecyl

sulfate

with

al

cetyltrimethylammonium bromide in aqueous/urea solution at various temperatures, Korean J. Chem. Eng. 35(2018) 2269–2282. S.M.I.H. Sristy, S. Mahbub, M.M. Alam, S.M. Wabaidur, S. Rana, M.A. Hoque, M.A.

urn

[36]

Rub, Interaction of tetradecyltrimethylammonium bromide with sodium dodecyl sulfate

(2019) 12-22. [37]

Jo

in aqueous/urea medium at several temperatures and compositions, J. Mol. Liq. 284

S. Mahbub, M.L. Mia, T. Roy, P. Akter, A.K.M.R. Uddin, M.A. Rub, M.A. Hoque, A.M. Asiri, Influence of ammonium salts on the interaction of fluoroquinolone antibiotic drug with sodium dodecyl sulfate at different temperatures and compositions, J. Mol. Liq. 2019, 111583. doi:10.1016/j.molliq.2019.111583.

[38]

M.R. Molla, S. Rana, M.A. Rub, A. Ahmed, M.A. Hoque, Conductometric probe analysis of

the

effect

of

benzyldimethylhexadecylammonium

chloride

on

the

micellizationbehaviour of dodecyltrimethylammonium bromide in aqueous /urea solution: Investigation of concentration and temperature effect, J. Surf. Deterg. 21 (2018) 231-246 [39]

S. Mahbub, M.R. Molla, M. Saha, I. Shahriar, M.A. Hoque, M.A. Halim, M.A. Rub, M.A. Khan, N. Azum, Conductometric and molecular dynamics studies of the aggregation behavior of sodium dodecyl sulfate (SDS) and cetyltrimethylammonium bromide (CTAB) in aqueous and electrolytes solution, J. Mol. Liq. 283 (2019) 263–275.

[40]

M.N. Islam, T. Kato, Temperature dependence of the surface phase behavior and micelle formation of some nonionic surfactants, J. Phys. Chem. B 107 (2003) 965–971. 24

Journal Pre-proof [41]

N. Azum, M.A. Rub, A.M. Asiri, Self-association and micro-environmental properties of sodium salt of ibuprofen with BRIJ-56 under the influence of aqueous/urea solution, J. Dispersion Sci. Technol. 38 (2017) 96–104.

[42]

M.A. Rub, N. Azum, A.M. Asiri, Self-association behavior of an amphiphilic drug nortriptyline hydrochloride under the influence of inorganic salts, Russian J. Phys. Chem. B 10 (2016) 1007–1013.

[43]

S. Mahbub, M.A. Rub, M.A. Hoque, M.A. Khan, Mixed micellization study of dodecyltrimethylammonium chloride and cetyltrimethylammonium bromide mixture in aqueous/urea medium at different temperatures: theoretical and experimental view, J. Phys. Org. Chem. 31 (2018) e3872.

[44]

H.-U. Kim, K.-H. Lim, A model on the temperature dependence of critical micelle concentration, Colloids Surf. A, 235 (2004) 121-128.

[45]

A. Beesley, D.F. Evans, R.G. Laughlin, Evidence for the essential role of hydrogen

pro of

bonding in promoting amphiphilic self-assembly: measurements in 3-methylsydnone, J. Phys. Chem. 92 (1988) 791-793. [46]

A.B. Khan, M. Ali, N. Dohare, P. Singh, R. Patel, Micellization behavior of the amphiphilic drug promethazine hydrochloride with 1-decyl-3-methylimidazolium

[47]

Pr e-

chloride and its thermodynamic characteristics, J. Mol. Liq. 198 (2014) 341-346. M. Rahman, M.A. Hoque, M. A. Khan, M.A. Rub, A.M. Asiri, Effect of different additives on the phase separation behavior and thermodynamics of p-tert-alkylphenoxy poly (oxyethylene) ether in absence and presence of drug, Chinese J. Chem. Eng. 26

[48]

M.R.

Molla,

M.A.

al

(2018) 1110-1118 Rub,

urn

tetradecyltrimethylammonium

A.

Ahmed,

bromide

and

M.A.

