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Evaluation of the biological activity of the prepared nonionic polymeric based on the acrylated polyethylene glycol
Journal of Molecular Liquids 288 (2019) 111010
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Evaluation of the biological activity of the prepared nonionic polymeric based on the acrylated polyethylene glycol Ahmed I. Adawy a,⁎, Zizi I. Abdeen b, Nasser R. Abdel Rahman b, Hanan E.-S. Ali a a b
Surfactants Laboratory, Petrochemicals Department, Egyptian Petroleum Research Institute (EPRI), 11727 Cairo, Egypt Polymer Laboratory, Petrochemicals Department, Egyptian Petroleum Research Institute (EPRI), 11727 Cairo, Egypt
a r t i c l e
i n f o
Article history: Received 9 February 2019 Received in revised form 10 May 2019 Accepted 19 May 2019 Available online 22 May 2019 Keywords: Nonionic polymeric surfactant Biological activity Surface tension Surface parameters
a b s t r a c t Nonionic polymeric surfactants were prepared by acrylated of poly (ethylene glycol) (PEG) esterfied with oleic or palmitic acid. The unique structural features of these polymeric surfactants were investigated by using Fourier transformer infrared spectroscopy (FTIR) and X-ray diffraction (XRD). The surface tension at different temperatures of these compounds was investigated. The surface parameters including critical micelle concentration (CMC), maximum surface excess (Γmax), minimum surface area (Amin), efficiency (Pc20) and effectiveness (πCMC) were studied and calculated. The biological activity of these prepared compounds was evaluated and determined via the inhibition zone diameter against different microorganisms. From the outcomes, it was noticed that these compounds possess superior surface properties and perfect antimicrobial action. © 2019 Elsevier B.V. All rights reserved.
1. Introduction Several microbiologically sensitive environments require a microbial growth introduction where the wet surfaces provide favorable conditions for the microorganisms proliferation [1–3]. Mean of a disinfection method is to decrease the workable microorganisms and to stop the growing of microbe on the surfaces [4,5]. Referring to Russell [6] and Simões [7], it was found that the investigation was needed urgently to increase fully the inhibitor nature and lethal effects of each biocides and disinfectants. The order of possibilities sites of cell multi-target may be form a significant feature of such studies. With respect to the European Standard [8], the suggested method to estimate the efficiency of chemical antimicrobial is stood on investigation using suspended cells. New types of agents named surface active agents (surfactants) have less power as medium germicide to harm human tissues. They have a power to reduce surface and interfacial tensions of liquids so, they can utilize in blends of purifying products [9,10]. These chemicals have a great tendency to wet surfaces, get into the soil and solubilize fatty compounds [11]. Specially, surfactants have the ability to utilize as antimicrobial agents owing to their amphiphilic kind and reaction with the membranes of microorganisms [12,13]. Nonionic surfactants have a lot of applications in industry, e.g., cosmetics, detergents, corrosion inhibitors and biocides as a result of their low cost. Also, their surface properties can be improved by addition of other types of surfactants [14].
⁎ Corresponding author. E-mail address: [email protected] (A.I. Adawy).
https://doi.org/10.1016/j.molliq.2019.111010 0167-7322/© 2019 Elsevier B.V. All rights reserved.
It was found that in aqueous solution, the nonionic surfactants do not produce ions, so, they are well-matched with other kinds and are brilliant applicants to go through mixtures of complex, since it was created in several marketable outputs. Today, they are available in a huge diversity of industrial and domestic products in powdered in addition to liquid formulations. Though, the polyethoxylated products are dominated in the market, which are the chain of polyethylene glycols has those of hydrophilic groups, is prepared by polycondensation of ethylene oxide with an amine or hydroxyl group. Generally, the acceptable, that the industrial applicability of nonionic surfactants was improved by the presence of a polyoxyethylene chain. Such as, in the textile industry as soon as using surfactants as dyeing auxiliaries, polyoxyethylene nonionic surfactants provide a good wetting, emulsifying and dye dispersion ability and enhanced dyeing behavior [15–17]. In this paper, nonionic polymeric surfactants were prepared by acrylated of poly (ethylene glycol) (PEG) esterfied with oleic or palmitic acid. The syntheses of these polymeric surfactants were reported and their surface activities and their structures were investigated. Also, their biological activity was evaluated and determined by means of the diameter of inhibition zone against diverse microorganisms. 2. Experimental procedure 2.1. Materials Acrylic acid, thionyl chloride, PEG (Mw = 600) and trimethyl amine were Merck products. Fatty acids (palmitic acid and oleic acid) were bringing from Aldrich (Steinheim, Germany). The solvents utilized are of analytical grade and the utilized water was distilled twice.
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tension of several concentrations scope of 0.1 to 1.9 × 10−5 mol/l at different temperature (25, 35, 45 and 55 °C) was measured. 2.6.2. Surface parameters of the synthesized compounds a) Critical micelle concentration (CMC)
The scores of the critical micelle concentration of the synthesized compounds were strong-minded using the surface tension technique. The scores of the resulted surface tension were plotted against the corresponding concentrations. The interrupt, change in the SC curves clear the CMC. b) Effectiveness (πCMC) Scheme 1. Nonionic acrylated oleate polyethylene glycol (Ia) and acrylated palmitate polyethylene glycol (IIa), n = Ethylene glycol repeated units (Mw = 600).
2.2. Synthesis of acrylated acid chloride (RCOCL) To synthesis the acrylated acid chloride, (RCOCL) the thionyl chloride (0.5 mol) was added drop wise to 1 mol of the equivalent acrylic acid in accordance with the reaction explained by Ralston et al. [18] During the thionyl chloride addition, the reaction mixture was cooled to 0–5 °C. The reaction temperature was raised to 10 °C for 2 h, after the addition was completed. 2.3. Synthesis of the polyethylene glycol esters Polyethylene glycol, Mw = 600, (0.10 mol, 60 g) and 0.10 mol of fatty acids (palmitic acid, 25.64 g, oleic acid, and 28.24 g) were reacted in xylene (150 ml) using Dean-Stark connection and condenser. The reaction was progressed under heating, condition (140 °C) to result 1.8 ml of water. At last, the solvent was evaporated under reduced pressure at 70 °C. The obtained esters were designated as TS (Ia) and TP (IIa), for oleate and palmitate respectively, Scheme 1. 2.4. Preparation of the nonionic polymeric surfactants The nonionic polymeric surfactants were prepared by acrylated of poly (ethylene glycol) (PEG) esterfied with oleic TS or palmitic acid TP. TS or TP (30 mmol) was soluble using chloroform (25 ml) with stirring and a catalyst such as trimethyl amine was added as a one drop. An equivalent mole quantity of acrylated acid chloride (RCOCL) was added drop wise during 3 min at 0–5 °C. At this temperature, stirring was continuously for 24 h. At achievement of the reaction, under vacuum, the solvent was evaporated [19].
