Synthesis and study of antimicrobial properties of surfactants on the basis of cotton-seed oil, methyl diethanolamine and orthophosphoric acid

Размещено на http://www.allbest.ru/

SYNTHESIS AND STUDY OF ANTIMICROBIAL PROPERTIES OF SURFACTANTS ON THE BASIS OF COTTON-SEED OIL, METHYLDIETHANOLAMINE AND ORTHOPHOSPHORIC ACID

antimicrobial property synthesized surfactant

¹Asadov Z.H.

Doctor of Chemical Sciences, Professor, Corresponding member of Azerbaijan National Academy of Sciences (ANAS); Head of Laboratory of Surfactants of Institute of Petrochemical Processes (IPCP) of ANAS

²'3Tagiyev D.B. Doctor of Chemical Sciences, Professor, Academician of ANAS; Head of Department of “Biophysical and Bioorganic Chemistry ”

of Azerbaijan Medical University, Director, Institute of Catalysis and Inorganic Chemistry,

^1,2Zarbaliyeva I.A. Doctor of Chemical Sciences, Associate Professor,

Leading Researcher of laboratory of Surfactants of IPCP of ANAS and Associate Professor of Department of “Biophysical and Bioorganic Chemistry ”

of Azerbaijan Medical University 2Seyidova G. Mir J. Doctor of Medical Sciences, Professor of Department of “Microbiological and Immunological”

of Azerbaijan Medical University 2Hajizade H.N.

PhD on Chemistry,

Senior Instructor of Department of “Biophysical and Bioorganic Chemistry”

of Azerbaijan Medical University

⁴Asadova N.Z.

Instructor of Faculty of Biology of Baku State University

Abstract

Methyldiethanolamine esters have been synthesized on the basis of cotton-seed oil tnglycendes and phosphated by orthophosphoric acid. The obtained products were identified by method of IRspectroscopy. The surface activity of the synthesized substances was determined by tensiometric method. Based on these studies, the maximum adsorption and the minimum area of the molecule at the water /air interface, the surface pressure, the standard free Gibbs energies of adsorption and micellization have been calculated. Specific electroconductivity of the aqueous solutions of the surfactants were measured by electroconductometric method. Strong bactericide properties of the obtained surfactants were revelaed.

Key words: cotton-seed oil triglycerides, methyldiethanolamine, phosphate derivative of methyldiethanolamine, ester, surfactant, electroconductivity, micellization, bactericide

antimicrobial property synthesized surfactant

Introduction

Surfactants are widely used in various spheres of national economy [1,2]. Among them, the reagents obtained from ecologically -safe, and reproducible raw materials attract a special attention [3-5]. The present paper is devoted to synthesis of new representatives of such surfactants and a study of their antimicrobial properties.

Experimental

Cotton-seed oil is of a local production. Among residues of fatty acids contained in this oil triglycerides, of saturated ones, miristic acid (C14) constitutes 0.3-0.5%, palmitic acid (C16) 20.0-22.0%, stearic acid (C18) 2.0%, arachinic acid (C20) 0.1-0.6% of unsaturated fatty acids, the content of residues of oleic acid (C18) is 30.5-35.2% and that of linoleic acid (C18) is 41.7-44.0%.

Methyldiethanolamine (MDEA) was the product of Russian Federation, molar mass-119.164 g-mol^-1, density-1.038 g-ml^-1, boiling point 247.1 °C; melting point-21 °C.

Surface activity of the synthesized substances was investigated at the air-water interface by tensiometer “KSV Sigma 702” (Finland) using Du Nouy ring [6]. The method consists in measurement of the maximum force required for detaching the ring from the liquid surface. Orthophophoric acid was used as the product of “Component-Reactant” Joint Stock Company (Moscow, Russian Federation) which is 86% wt. aqueous solution

Water was used as a bidistillate.