Hoque,

Interaction

between

benzyldimethylhexadecylammonium

chloride in aqueous/urea solution at various temperatures: an experimental and theoretical investigation, J. Mol. Liq. 238 (2017) 62–70. M.A. Rub, N. Azum, F. Khan, A.M. Asiri, Aggregation of sodium salt of ibuprofen and

Jo

[49]

sodium taurocholate mixture in different media: a tensiometry and fluorometry study, J. Chem. Thermodyn. 121 (2018) 199–210. [50]

M.A. Rub, N. Azum, A.M. Asiri, Binary mixtures of sodium salt of ibuprofen and selected bile salts: interface, micellar, thermodynamic, and spectroscopic study, J. Chem. Eng. Data 62 (2017) 3216–3228.

[51]

S.M.A. Ahsan, M.R. Molla, M.S. Rahman, M.F. Hossain, S.M. Wabaidur, M.A. Hoque, M.A. Rub, M.A. Khan, Investigation of the interaction of levofloxacin hemihydrate with surfactants in the occurrence of salts: Conductivity and cloud point measurement, J. Mol. Liq. 274 (2019) 484–496.

[52]

J.J.H. Nusselder, J.B. Engberts, Toward a better understanding of the driving force for micelle formation and micellar growth, J. Colloid Interface Sci. 148 (1992) 353–361.

[53]

L.-J. Chen, S.-Y. Lin, C.-C. Huang, Effect of hydrophobic chain length of surfactants on enthalpy-entropy compensation of micellization, J. Phys. Chem. B 102 (1998) 4350– 4356.

25

Journal Pre-proof [54]

M.A. Hoque, M.-O.-F. Patoary, M.M. Rashid, M.R. Molla, M.A. Rub, Physico-chemical investigation of the mixed micelle formation between tetradecyltrimethylammonium bromide and dodecyltrimethylammonium chloride in water and aqueous solution of sodium chloride, J. Sol. Chem. 46 (2017) 682–703.

[55]

I. Jelesarov, H.R. Bosshard, Isothermal titration calorimetry and differential scanning calorimetry as complementary tools to investigate the energetic of biomolecular recognition, J. Mol. Recognit. 12 (1999) 3–18.

[56]

S.K. Shivaji, A. K.. Rakshit, Investigation of the properties of decaoxyethylene n-dodecyl ether, C12E10, in the aqueous sugar-rich region, J. Surf. Deterg. 7 (2004) 305-316.

[57]

M. Rahman, S. J. Anwar, M. R. Molla, S. Rana, M. A. Hoque, M. A. Rub, D. Kumar, Influence of alcohols and varying temperatures on the interaction between drug ceftriaxone sodium trihydrate and surfactant: A multi-techniques study, J. Mol. Liq. 292 (2019) 111322. A. Rakshit, B. Sharma, The effect of amino acids on the surface and thermodynamic

pro of

[58]

properties of poly [oxyethylene (10)] lauryl ether in aqueous solution, Colloid Polym. Sci. 281 (2003) 45–51. [59]

R. Lumry, S. Rajender, Enthalpy–entropy compensation phenomena in water solutions of

Pr e-

proteins and small molecules: a ubiquitous properly of water, Biopolymers 9 (1970) 1125–1227. [60]

G. Sugihara, M. Hisatomi, Enthalpy–entropy compensation phenomenon observed for different surfactants in aqueous solution, J. Colloid Interface Sci. 219 (1999) 31–36. M. Rahman, M.A. Khan, M.A. Rub, M.A. Hoque, A.M. Asiri, Investigation of the effect

al

[61]

of various additives on the clouding behavior and thermodynamics of polyoxyethylene

urn

(20) sorbitan monooleate in absence and presence of ceftriaxone sodium trihydrate drug, J. Chem. Eng. Data 62 (2017) 1464-1474. [62]

M.A. Hoque, A. Mitu, M.-O.-F. Patoary, D.M.S. Islam, Physicochemical studies on

Jo

effect of additives on clouding behavior and thermodynamics of polyoxyethylene (20) sorbitan monooleate, Indian J. Chem. A 55 (2016) 793-802. [63]

R.K. Mahajan, J. Chawla, M.S. Bakshi, Depression in the cloud point of Tween in the presence of glycol additives and triblock polymers, Colloid Poly. Sci. 282 (2004) 11651168.