πCMC is the difference between the surface tension of the pure water (γo) and the surface tension of the surfactant solution (γ) at the critical micelle concentration. πCMC ¼ γo− γCMC
c) Efficiency (Pc20)
Efficiency (Pc20) is determined by the concentration (mol/l) of the surfactant solutions capable to suppress the surface tension by 20 mN/ m. d) Maximum surface excess Γmax
The scores of the maximum surface excess Γmax calculated from the surface or interfacial data by utilizing of the Gibbs equation [20]. Γmax ¼ −1=2:303 RT ðδ γ=δ log CÞT
ð2Þ
where Γmax: maximum surface excess in mole/cm2 R: universal gas constant 8.31 × 107 ergs mole−1 K−1 T; absolute temperature (273.2 + °C) δγ: surface pressure in dyne/cm C:surfactant concentration (δγ/δ log C)T: is the slope of a plot surface tension vs. –log concentration curves below CMC at constant temperature.
2.5. Characterization of the prepared nonionic polymeric surfactants The chemical structure of the examined surfactants was obtained, by using the Fourier transform infrared spectroscopy. The investigation was done at room temperature on FT-IR, JASCO, and Nicolet IS-10 (made in Japan) spectrometer using a KBr disc method with a spectral resolution of 4 cm − 1 over the wave number range of 400–4000 cm−1. Also, X-ray diffraction (XRD) studies were performed to recognize the presence of the crystalline species. XRD measurements were done in the 2θ angle in the range of 5–70°, on a Philips model PW 1050 diffractometer, using CuK radiation source refined by a graphic monochromatic operating at capacity of 30 kV and a current of 40 mA. 2.6. Evaluation method of the surface active properties 2.6.1. Surface tension The surface tension of the synthesized compounds solutions was measured using Du-Nouy Tensiometer (Kruss type 6). The surface
ð1Þ
Fig. 1. FTIR of non-ionic polymeric surfactants, A) Ia and B) IIa.
A.I. Adawy et al. / Journal of Molecular Liquids 288 (2019) 111010
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The average area (in square angstrom) occupied by each molecule adsorbed on the interface [21] is given by: Amin ¼ 1016 =Γmax N
ð3Þ
Γmax: maximum surface excess in mole/cm2 N: Avogadro's number 6.023 × 1023 f) Thermodynamic parameters of micellization and adsorption:
The thermodynamic parameters of adsorption and micellization of the synthesized nonionic surfactants were calculated according to the Gibb's adsorption equations number (4) as follows [22]: Fig. 2. The XRD patterns of synthesized compounds, A) Ia and B) IIa.
e) Minimum surface area (Amin)
The area per molecule at the interface gives information on the degree of packing and the orientation of the adsorbed surfactant molecule.
ΔGO mic ¼ RT ln ðCMC Þ ΔGO ads ¼ ΔGO mic –6:023 X10−1X π CMC X Amin ΔSmic ¼ −d ΔGO mic =ΔT ΔSads ¼ −d ΔGO ads =ΔT ΔHmic ¼ ΔGO mic þ T ΔSmic ΔHads ¼ ΔGO ads þ T ΔSads
Fig. 3. Surface tension vs. log concentration of synthesized compounds at: (a) 25 °C, (b) 35 °C, (c) 45 °C, (d) 55 °C.
ð4Þ
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2.7. Antimicrobial activity of the synthesized compounds The antimicrobial activity of the synthesized nonionic surfactants was measured separately in opposition to a large collection of microorganisms earlier isolated in Biotechnology Lab. in Institute of Egyptian Petroleum Research (EPRI) from diverse petroleum contaminated environments by means of dose equal to 1 mg/ml by the diffusion agar method. The tested compounds were evaluated against Gram −ve bacteria (Escherichia coli and Pseud. aeruginosa), Gram +ve bacteria (Bacillus subtilis and Staph. aureus) and Yeast (Candida albicans) and Filamentous Fungus (Aspergillus niger). The bacteria and yeast were cultivated on nutrient agar while the fungus was cultivated on Czapek's Dox agar environment. The negative control was DMF displayed no antimicrobial activity against the checking microorganism and the positive control was Erythromycin for bacteria and Metronidazole for yeast and fungus. All examinations were carried out in repeats and the recorded information is the mean of the gained outcomes. 3. Results and discussion 3.1. Structural characterizations IR spectra of A) Ia and B) IIa are as follows in Fig. 1. The spectra reveal that the several absorption bands as follow: The broad bands around 3397 cm−1, area owing to the O\\H stretching of un-esterified carboxylic acid groups (-COOH) as stated in (Kooter, 1997) [23], while those at 2920–2730 cm−1 is related to C\\H stretching asymmetric and symmetric vibrations respectively in aliphatic according to (Hong, 2009) [24]. The moderately sharp peak around 3005 cm−1, which is superimposed with the O\\H stretching band, is due to the C\\H stretching in vinyl moiety. The appearance of bands at 2069–1938 cm−1 is due to overtone, while the absorption bands at 1627-1536 cm−1 are according to C_C respectively, the bands of CH2 bending around 1471–1456 cm−1, the absorption bands at 1398.3–1398.4 cm−1 are related to CH2 = CH– group and many medium bands in the area 1400–1200 cm−1 was assigned to the C\\H bending and wagging modes, and O\\H bending mode. A strong intensity bands at 1088–1038 cm−1 was assigned to the stretching mode of the C\\O bond. The frequency at 2739 cm−1 was attributed to the C\\H stretching mode of the aliphatic chain of the fatty acids. The intense IR band at 1728 cm−1 and 1248 cm−1 corresponded to C_O and C\\O stretching mode, respectively, of acrylated of poly (ethylene glycol) (PEG) esterfied with oleic or palmitic acid. Fig. 2 shows the XRD pattern of A) Ia and B) IIa samples under ambient conditions. The broad peak at 2θ of 20° was revealed the existence of an amorphous phase of acrylated of PEG esterfied with palmitic acid. This is indicating the most acid is interchelated and used into network of polymer but the characteristic sharp peak at 2θ of 23° indicates that the is some amount of oleic acid present without reacting in the sample and esterfication the with oleic acid give the best results. 3.2. Surface properties 3.2.1. Surface tension It was measured for aqueous solutions of the synthesized non-ionic polymeric surfactants using diverse concentrations (0.1 to 1.9 × 10−5 mol/l) and at various temperatures 25, 35, 45 and 55 °C. And the data are represented in surface tension-concentration curves as displayed in Fig. 3. As a result of hydrophobicity, the surface tension decrease by raising the concentration of the surfactants due to growing the migration of the surfactant molecules from the bulky to the interface of the solution [25]. In addition the surface tension values minimized as the temperature raise from 25 to 55 °C due to the surfactants begin to be lack of solubility as the temperature raises because of the dehydration of the hydrophobic chain from the bulky to concentrate in the surface [26–28].