Specific electroconductivity (k) of the aqueous solutions of the obtained surfactants was measured by “Anion-4120” electroconductometer (Russian Federation).

IR-spectra were registered by Vertex 70 (Bruker) spectrometer in the range 4000-400 cm^-1 using KBr tablets.

Aminoester was synthesized on the basis of cotton-seed oil triglycerides and MDEA at 140-150^oC during 13-14 hours in an autoclave equipped with a temperature regulator. Subsequently, phosphation of the synthesized aminoester was carried out by reacting the aminoester with orthophosphoric acid at 50-60^oC during 5-6 hours. Both surfactants are brown viscous liquids.

To study antimicrobial properties of the synthesized surfactants, the method of consequent dilution was used. The experiments were carried out in the test tubes which contained a surfactant at different concentrations and 1ml of the physiological solution. The 1-st test tube is filled with 1ml of 1% wt. solution of the surfactant. Afterwards, the solutions of the surfactant were prepared in the order of concentrations lowering twice. With this aim, the content of the 1-st tube was stirred and 1ml of it was introduced into the 2-nd tube, from the 2-nd into the 3-rd one and so on. From the last tube, 1ml was taken out to have equal volumes of the solutions in all tubes. In this way, four consequently diluted solutions of the surfactant were prepared at dilutions 1:100 (solution 1), 1:200 (solution 2), 1:400 (solution 3) and 1:800 (solution 4) at equal volumes of the physilogical solution. As a test culture, two gram positive bacteria (Staphylococcus aureus and spore forming BacillusAntracoides), three gram-negative bacteria (Pseudomonas aeruginosa, Escherichia coli and capsule forming Klebsiella pneumoniae) and fungus (Candida albicans) laboratory strains were applied. From 1 day culture of each microorganism, suspensions were made in the physiological solution provided that 1ml of the suspension contains 1 bln of microbacterial cells. After dilution procedure, with Pasteur pipette, 1 drop of microbial suspension having 500 mln microbial cells in 1 ml was added to each test cube. After 10, 20, 40 and 60 min exposition, the samples were taken away from each test tube using a bacteriological loop and inoculated onto the surface of the feeding media (for bacteria-meaty-peptonian (peptone) agar and for fungusSabouraud medium). Incubation for fungus was performed in the thermostat at 28^OC, for 24-48 h, for bacteria-at 37^OC for 24 h. Intensive growth of a microorganism was noted as “+”, growth of separate colonies-by the mark “+-” and absence of the growth of a microorganism-by the sign”-”.

Results and their discussion

The scheme of the interaction of cotton-seed oil triglycerides with MDEA is described as follows:

where R is alkyl group glycerol was removed from the mixture by washing with cold water. The final aminoester is soluble in water and kerosene.

In the next step,the MDEA ester obtained from the cotton-seed oil triglycerides was phosphated with orthophosphoric acid. The chemical formula of the synthesized surfactant is illustrated as following:

where R is a saturated or unsaturated hydrocarbon group. The reaction product is a brown substance of low viscosity.

Structure and composition of the obtained products were confirmed by using IR-spectroscopy. The IR-spectra are shown in Fig. 1 and 2.

Fig. 1. IR-spectrum of MDEA ester synthesized from cotton-seed oil triglycerides

In the IR-spectrum of MDEA ester (Fig.1), the following bands (Vmax, cm^-1) are present: 3336.50 (O-H valence vibration band, 3008.1 (C-H valence vibration band of the double bond), (2923.2 C-H valence vibration band of -CH2group) and 2853.3 (valence vibration band of C-H in CH3 group), 1736.9 (valence vibration band of carbonyl group of ester fragment,1650.8 (valence vibration band of C=C), 1564.4 (deformation vibration band of OH) and 1400.5 (deformation vibration bands of C-H in CH2 and CH3), 1243.0 (valence vibration band of C-N), 1171.4 and (ester group deformational vibrations bands), 1038.4 (valence vibration band of C-O in COH), 720.4 pendulum vibration band of (CH2).