[64]

V.B. Jadhav, T.J. Patil, Influence of polyvinyl sulphonic acid (PVSA) on the thermodynamics of clouding behaviour of non-ionic surfactant Tween 80, Oriental J. Chem. 26 (2010) 623-627.

[65]

Z. Yuanyuan, C. Yang, F. Baishan, Cloning and sequence analysis of the dhaT gene of the 1, 3-propanediol regulon from Klebsiella pneumoniae, Biotechnology Letters 26 (2004) 251-255.

[66]

A.B. Mandal, S. Ray, A.M. Biswas, S.P. Moulik, Physicochemical studies on the characterization of Triton X 100 micelles in an aqueous environment and in the presence of additives, J. Phys. Chem. 84 (1980) 856-859.

26

Journal Pre-proof [67]

R.C. da Silva, W. Loh, Effect of additives on the cloud points of aqueous solutions of ethylene oxide–propylene oxide–ethylene oxide block copolymers, J. Colloid Interface Sci. 202 (1998) 385-390.

[68]

J.-L. Li, D.-S. Bai, B.-H. Chen, Effects of additives on the cloud points of selected nonionic linear ethoxylated alcohol surfactant, Colloids and Surfaces A: Physicochemical Eng. Asp. 346 (2009) 237-243.

[69]

D. Kumar, M.A. Rub, Effect of anionic surfactant and temperature on micellization behavior of promethazine hydrochloride drug in absence and presence of urea, J. Mol. Liquids 238 (2017) 389–396.

[70]

D. Kumar, S. Hidayathulla, M.A. Rub, Association behavior of a mixed system of the antidepressant drug imipramine hydrochloride and dioctyl sulfosuccinate sodium salt: Effect of temperature and salt, J. Mol. Liquids 271 (2018) 254-264.

[71]

J. M. Bolivar, J. Aguiar, C. C Ruiz. Growth and hydration of Triton X-100 micelles in

[72]

pro of

monovalent alkali salts: a light scattering study, J. Phy. Chem. B 106 (2002) 870-877. L.E. Buckingham, M. Balasubramanian, R.M. Emanuele, K.E. Clodfelter, J.S. Coon, Comparison of solutol HS 15, Cremophor EL and novel ethoxylated fatty acid surfactants as multidrug resistance modification agents, Int. J. cancer. 62 (1995) 436-442. K. Shinod, H. Taked, The effect of added salts in water on the hydrophile-lipophile

Pr e-

[73]

balance of nonionic surfactants: the effect of added salts on the phase inversion temperature of emulsions, J. Colloid Inter. Sci. 32 (1970) 642-646. [74]

R. Heusch, Structures in surfactant/water mixtures and their use in blotechnology, BTF:

[75]

al

Biotech-Forum 3 (1986) 1-18.

D. Blankschtein, G.M. Thurston, G.B. Benedek, Phenomenological theory of equilibrium

(1986) 7268-7288. [76]

urn

thermodynamic properties and phase separation of micellar solutions, J. Chem. Phy. 85 Ç. Batıgöç, H. Akbaş, M. Boz, Thermodynamics of non-ionic surfactant Triton X-100-

1803. [77]

Jo

cationic surfactants mixtures at the cloud point, J. Chem. Thermodyn. 43 (2011) 1800-

S. Mahajan, A. Shaheen, T.S. Banipal, R.K. Mahajan, 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. 55 (2010) 3995-4001.

[78]

M.A. Rub, N. Azum, F. Khan, A.M. Asiri, Surface, micellar, and thermodynamic properties of antidepressant drug nortriptyline hydrochloride with TX-114 in aqueous/urea solution, J. Phys. Org. Chem. 30 (2017) e3676.

[79]

R. Amin, M.R. Molla, S. Rana, M.A. Hoque, M.A. Rub, M. Kabir, A.M. Asiri, Influence of electrolytes/urea on the interaction of tetradecyltrimethylammonium bromide and antibiotic levofloxacin hemihydrate drug, Phys. Chem. Liq. 57 (2019) 703-719.