Table 1 Surface properties of polymeric surfactants at 25, 35, 45, 55 °C. Surfactant
CMC X 10−3, Mole/l
πCMC, mN/m
Pc20 X 10−4, Mole/l
Γmax X 10−10, Mole/cm2
Amin, nm2
Ia IIa 25 °C Ia IIa 35 °C Ia IIa 45 °C Ia IIa 55 °C
1.1 1.3 0.9 1 0.7 0.8 0.6 0.7
35 32 36 35 37 36 38 37
1.48 1.53 1.29 1.52 1.13 1.31 1.12 1.21
3.44 2.92 2.86 2.81 2.77 2.76 2.68 2.55
0.48 0.57 0.58 0.59 0.59 0.6 0.62 0.65
3.2.2. The critical micelle concentration (CMC) Critical micelle concentration values of the synthesized polymeric surfactant were determined by plotting the surface tension (γ) of surfactant solutions versus their bulk concentrations in mole/l at 25 °C, 35 °C, 45 °C and 55 °C. The values of the CMC listed in the Table 1 are showing a decrease in the CMC with increasing the alkyl chain length, i.e. from palmitate (IIa) to oleate (Ia) this is due to the repulsion force presence in the bulk of the solution increases with increasing the alkyl chain length leading to the surfactant molecules moving to the surface and the solution needs less molecules to reach the equilibrium state at which the micelles are present [29,30]. Moreover, the CMC decreases as the temperature increases due to the growing of temperature making minimize in the hydrophilic group hydration that support the micillization. Conversely, the rising in temperature causing disturbance of the organized water molecules encircle the hydrophobic group, an action that dislike micillization. The comparative amount of these two reverse actions, decided if the CMC growing or minimized over a particular temperature zone. As shown in the Table 1 the values of the CMC decrease upon rising the temperature, means that; there is an enhancement in the micellization.
3.2.3. Effectiveness (ПCMC) The supreme surfactant is one that offers the maximum decreasing in surface tension for a critical micelle concentration (CMC). As shown in the results of the effectiveness in Table 1 when the length of the alkyl chain and the temperature growing, there is a rise in the effectiveness of the polymeric surfactants owing to increasing the hydrophobicity. Compound (Ia) at 55 °C was found the most powerful one, it produces 38 mN/m; it attained the highest decreasing of surface tension at (CMC).
3.2.4. Efficiency (Pc20) Efficiency scores of the synthesized surfactants are displayed in the Table 1. From these scores it was noticed that; at increasing the alkyl chain length and temperature, the efficiency decreases as a result of rapid formation of mono layer of surfactants on the surface.
Table 2 Thermodynamic parameters of micellization of polymeric surfactants at 25, 35, 45, 55 °C. Surfactant
ΔG°mic, KJ/mol
ΔHmic, KJ/mol
Ia IIa 25 °C Ia IIa 35 °C Ia IIa 45 °C Ia IIa 55 °C
−16.9 −16.5 −17.9 −17.7 −19.2 −18.8 −20.2 −19.8
−46.7 −52.2 −48.8 −54.7 −51 −50.7 −53 −52.6
A.I. Adawy et al. / Journal of Molecular Liquids 288 (2019) 111010 Table 3 Thermodynamic parameters of adsorption of polymeric surfactants at 25, 35, 45, 55 °C. Surfactant
ΔG°ads, KJ/mol
ΔHads, KJ/mol
Ia IIa 25 °C Ia IIa 35 °C Ia IIa 45 °C Ia IIa 55 °C
−27 −27.4 −30.5 −30.1 −32.2 −31.8 −34 −34.3
−131.4 −107.9 −138.4 −113.3 −89.5 −111.4 −93.1 −116.4
3.2.5. Maximum surface excess (Γmax) The values of Γmax are represented in Table 1. In general, the maximum surface excess Γmax enlarges by growing the alkyl chain length owing to increase the repulsion forces with the water phase so the surfactant molecules concentrate in the interface. 3.2.6. Minimum surface area (Amin) The minimum area per molecule at the water/air interface for the synthesized surfactants is recorded in Table 1. The minimum surface area (Amin) reduces with growing in the chain length of the hydrophobic part in the surfactant molecules owing to the elevated accumulation of these molecules at the interface and a minor obtainable area per molecule. 3.2.7. Standard free energies of micellization and adsorption (ΔG°mic, ΔG°ads) As shown in the Tables 2, 3, the scores of ΔGmic and ΔGads are always negatives referring that the two operations are spontaneous; however, there is a high raise in the negative value of ΔGads compared to those of micellization. This means that the inclination of the molecules to be adsorbed at the interface [31]. 3.3. Antimicrobial activity of the prepared compounds The mechanism of the biocide is accumulation onto the outer section of the cells due to existing of the polar groups in their structure which lower their osmotic balance leading to death of the cells as shown in Table 4 [32]. The skeleton structure of the surfactant affected on its biological activity [33,34]. One of the highly active biocide is the nonionic surfactants because of their action mode; the electronegativity of the oxygen atoms forces the nonionic surfactants from approach to the connected area. The existing hydrogen bonds will be disrupted because the oxygens are hydrogen bond acceptors but the connected area may not be special. In addition to hydrophobic and electrostatic forces, the hydrogen bonding made the intrinsic proteins that surrounding the membranes to be held in position, and also the breaking of membranes by proteins is mediated by the hydrogen bonding. The hydrophilic moiety of the nonionic surfactants (polyethoxy) connects to the hydrophilic portion of the membrane surface through the intermolecular hydrogen bond.