Fig. 2. IR-spectrum of the phosphate derivative of MDEA ester based on cotton-seed oil triglycerides

In the IR-spectrum of the phosphate of MDEA ester, the following changes are observed (Vmax, cm^-1): the band at 3202.4 (O-H valence vibration band of the phosphate group) appears and the band at 3336.50 of

OH valence vibrations disappears; the bands at 2100-+ 2700 of NH group appear; the band 1564.4 of OHdeformational vibrations and 1038.4 (valence vibration band of C-O band of C-OH group) disappear; the bands at 1116.6 of valence vibrations of P-O band in P-OH group and at 943.2 of valence vibrations of C-O band in C-O-P group appear.

The data of the given IR-spectra prove proceeding of modification with H3PO4.

MDEA ester and its phosphate have a good solubility in isopropanol, isooctane, kerosene, benzene, carbon tetrachloride, a partial solubility in ethanol and water.

Surface tension data of surfactants 1and 2 were recorded at 25 and 26^oC, respectively, y versus concentration -c plots of the surfactants are given in Fig. 3.

Fig. 3. Surface tension at the water-air interface versus concentration plots of the MDEA ester (grey line; 25 oC) and its phosphation derivative (orange; 26 oC)

Using these isotherms, important parameters of the surface activity may be determined. The values of critical micelle concentrations (CMC) of the surfactants were found. Moreover, ycmc, surface pressure (ncMc), C20 (the concentration for reduction of y by 20 mN/m), adsorption efficiency (pC₂₀ = -logC₂₀) values for surfactants were calculated according to [6] and given in Table 1.

Maximum adsorption-r_maxvalues were determined by the following equation:

Where R is universal gas constant (R=8.3145 C/mol*K) and T is absolute temperature. The value of n was taken as 2 because 2 ions are formed by dissociation of the surfactants (explained later page).

The minimal value of the area per surfactant molecule after adsorption at the water-air interface (Amin) was calculated from the equation

Specific electrical conductivity versus concentration plot was built for MDEA ester at 27 ^oC and for the phosphate of MDEA ester at 27.5 ^oC. These dependence are given in Fig. 4:

Fig. 4. Specific electrical conductivity versus concentration plots of the synthesized surfactants: grey lineMDEA ester, red linephosphate of MDEA ester

Despite the fact that the structure of MDEA ester is non-ionic, its aqueous solution has electrical conductivity. This is explained by the fact that tertiary amine fragment reacting with water forms the ionic structure according to this scheme:

Table 1.

Main colloidal-chemical and thermodynamic parameters . of the obtained surfactants

Slopes of the straight line before (Si) and after (S2) CMC value for each surfactant were determined. Such important thermodynamic indices as Gibbs free energy of micellization (AGmic) and Gibbs free energy of adsorption (AG_ad) values were determined by the following equations:

where A_CMC is surface area per surfactant molecule at the interface in terms of A².

Degree of dissociation a and degree of the counter-ion binding -p were computed by the formulas:

= S₂/S₁ and в=i-

As is evident, the AGad values are more negative than the AGmic values which indicates a preference of the adsorption of the surfactant molecules rather than their micelle formation.

The results of studies of antimicrobial properties of MDEA ester and its phosphate derivative are set in Table 2. These results show that MDEA ester is effective against Pseudomonas aeruginosa at each exposure time and each dilution. Against Klebsiella pneumoniae, an effectiveness is exhibited at all times of exposure in the case of 1:100 and 1:200 dilution. At dilution 1:400 and 1:800, the bacterium is suppressed after 40 min of exposure. Against Staphylococcus aureus, a bactericide action is manifested at each degree of dilution after 40 min of exposure.