[80]

W. Kauzmann, Some Factors in the interpretation of protein denaturation1, Advances in Protein Chem. 14 (1959) 1-63.

[81]

C. Bahal, H. Kostenbauder Interaction of preservatives with macromolecules V binding of chlorobutanol, benzyl alcohol, and phenylethyl alcohol by nonionic agents, J. Pharm. Sci. 53 (1964) 1027-1029. 27

Journal Pre-proof [82]

J.M. Hierrezuelo, J. A. M-. Bolívar, C.C. Ruiz, An energetic analysis of the phase separation in non-ionic surfactant mixtures: the role of the head group structure, Entropy. 16 (2014) 4375-4391.

[83]

A.Z. Naqvi, M.A. Rub, Kabir-ud-Din. Study of phospholipid-induced phase-separation in amphiphilic drugs, Colloid J. 77 (2015) 525-531.

[84]

M. Jan, A.A. Dar, A. Amin, N. Rehman, G.M. Rather, Clouding behavior of nonionic– cationic and nonionic–anionic mixed surfactant systems in presence of carboxylic acids and their sodium salts, Colloid Poly. Sci. 285 (2007) 631-640.

[85]

T. Iwanaga, H. Kunieda, Effect of added salts or polyols on the cloud point and the liquid-crystalline structures of polyoxyethylene-modified silicone, J. Colloid Interface Sci. 227 (2000) 349-355.

[86]

M.B. Khan, M.A. Hoque, D.S. Islam, Physicochemical investigation of the clouding behavior and thermodynamics of p-tert-alkylphenoxy poly (oxyethylene) ether micelles

177-182. [87]

pro of

in aqueous environment and in the presence of diols, J. Chem. Thermodyn. 89 (2015)

D. Robins, I. Thomas, The effect of counter ions on micellar properties of 2dodecylaminoethanol salts: I. Surface tension and electrical conductivity studies, J.

M.A.R. Khan, M.R. Amin, M. Rahman, M.A. Rub, M.A. Hoque, M.A. Khan, A.M. Asiri, 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, J. Chem.

urn

al

Eng. Data 64 (2019) 668-675.

Jo

[88]

Pr e-

Colloid Interface Sci. 26 (1968) 407-414.

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Journal Pre-proof Declaration of competing interest

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pro of

The authors have declared that no competing interests exist.

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Author Statement Conceptualization: Md. Ruhul Amin, Mohammad Robel Molla, Shahina Akter, Md. Masud Alam, Md. Anamul Hoque, Mohammed Abdullah Khan Investigation: Sk. Md. Ali Ahsan, Md. Ruhul Amin, Mohammad Robel Molla, Shahina Akter, Md. Anamul Hoque Validation: Sk. Md. Ali Ahsan, Md. Ruhul Amin, Shahina Akter, Md. Masud Alam, Malik Abdul Rub, Md. Anamul Hoque, Mohammed Abdullah Khan Formal analysis: Sk. Md. Ali Ahsan, Mohammad Robel Molla, Malik Abdul Rub, Md. Anamul Hoque, Mohammed Abdullah Khan Methodology: Sk. Md. Ali Ahsan, Mohammad Robel Molla, Shahina Akter, Md. Masud Alam, Malik Abdul Rub, Md. Anamul Hoque Project administration: Mohammad Robel Molla, Md. Anamul Hoque, Mohammed Abdullah

pro of

Khan

Visualization: Malik Abdul Rub, Naved Azum, Abdullah M. Asiri

Supervision: Malik Abdul Rub, Md. Anamul Hoque, Mohammed Abdullah Khan Writing – original draft: Sk. Md. Ali Ahsan, Md. Ruhul Amin, Mohammad Robel Molla, Md.

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Masud Alam, Malik Abdul Rub, Md. Anamul Hoque, Mohammed Abdullah Khan Writing – review & editing: Sk. Md. Ali Ahsan, Nora Hamad Al-Shaalan, Md. Ruhul Amin,

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Malik Abdul Rubd, Saikh Mohammad Wabaidur, Md. Anamul Hoque

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Highlights: 

Interaction of moxifloxacin hydrochloride (MFH), SDS and Tw-80 were studied.



Critical micelle concentrations are obtained to be dependent on temperature.



Effect of salts on the critical micelle concentrations of surfactant is observed.



Micellization of SDS/ SDS+drug is found spontaneous while clouding of Tw-80/Tw80+drug is found nonspontaneous. The ∆H0m and ∆S0m show that hydrophobic and electrostatic interactions are present

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pro of

between SDS and MFH.

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

31