Table 4 The results of biological activity of the synthesized nonionic surfactants against different microorganisms at 1 mg/ml measured by mm. Test organism
Bacillus subtilis
Staph. aureus
Escherichia coli
Pseud. aeruginosa
Candida albicans
Aspergillus niger
21 20 31
20 20 32
19 18 32
15 20 33
25 30 28
15 15 27
Compound ID Ia IIa Reference
5
Although this is the way of the antimicrobial action as a surfactant, the connected area of the biocide is unknown [35,36]. The accumulation of the biocide at the different substrates (aqueous or microorganism's membranes) increasing with increase the concentration of the nonionic surfactants. Hence, the potent action of the molecules is increased as a result of their aggregate at the membrane of the cells [37,38]. 4. Conclusions The main conclusions of this research present in the following points: 1. The synthesized non-ionic polymeric surfactants have superior surface activity. 2. The thermodynamic parameters of adsorption and micellization showed the inclination of these compounds toward adsorption at the interfaces and also micellization in the bulky of the solutions. 3. The activity against microbes for these compounds was high against of diverse microorganisms as a result we could utilize these novel surfactants as biocides. Acknowledgments The authors are thankful of the Egyptian Petroleum Research Institute (EPRI) for technical support. References [1] I.S.I. AL-Adham, A.J. Dinning, I.M. Eastwood, P. Austin, P.J. Collier, Cell membrane effects of some common biocides, J. Ind. Microbiol. Biotechnol. 21 (1998) 6–10, https://doi.org/10.1038/sj.jim.2900554. [2] Copello, G.J., Teves, S., Degrossi, J., D'Aquino, M., Desimone, M.F. and Diaz, L.E. Antimicrobial activity on glass materials subject to disinfectant xerogel coating. J. Ind. Microbiol. Biotechnol. 33 (2006) 343–348; doi:https://doi.org/10.1007/s10295005-0066-z. [3] A.J. McBain, A.H. Rickard, P. Gilbert, Possible implications of biocide accumulation in the environment on the prevalence of bacterial antibiotic resistance, J. Ind. Microbiol. Biotechnol. 29 (2002) 326–330, https://doi.org/10.1038/sj.jim.7000324. [4] M. Simões, M.O. Pereira, M.J. Vieira, Effect of mechanical stress on biofilms challenged by different chemicals, Water Res. 39 (2005) 5142–5152, https://doi.org/ 10.1016/j.watres.2005.09.028. [5] M. Simo˜es, M.O. Pereira, M.J. Vieira, Validation of respirometry as a short-term method to assess the toxic effect of a biocide, Biofouling 47 (2005) 217–223, https://doi.org/10.1080/08927010 500066982. [6] A.D. Russell, Mechanisms of antimicrobial action of antiseptics and disinfectants: an increasingly important area of investigation, J. Antimicrob. Chemother. 49 (2002) 597–599, https://doi.org/10.1093/jac/49.4.597. [7] M. Simões, M.O. Pereira, I. Machado, L.C. Simões, M.J. Vieira, Comparative antibacterial potential of selected aldehyde-based biocides and surfactants against planktonic Pseudomonas fluorescens, J. Ind. Microbiol. Biotechnol. (9) (2006) 741–749, https:// doi.org/10.1007/s10295-006-0120-5. [8] European Standard EN 1276, Chemical Disinfectants and Antiseptics—Quantitative Suspension Test for the Evaluation of Bactericidal Activity of Chemical Disinfectants and Antiseptics Used in Food, Industrial, Domestic, and Institutional Areas—Test Method and Requirements (Phase 2, Step 1), 1997. [9] N. Christofi, I.B. Ivshina, Microbial surfactants and their use in field studies of soil remediation, J. Appl. Microbiol. 93 (2002) 915–929, https://doi.org/10.1046/j.13652672.2002.01774.x. [10] H. Jerabkova, B. Kralova, J. Nahlik, Biofilm of Pseudomonas C12B on glass support as catalyitic agent for continuous SDS removal, Int. Biodeterior. Biodegradation 44 (1999) 233–241, https://doi.org/10.1016/S0964-8305(99)00084-0. [11] E.R. Glover, R.R. Smith, V.M. Jones, K.S. Jackson, C.C. Rowlands, An EPR investigation of surfactant action on bacterial membranes, FEMS Microbiol. Lett. 177 (1999) 57–62, https://doi.org/10.1111/j.1574-6968.1999.tb13713.x. [12] M. Vaara, Agents that increase the permeability of the outer membrane, Microbiol. Rev. 56 (1992) 395–411. [13] S. Schreier, S. Malheirosb, E. de Paulab, Surface active drugs: self-association and interaction with membranes and surfactants. Physicochemical and biological aspects, Biochim. Biophys. Acta Biomembr. 1508 (2000) 210–234, https://doi.org/10.1016/ S0304-4157(00) 00012-5. [14] A. Eissa, M. El Hefnawy, M. Deef Allah, Synthesis and evaluation of nonionic polymeric surfactants based on Acrylated polyethylene glycol, J. Surfactant Deterg. 16 (2013) 161–171, https://doi.org/10.1007/s11743-012-1381-9. [15] K.R.F. Cockett, Industrial Application of Surfactants, Royal Society of Chemistry, London, 1988 205. [16] J.C. Lopez-Montilla, M.A. James, D.D. Crisalle, D.O. Shah, Surfactant and protocols to induce spontaneous emulsification and enhance detergency, J. Surfactant Deterg. 8 (2005) 45–53, https://doi.org/10.1007/s11743-005-0329-3. [17] H.J. Liu, L.H. Lin, K.M. Chen, Polyethylene glycol/polydimethyl siloxane polyester products as leveling agents in nylon dyeing, Text. Res. J. 73 (2003) 583–590.