The phosphate of MDEA ester shows an effect against Esherichia coli and Pseudomonas aeruginosa at all times of exposure at dilution 1:100 and 1:200. In the case of dilution 1:400 and 1:800, a bactericide action is displayed after 40 min. Against Bacillus antracoides, at dilutions 1:100, 1:200 and 1:400, a bactericide effect is observed at all exposure times but at dilution 1:800after 10 min. In the case of Klebsiella pneumoniae, the following results are found. At dilution 1:100, an effect is manifested at all exposure times, at dilution 1:200after 20 min, at dilution 1:400-after 40 min and, in the case of dilution 1:800only after 60 min. The phosphate also exhibits moderate antifungal properties against Candida albicans. An effect is observed at all dilution degrees after 40 min.

Table 2

Results of study of antimicrobial properties of MDEA ester (1) and its phosphate (2)

Note: 1,2,3,41: 100, 1: 200, 1: 400, 1: 800; "+" Indicates “growth”; "-" indicates “suppression”, “±” indicates existence of colonies

References

[1] . H.H.Humbatov, R.A.Dashdiyev, Z.H.Asadov et.al. Chemical Reagents and Petroleum Production, Baku:Elm, 2001,448 pp.

[2] . Z.H. Asadov Azerbaijan oil industry. 2009, №2, p. 60-65.

[3] . Z.H.Asadov, I.A. Zarbaliyeva, S.H. Zargarova. Propoxylation of Aliphatic Amines by Propylene Oxide, Journal of Chemical Problems, 2017,1. p.44-50.

[4] . S.H.Zargarova, I.A.Zarbaliyeva, R.A.Rahimov, Z.H.Asadov. Synthesis and Study of Surface-Active Salts Based on Propoxy Derivatives of Dodecylamine and Monocarboxylic Aliphatic Acids. Proceedings of International Scientific-Practical Conference on Petroleum and Gas Industry, Almetyevsk (Russia), 2018, p.587-589.

[5] . H.H.Humbatov, R.A.Dashdiyev. Application of Surfactants for Liquidation of Petroleum Spills. Baku: Elm, 1998, 210 pp. (in Russian)

[6] . M.J.Rosen. Surfactants and Interfacial Phenomena, 3^rd Edn.NewYork:JohnWiley and Sons, Inc. 2004,444 pp.

[7] . Lange K.P. Surfaceactive substances . SanktPetersburg: Professiya, 2005. 239p.

[8] . Asadov Z.H., Zarbaliyeva I.A. Synthesis and Study of Surface-Active Substances Based on Cotton-Seed Oil Triglycerides, Methyldiethanolamine and Orthophosphoric Acid. Polish Journal of Science № 15, 2019, p. 11-15

[9] . Zarbaliyeva I.A. Synthesis and study of new surface-active nitrogen-and phosphorus-containing derivatives of aliphatic C11-C18 monocarboxylic acids. Thesis of diss. For the scientific degree Doctor of Chemical Sciences. Baku, Institute of Petrochemical Processes of NASA, 2018, p. 427

[10] . Asadov Z.H., Tantawy A.H., Azizov A. H., Zarbaliyeva I.A., Rahimov R.A. Synthesis Of New Complexes-Surfactants Based on Fatty Acids and Study of The Effect of Length of Fatty Acid Chain on The Petroleum-Collecting and Surface-Active Properties // Caspian Journal of Applied Sciences Research, (Malaziya), 2013, V.2, No.3, p. 13-23.

[11] . Asadov Z.H., Tantawy A.H., Azizov A. H., Zarbaliyeva I.A., Rahimov R.A. Synthesis of new complexes-surfactants based on fatty acids and Study of the effect of length of fatty acid chain on the petroleum-collecting and surface-active properties // Caspian Journal of Applied Sciences Research, 2013, V.2, No.3, p. 13-23.

[12] M.J. Rosen. Surfactants and Interfacial Phenomena, 3^rd Edn.NewYork:JohnWiley and Sons, Inc. 2004,444 pp.

Размещено на Allbest.ru