Adsorption of Atenolol drug from Aqueous solution by poly (AAM_MA) hydrogel and used in Drug Delivery System: Study kinetic and Thermodynamic

 

Asawer A. Mhammed Alzayd¹, Faiq F. Karam ²*

¹College of Veterinary Medicine, Univercity of Kerbala

²Department of Chemistry, College of Science, University of Al-Qadisiyah, Diwaniya, Iraq

 

ABSTRACT:

In this study using poly acryl amid-co-maleic acid as effective adsorbent for Atenolol to adsorption from aqueous solution, Batch experiments done to study influencing some parameters such as contact time, weight of adsorbent,  temperature, pH and ionic intensity to adsorption atenolol drug on hydrogel prepared previously by free radical polymerization from acrylamide (AAM) maleic acid(MA), by adsorption process of Atenolol we obtained data about kinetic and thermodynamic, describe kinetic by two models equation first and second pseudo order, also applied data on Langmuir, freundlich and Timken models equation to get it information on adsorption process, the  study clarify effect some parameter on quantity of adsorbate such as pH  at range (1.2-11). ionic strength by used three types of salts, temperature at rang (5-35) ^oC, contact time(1-300 min) and weight of adsorbate at range(0.01-0.20 g), its found when increase of temperature and ionic strength will decrease of quantity the adsorbate presences by using poly (AAM-MA) hydrogel under the following optimum condition at temperature 15^oc, contact time 120 min, pH =6 found can removed 94.2% from drug in aqueous solution and adsorption process follow second pseudo order)R² = 0.999).The adsorption isotherm appears that adsorption process  applied models freundlich and Timken. Thermodynamic functions process calculated and appeared the adsorption non spontaneous and exothermic process, The aim of study kinetic and thermodynamic of adsorption Atenolol drug from aqueous solution to achieve highest level from therapeutic effectiveness to atenolol drug by cross linked hydrogel in controlled release system

 

1. INTRODUCTION:

Hydrogels: it’s a hydrophilic polymers have highly capable to imbibe large quantity from water and biological fluids [1] so at similar biological tissue system and rubbery because contain loving water group like (SO₃, COOH, OH, NH₃, CONH₂) [2], Hydrogel differentiate presences three dimensional network, hydrogel biocompatible and nontoxic [3], under physiological conditions when exposure change in pH, T, glucose contact, enzyme, ionic strength, magnetic or electric field will suffer swelling [4] Phenomena this characterized will submit for many factors to make increase or decrease, such as number of hydrophilic group in structure polymer [5], found two kinds from interlacement Physical and chemical cross linked in the first type the bonds may be hydrogen bonding or hydrophobic or Vandervals forces and electrostatic attraction [6], the hydrogels used in many fields medical, industrial, agricultural, in medical used as eyes lenses, engineering member and controlled released system, to treatment some problems are given to the drug orally as frequency concentration of drug, reduce side effect, increase biological half-life, increase Commitment from patient [7], the hydrogel work as drug carries to diminishing all this negative effect and protect the medicine from gastrointestinal effects and increase pharmacological effectiveness [8] so that lead to reduce pollution atenolol drug in sewage [9], Atenolol is one of the pharmacological Beta-blockers group and is widely descried to hypertension [10] and cardiovascular disease such as angina pectoris cardiac arrhythmias as well as myocardial infraction, several studies have shown that drug is low absorption in the colon and intestines so the body get rid speedily so this drug have shortening biological half-life and low bioavailability and dumping in the concentration of doses in blood plasma levels thus showing the undesirable effect as related the central nervous system [11], sheltering pharmacological contrapuntal to finding methods to assuring drug reached in the tissue body by designing ( carries/ vehicles-drags) system, The drug carrier define: a single molecule or system used to transport drug to specific location either in the packing of drug or carry on surface [12].

 

2. EXPERIMENTAL (METHODS AND MATERIALS):

2-1. Materials Used:

A hydrogel prepared from: Acryl amide)AAM) and maleic acid(MA) were supplied by (Himedia, India), as an accelerator N, N, N', N'-tetramethylethylenediamine (TEMED) supplied from Merck(Darmstadt, Germany) and were used as the redox initiator pair, The initiator, potassium persulfate (KPS) was supplied by(merck, Germany), as crosslinking agent is N,N'-methylene biascrylamide (NMBA) was purchase from (Fluka, Germany). Sodium chloride, Carbonate Calcium and Potassium chloride was obtained from (Fluka, Germany). Atenolol was purchase from (Basic Pharma Life Science Pvt.Ltd, india). Sodium Hydroxide and Hydrochloric acid were supplied from (Fluka, Germany), double-distilled water (DDW)

 

2-2. Instruments:

1    UV-Visible spectrophotometer, Double Beam, Shimadzu. PC 1800, Japan.

2    Electronic Balance, Sartorius Lab. L420 B, +0.0001.

3    Dunboff metabolic shaking Incubater GCA/ precision Scientific.

4    Centrifuge tubes D-78532 Tuttlingen 6000 U/min. Germany

5    pH-meter, pH-3110, Intertek, Germany.