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Evaluation of the biological activity of the prepared nonionic polymeric based on the acrylated polyethylene glycol Ahmed I. Adawy a,⁎, Zizi I. Abdeen b, Nasser R. Abdel Rahman b, Hanan E.-S. Ali a a b
Surfactants Laboratory, Petrochemicals Department, Egyptian Petroleum Research Institute (EPRI), 11727 Cairo, Egypt Polymer Laboratory, Petrochemicals Department, Egyptian Petroleum Research Institute (EPRI), 11727 Cairo, Egypt
a r t i c l e
i n f o
Article history: Received 9 February 2019 Received in revised form 10 May 2019 Accepted 19 May 2019 Available online 22 May 2019 Keywords: Nonionic polymeric surfactant Biological activity Surface tension Surface parameters
a b s t r a c t Nonionic polymeric surfactants were prepared by acrylated of poly (ethylene glycol) (PEG) esterfied with oleic or palmitic acid. The unique structural features of these polymeric surfactants were investigated by using Fourier transformer infrared spectroscopy (FTIR) and X-ray diffraction (XRD). The surface tension at different temperatures of these compounds was investigated. The surface parameters including critical micelle concentration (CMC), maximum surface excess (Γmax), minimum surface area (Amin), efficiency (Pc20) and effectiveness (πCMC) were studied and calculated. The biological activity of these prepared compounds was evaluated and determined via the inhibition zone diameter against different microorganisms. From the outcomes, it was noticed that these compounds possess superior surface properties and perfect antimicrobial action. © 2019 Elsevier B.V. All rights reserved.
1. Introduction Several microbiologically sensitive environments require a microbial growth introduction where the wet surfaces provide favorable conditions for the microorganisms proliferation [1–3]. Mean of a disinfection method is to decrease the workable microorganisms and to stop the growing of microbe on the surfaces [4,5]. Referring to Russell [6] and Simões [7], it was found that the investigation was needed urgently to increase fully the inhibitor nature and lethal effects of each biocides and disinfectants. The order of possibilities sites of cell multi-target may be form a significant feature of such studies. With respect to the European Standard [8], the suggested method to estimate the efficiency of chemical antimicrobial is stood on investigation using suspended cells. New types of agents named surface active agents (surfactants) have less power as medium germicide to harm human tissues. They have a power to reduce surface and interfacial tensions of liquids so, they can utilize in blends of purifying products [9,10]. These chemicals have a great tendency to wet surfaces, get into the soil and solubilize fatty compounds [11]. Specially, surfactants have the ability to utilize as antimicrobial agents owing to their amphiphilic kind and reaction with the membranes of microorganisms [12,13]. Nonionic surfactants have a lot of applications in industry, e.g., cosmetics, detergents, corrosion inhibitors and biocides as a result of their low cost. Also, their surface properties can be improved by addition of other types of surfactants [14].
⁎ Corresponding author. E-mail address: [email protected] (A.I. Adawy).
https://doi.org/10.1016/j.molliq.2019.111010 0167-7322/© 2019 Elsevier B.V. All rights reserved.
It was found that in aqueous solution, the nonionic surfactants do not produce ions, so, they are well-matched with other kinds and are brilliant applicants to go through mixtures of complex, since it was created in several marketable outputs. Today, they are available in a huge diversity of industrial and domestic products in powdered in addition to liquid formulations. Though, the polyethoxylated products are dominated in the market, which are the chain of polyethylene glycols has those of hydrophilic groups, is prepared by polycondensation of ethylene oxide with an amine or hydroxyl group. Generally, the acceptable, that the industrial applicability of nonionic surfactants was improved by the presence of a polyoxyethylene chain. Such as, in the textile industry as soon as using surfactants as dyeing auxiliaries, polyoxyethylene nonionic surfactants provide a good wetting, emulsifying and dye dispersion ability and enhanced dyeing behavior [15–17]. In this paper, nonionic polymeric surfactants were prepared by acrylated of poly (ethylene glycol) (PEG) esterfied with oleic or palmitic acid. The syntheses of these polymeric surfactants were reported and their surface activities and their structures were investigated. Also, their biological activity was evaluated and determined by means of the diameter of inhibition zone against diverse microorganisms. 2. Experimental procedure 2.1. Materials Acrylic acid, thionyl chloride, PEG (Mw = 600) and trimethyl amine were Merck products. Fatty acids (palmitic acid and oleic acid) were bringing from Aldrich (Steinheim, Germany). The solvents utilized are of analytical grade and the utilized water was distilled twice.
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tension of several concentrations scope of 0.1 to 1.9 × 10−5 mol/l at different temperature (25, 35, 45 and 55 °C) was measured. 2.6.2. Surface parameters of the synthesized compounds a) Critical micelle concentration (CMC)
The scores of the critical micelle concentration of the synthesized compounds were strong-minded using the surface tension technique. The scores of the resulted surface tension were plotted against the corresponding concentrations. The interrupt, change in the SC curves clear the CMC. b) Effectiveness (πCMC) Scheme 1. Nonionic acrylated oleate polyethylene glycol (Ia) and acrylated palmitate polyethylene glycol (IIa), n = Ethylene glycol repeated units (Mw = 600).
2.2. Synthesis of acrylated acid chloride (RCOCL) To synthesis the acrylated acid chloride, (RCOCL) the thionyl chloride (0.5 mol) was added drop wise to 1 mol of the equivalent acrylic acid in accordance with the reaction explained by Ralston et al. [18] During the thionyl chloride addition, the reaction mixture was cooled to 0–5 °C. The reaction temperature was raised to 10 °C for 2 h, after the addition was completed. 2.3. Synthesis of the polyethylene glycol esters Polyethylene glycol, Mw = 600, (0.10 mol, 60 g) and 0.10 mol of fatty acids (palmitic acid, 25.64 g, oleic acid, and 28.24 g) were reacted in xylene (150 ml) using Dean-Stark connection and condenser. The reaction was progressed under heating, condition (140 °C) to result 1.8 ml of water. At last, the solvent was evaporated under reduced pressure at 70 °C. The obtained esters were designated as TS (Ia) and TP (IIa), for oleate and palmitate respectively, Scheme 1. 2.4. Preparation of the nonionic polymeric surfactants The nonionic polymeric surfactants were prepared by acrylated of poly (ethylene glycol) (PEG) esterfied with oleic TS or palmitic acid TP. TS or TP (30 mmol) was soluble using chloroform (25 ml) with stirring and a catalyst such as trimethyl amine was added as a one drop. An equivalent mole quantity of acrylated acid chloride (RCOCL) was added drop wise during 3 min at 0–5 °C. At this temperature, stirring was continuously for 24 h. At achievement of the reaction, under vacuum, the solvent was evaporated [19].
πCMC is the difference between the surface tension of the pure water (γo) and the surface tension of the surfactant solution (γ) at the critical micelle concentration. πCMC ¼ γo− γCMC
c) Efficiency (Pc20)
Efficiency (Pc20) is determined by the concentration (mol/l) of the surfactant solutions capable to suppress the surface tension by 20 mN/ m. d) Maximum surface excess Γmax
The scores of the maximum surface excess Γmax calculated from the surface or interfacial data by utilizing of the Gibbs equation [20]. Γmax ¼ −1=2:303 RT ðδ γ=δ log CÞT
ð2Þ
where Γmax: maximum surface excess in mole/cm2 R: universal gas constant 8.31 × 107 ergs mole−1 K−1 T; absolute temperature (273.2 + °C) δγ: surface pressure in dyne/cm C:surfactant concentration (δγ/δ log C)T: is the slope of a plot surface tension vs. –log concentration curves below CMC at constant temperature.
2.5. Characterization of the prepared nonionic polymeric surfactants The chemical structure of the examined surfactants was obtained, by using the Fourier transform infrared spectroscopy. The investigation was done at room temperature on FT-IR, JASCO, and Nicolet IS-10 (made in Japan) spectrometer using a KBr disc method with a spectral resolution of 4 cm − 1 over the wave number range of 400–4000 cm−1. Also, X-ray diffraction (XRD) studies were performed to recognize the presence of the crystalline species. XRD measurements were done in the 2θ angle in the range of 5–70°, on a Philips model PW 1050 diffractometer, using CuK radiation source refined by a graphic monochromatic operating at capacity of 30 kV and a current of 40 mA. 2.6. Evaluation method of the surface active properties 2.6.1. Surface tension The surface tension of the synthesized compounds solutions was measured using Du-Nouy Tensiometer (Kruss type 6). The surface
ð1Þ
Fig. 1. FTIR of non-ionic polymeric surfactants, A) Ia and B) IIa.
A.I. Adawy et al. / Journal of Molecular Liquids 288 (2019) 111010
3
The average area (in square angstrom) occupied by each molecule adsorbed on the interface [21] is given by: Amin ¼ 1016 =Γmax N
ð3Þ
Γmax: maximum surface excess in mole/cm2 N: Avogadro's number 6.023 × 1023 f) Thermodynamic parameters of micellization and adsorption:
The thermodynamic parameters of adsorption and micellization of the synthesized nonionic surfactants were calculated according to the Gibb's adsorption equations number (4) as follows [22]: Fig. 2. The XRD patterns of synthesized compounds, A) Ia and B) IIa.
e) Minimum surface area (Amin)
The area per molecule at the interface gives information on the degree of packing and the orientation of the adsorbed surfactant molecule.
ΔGO mic ¼ RT ln ðCMC Þ ΔGO ads ¼ ΔGO mic –6:023 X10−1X π CMC X Amin ΔSmic ¼ −d ΔGO mic =ΔT ΔSads ¼ −d ΔGO ads =ΔT ΔHmic ¼ ΔGO mic þ T ΔSmic ΔHads ¼ ΔGO ads þ T ΔSads
Fig. 3. Surface tension vs. log concentration of synthesized compounds at: (a) 25 °C, (b) 35 °C, (c) 45 °C, (d) 55 °C.
ð4Þ
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A.I. Adawy et al. / Journal of Molecular Liquids 288 (2019) 111010
2.7. Antimicrobial activity of the synthesized compounds The antimicrobial activity of the synthesized nonionic surfactants was measured separately in opposition to a large collection of microorganisms earlier isolated in Biotechnology Lab. in Institute of Egyptian Petroleum Research (EPRI) from diverse petroleum contaminated environments by means of dose equal to 1 mg/ml by the diffusion agar method. The tested compounds were evaluated against Gram −ve bacteria (Escherichia coli and Pseud. aeruginosa), Gram +ve bacteria (Bacillus subtilis and Staph. aureus) and Yeast (Candida albicans) and Filamentous Fungus (Aspergillus niger). The bacteria and yeast were cultivated on nutrient agar while the fungus was cultivated on Czapek's Dox agar environment. The negative control was DMF displayed no antimicrobial activity against the checking microorganism and the positive control was Erythromycin for bacteria and Metronidazole for yeast and fungus. All examinations were carried out in repeats and the recorded information is the mean of the gained outcomes. 3. Results and discussion 3.1. Structural characterizations IR spectra of A) Ia and B) IIa are as follows in Fig. 1. The spectra reveal that the several absorption bands as follow: The broad bands around 3397 cm−1, area owing to the O\\H stretching of un-esterified carboxylic acid groups (-COOH) as stated in (Kooter, 1997) [23], while those at 2920–2730 cm−1 is related to C\\H stretching asymmetric and symmetric vibrations respectively in aliphatic according to (Hong, 2009) [24]. The moderately sharp peak around 3005 cm−1, which is superimposed with the O\\H stretching band, is due to the C\\H stretching in vinyl moiety. The appearance of bands at 2069–1938 cm−1 is due to overtone, while the absorption bands at 1627-1536 cm−1 are according to C_C respectively, the bands of CH2 bending around 1471–1456 cm−1, the absorption bands at 1398.3–1398.4 cm−1 are related to CH2 = CH– group and many medium bands in the area 1400–1200 cm−1 was assigned to the C\\H bending and wagging modes, and O\\H bending mode. A strong intensity bands at 1088–1038 cm−1 was assigned to the stretching mode of the C\\O bond. The frequency at 2739 cm−1 was attributed to the C\\H stretching mode of the aliphatic chain of the fatty acids. The intense IR band at 1728 cm−1 and 1248 cm−1 corresponded to C_O and C\\O stretching mode, respectively, of acrylated of poly (ethylene glycol) (PEG) esterfied with oleic or palmitic acid. Fig. 2 shows the XRD pattern of A) Ia and B) IIa samples under ambient conditions. The broad peak at 2θ of 20° was revealed the existence of an amorphous phase of acrylated of PEG esterfied with palmitic acid. This is indicating the most acid is interchelated and used into network of polymer but the characteristic sharp peak at 2θ of 23° indicates that the is some amount of oleic acid present without reacting in the sample and esterfication the with oleic acid give the best results. 3.2. Surface properties 3.2.1. Surface tension It was measured for aqueous solutions of the synthesized non-ionic polymeric surfactants using diverse concentrations (0.1 to 1.9 × 10−5 mol/l) and at various temperatures 25, 35, 45 and 55 °C. And the data are represented in surface tension-concentration curves as displayed in Fig. 3. As a result of hydrophobicity, the surface tension decrease by raising the concentration of the surfactants due to growing the migration of the surfactant molecules from the bulky to the interface of the solution [25]. In addition the surface tension values minimized as the temperature raise from 25 to 55 °C due to the surfactants begin to be lack of solubility as the temperature raises because of the dehydration of the hydrophobic chain from the bulky to concentrate in the surface [26–28].
Table 1 Surface properties of polymeric surfactants at 25, 35, 45, 55 °C. Surfactant
CMC X 10−3, Mole/l
πCMC, mN/m
Pc20 X 10−4, Mole/l
Γmax X 10−10, Mole/cm2
Amin, nm2
Ia IIa 25 °C Ia IIa 35 °C Ia IIa 45 °C Ia IIa 55 °C
1.1 1.3 0.9 1 0.7 0.8 0.6 0.7
35 32 36 35 37 36 38 37
1.48 1.53 1.29 1.52 1.13 1.31 1.12 1.21
3.44 2.92 2.86 2.81 2.77 2.76 2.68 2.55
0.48 0.57 0.58 0.59 0.59 0.6 0.62 0.65
3.2.2. The critical micelle concentration (CMC) Critical micelle concentration values of the synthesized polymeric surfactant were determined by plotting the surface tension (γ) of surfactant solutions versus their bulk concentrations in mole/l at 25 °C, 35 °C, 45 °C and 55 °C. The values of the CMC listed in the Table 1 are showing a decrease in the CMC with increasing the alkyl chain length, i.e. from palmitate (IIa) to oleate (Ia) this is due to the repulsion force presence in the bulk of the solution increases with increasing the alkyl chain length leading to the surfactant molecules moving to the surface and the solution needs less molecules to reach the equilibrium state at which the micelles are present [29,30]. Moreover, the CMC decreases as the temperature increases due to the growing of temperature making minimize in the hydrophilic group hydration that support the micillization. Conversely, the rising in temperature causing disturbance of the organized water molecules encircle the hydrophobic group, an action that dislike micillization. The comparative amount of these two reverse actions, decided if the CMC growing or minimized over a particular temperature zone. As shown in the Table 1 the values of the CMC decrease upon rising the temperature, means that; there is an enhancement in the micellization.
3.2.3. Effectiveness (ПCMC) The supreme surfactant is one that offers the maximum decreasing in surface tension for a critical micelle concentration (CMC). As shown in the results of the effectiveness in Table 1 when the length of the alkyl chain and the temperature growing, there is a rise in the effectiveness of the polymeric surfactants owing to increasing the hydrophobicity. Compound (Ia) at 55 °C was found the most powerful one, it produces 38 mN/m; it attained the highest decreasing of surface tension at (CMC).
3.2.4. Efficiency (Pc20) Efficiency scores of the synthesized surfactants are displayed in the Table 1. From these scores it was noticed that; at increasing the alkyl chain length and temperature, the efficiency decreases as a result of rapid formation of mono layer of surfactants on the surface.
Table 2 Thermodynamic parameters of micellization of polymeric surfactants at 25, 35, 45, 55 °C. Surfactant
ΔG°mic, KJ/mol
ΔHmic, KJ/mol
Ia IIa 25 °C Ia IIa 35 °C Ia IIa 45 °C Ia IIa 55 °C
−16.9 −16.5 −17.9 −17.7 −19.2 −18.8 −20.2 −19.8
−46.7 −52.2 −48.8 −54.7 −51 −50.7 −53 −52.6
A.I. Adawy et al. / Journal of Molecular Liquids 288 (2019) 111010 Table 3 Thermodynamic parameters of adsorption of polymeric surfactants at 25, 35, 45, 55 °C. Surfactant
ΔG°ads, KJ/mol
ΔHads, KJ/mol
Ia IIa 25 °C Ia IIa 35 °C Ia IIa 45 °C Ia IIa 55 °C
−27 −27.4 −30.5 −30.1 −32.2 −31.8 −34 −34.3
−131.4 −107.9 −138.4 −113.3 −89.5 −111.4 −93.1 −116.4
3.2.5. Maximum surface excess (Γmax) The values of Γmax are represented in Table 1. In general, the maximum surface excess Γmax enlarges by growing the alkyl chain length owing to increase the repulsion forces with the water phase so the surfactant molecules concentrate in the interface. 3.2.6. Minimum surface area (Amin) The minimum area per molecule at the water/air interface for the synthesized surfactants is recorded in Table 1. The minimum surface area (Amin) reduces with growing in the chain length of the hydrophobic part in the surfactant molecules owing to the elevated accumulation of these molecules at the interface and a minor obtainable area per molecule. 3.2.7. Standard free energies of micellization and adsorption (ΔG°mic, ΔG°ads) As shown in the Tables 2, 3, the scores of ΔGmic and ΔGads are always negatives referring that the two operations are spontaneous; however, there is a high raise in the negative value of ΔGads compared to those of micellization. This means that the inclination of the molecules to be adsorbed at the interface [31]. 3.3. Antimicrobial activity of the prepared compounds The mechanism of the biocide is accumulation onto the outer section of the cells due to existing of the polar groups in their structure which lower their osmotic balance leading to death of the cells as shown in Table 4 [32]. The skeleton structure of the surfactant affected on its biological activity [33,34]. One of the highly active biocide is the nonionic surfactants because of their action mode; the electronegativity of the oxygen atoms forces the nonionic surfactants from approach to the connected area. The existing hydrogen bonds will be disrupted because the oxygens are hydrogen bond acceptors but the connected area may not be special. In addition to hydrophobic and electrostatic forces, the hydrogen bonding made the intrinsic proteins that surrounding the membranes to be held in position, and also the breaking of membranes by proteins is mediated by the hydrogen bonding. The hydrophilic moiety of the nonionic surfactants (polyethoxy) connects to the hydrophilic portion of the membrane surface through the intermolecular hydrogen bond.
Table 4 The results of biological activity of the synthesized nonionic surfactants against different microorganisms at 1 mg/ml measured by mm. Test organism
Bacillus subtilis
Staph. aureus
Escherichia coli
Pseud. aeruginosa
Candida albicans
Aspergillus niger
21 20 31
20 20 32
19 18 32
15 20 33
25 30 28
15 15 27
Compound ID Ia IIa Reference
5
Although this is the way of the antimicrobial action as a surfactant, the connected area of the biocide is unknown [35,36]. The accumulation of the biocide at the different substrates (aqueous or microorganism's membranes) increasing with increase the concentration of the nonionic surfactants. Hence, the potent action of the molecules is increased as a result of their aggregate at the membrane of the cells [37,38]. 4. Conclusions The main conclusions of this research present in the following points: 1. The synthesized non-ionic polymeric surfactants have superior surface activity. 2. The thermodynamic parameters of adsorption and micellization showed the inclination of these compounds toward adsorption at the interfaces and also micellization in the bulky of the solutions. 3. The activity against microbes for these compounds was high against of diverse microorganisms as a result we could utilize these novel surfactants as biocides. Acknowledgments The authors are thankful of the Egyptian Petroleum Research Institute (EPRI) for technical support. References [1] I.S.I. AL-Adham, A.J. Dinning, I.M. Eastwood, P. Austin, P.J. Collier, Cell membrane effects of some common biocides, J. Ind. Microbiol. Biotechnol. 21 (1998) 6–10, https://doi.org/10.1038/sj.jim.2900554. [2] Copello, G.J., Teves, S., Degrossi, J., D'Aquino, M., Desimone, M.F. and Diaz, L.E. Antimicrobial activity on glass materials subject to disinfectant xerogel coating. J. Ind. Microbiol. Biotechnol. 33 (2006) 343–348; doi:https://doi.org/10.1007/s10295005-0066-z. [3] A.J. McBain, A.H. Rickard, P. Gilbert, Possible implications of biocide accumulation in the environment on the prevalence of bacterial antibiotic resistance, J. Ind. Microbiol. Biotechnol. 29 (2002) 326–330, https://doi.org/10.1038/sj.jim.7000324. [4] M. Simões, M.O. Pereira, M.J. Vieira, Effect of mechanical stress on biofilms challenged by different chemicals, Water Res. 39 (2005) 5142–5152, https://doi.org/ 10.1016/j.watres.2005.09.028. [5] M. Simo˜es, M.O. Pereira, M.J. Vieira, Validation of respirometry as a short-term method to assess the toxic effect of a biocide, Biofouling 47 (2005) 217–223, https://doi.org/10.1080/08927010 500066982. [6] A.D. Russell, Mechanisms of antimicrobial action of antiseptics and disinfectants: an increasingly important area of investigation, J. Antimicrob. Chemother. 49 (2002) 597–599, https://doi.org/10.1093/jac/49.4.597. [7] M. Simões, M.O. Pereira, I. Machado, L.C. Simões, M.J. Vieira, Comparative antibacterial potential of selected aldehyde-based biocides and surfactants against planktonic Pseudomonas fluorescens, J. Ind. Microbiol. Biotechnol. (9) (2006) 741–749, https:// doi.org/10.1007/s10295-006-0120-5. [8] European Standard EN 1276, Chemical Disinfectants and Antiseptics—Quantitative Suspension Test for the Evaluation of Bactericidal Activity of Chemical Disinfectants and Antiseptics Used in Food, Industrial, Domestic, and Institutional Areas—Test Method and Requirements (Phase 2, Step 1), 1997. [9] N. Christofi, I.B. Ivshina, Microbial surfactants and their use in field studies of soil remediation, J. Appl. Microbiol. 93 (2002) 915–929, https://doi.org/10.1046/j.13652672.2002.01774.x. [10] H. Jerabkova, B. Kralova, J. Nahlik, Biofilm of Pseudomonas C12B on glass support as catalyitic agent for continuous SDS removal, Int. Biodeterior. Biodegradation 44 (1999) 233–241, https://doi.org/10.1016/S0964-8305(99)00084-0. [11] E.R. Glover, R.R. Smith, V.M. Jones, K.S. Jackson, C.C. Rowlands, An EPR investigation of surfactant action on bacterial membranes, FEMS Microbiol. Lett. 177 (1999) 57–62, https://doi.org/10.1111/j.1574-6968.1999.tb13713.x. [12] M. Vaara, Agents that increase the permeability of the outer membrane, Microbiol. Rev. 56 (1992) 395–411. [13] S. Schreier, S. Malheirosb, E. de Paulab, Surface active drugs: self-association and interaction with membranes and surfactants. Physicochemical and biological aspects, Biochim. Biophys. Acta Biomembr. 1508 (2000) 210–234, https://doi.org/10.1016/ S0304-4157(00) 00012-5. [14] A. Eissa, M. El Hefnawy, M. Deef Allah, Synthesis and evaluation of nonionic polymeric surfactants based on Acrylated polyethylene glycol, J. Surfactant Deterg. 16 (2013) 161–171, https://doi.org/10.1007/s11743-012-1381-9. [15] K.R.F. Cockett, Industrial Application of Surfactants, Royal Society of Chemistry, London, 1988 205. [16] J.C. Lopez-Montilla, M.A. James, D.D. Crisalle, D.O. Shah, Surfactant and protocols to induce spontaneous emulsification and enhance detergency, J. Surfactant Deterg. 8 (2005) 45–53, https://doi.org/10.1007/s11743-005-0329-3. [17] H.J. Liu, L.H. Lin, K.M. Chen, Polyethylene glycol/polydimethyl siloxane polyester products as leveling agents in nylon dyeing, Text. Res. J. 73 (2003) 583–590.
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