6    Oven, Memort LOD–080N, Jlabtech, Korea.

7    Hotplate-Stirrer, L-81, Jlabtech, Korea

8    Tablet Machine TP1.5 China

2-3. Batch adsorption test:

all of experiments were achieved in stoppered Erlenmeyer flasks containing o.05g from hydrogel and 10ml from drugs of aqueous solution concentration 10-100ppm the mixture in stoppered flask was shaken in a shaker incubator a thermostatically at speed of 150 rpm until reached equilibrium in 120 min, the equilibrium time was fixed in all adsorption experiments the suspensions put a centrifuged at 6000 cycle/ min for 8 min, then estimate amounts of adsorbate by measure in U.V visible spectrophotometer at λmax (275.5), Abatch of experiments to investigated different parameters as weight of adsorbent contact time pH, temperature and ionic intensity calculate amount of drug adsorbed by the following equation

          Vsol(C₀- C_e)

q_e =-----------------------------                  ……1

                     m

                      

Where q_e is the sorption capacity (mg/g), V is the volume of solution (L), C_e is the equilibrium concentration (mg/L), m is the weight of adsorbent (g), and C_o is the initial concentration (mg/L) [13].

 

3-RESULTS AND DISCUSSION:

3-1. Adsorption Study:

3-1-1. Effect of the Weight of adsorbent:

to adsorption drug from solution usage of different range from weight of hydrogel (0.01-0.20)with 50 mg/L from atenolol drug when increase weight of adsorbent increase quantities of drug until reached 0.05 gm we get it higher removal percentage from drug reached 94.2% that to indicated fill all active site and that due to occurred saturation state and equilibrium also increase the electrostatic attraction forces between adsorbate and adsorbent, so Does not affect the increase weight hydrogel with specific drug concentration(50mg/L) [14], fig (1) clarify effect dose adsorbent.

 

Fig (1) Effect of different adsorbent dose on adsorption in 50mg/L

 

 

3-1-2. Contact time influence on adsorption drug:

Effect of contact time the adsorption of drug increase time until reached 120 min it will stopped because reached active site in surface adsorbate saturated state because conquer all of active site the Fig (2) appeared the equilibrium time in 120min.

 

Fig (2) effect contact time at 15^oC and 50 gm/L

 

3-1-3. Effect of temperature:

The temperature play important role in adsorption process, the effects of temperature was investigated at different temperature (5-35^oc),The fig(3) shown the amount of adsorbate decrease with increase temperature the fig appear effected increase temperature on amount of adsorbate that is indicate the adsorption process was exothermic and that belong the to the molecules adsorption acquisition kinetic energy with increase heat so separate from surface adsorbent also may be due to breaking some active functional group lie in a surface so decrease in number active site the highly of temperature made increase of solution drug in aqueous solutions in osmosis pressure to hydrogel network then lose the water molecular of the polymer and retraction and overlapping side chains so that is causes diminishing in active site[15,16]

 

Figure (3) Effect of increase temperature at 15^oC

 

thermodynamic function of adsorption process were calculated to knowledge free kipps energy, enthalpy value can be estimated by Vant -Hoff equation and plotted ln Xm Varus1/T can extracted reaction of enthalpy slop = (-ΔH/R) negative value to enthalpy indicate to exothermic, negative entropy value refer to adsorption regulars system and free energy have positive to refer to non-spontaneously process[17] the adsorption Isotherms according in Giles classification was (S₃), its assumed that the molecules drug towards perpendicularly on surface adsorbent and applied study accordance with Freundlich and Timken isotherms that indicate the adsorption multilayer because the surface its heterogeneous energy to active site the table (1) and clarify Langmuir, Freundlich and Timken equation isotherms and the table(2) show the value of parameter Table (3) Values of thermodynamic functions to adsorption process.

 

Fig (4) Effect of temperature on the maximum adsorbed quantity for adsorption of atenolol drug on the adsorbent surface

 

Table (1) Linear equation, plots and parameters to Langmuir, Freundlich and Timken isotherms

Isotherm models	Linear equation	plot	parameter
Langmuir	=	1/qe vs 1/Ce	KL = intercept / slope qm = 1/intercept
Freundlich		log qe vs log Ce	KF = 10intercept 1/n = slope
Timken	qe = B ln KT + B ln Ce	qe vs lnCe	KT = eintercept/slope B = slope

 

 

 

Table (2) Amounts of Ciprofloxacin uptake by hydrogel at 15 ^oC calculations and application of Langmuir, Freundlich and Timken equation

 

Table (3) Values of thermodynamic functions to adsorption process of atenolol drug on the adsorbent surface at 15 ^oC

 

Table (4) Adsorption kinetics parameters of adsorption of atenolol drug on asdorbent surface

 

3-1-4. Adsorpition kinetic:

To describe speed adsorption drug on surface hydrogel examined two equation models: pseudo-first order and pseudo-second order the table (4) shows the values of kinetic parameters, qe, coefficient and R^2, presence the process of adsorption follow pseudo-second order [18].

 

3-1-5. Effect of change pH:

In the fig(5 ) appeared influent different acidic function on adsorption atenolol drug, the resut shown increase quantity of adsorbate with increase pH until reached pH=6 we get it maximum amount of adsorbate that due increase ionization in active site then occurred electrostatic attraction between (+CONH3) on atenolol drug and carboxylate ions on surface hydrogel, atenolol have pka (9.4) so its have positive charge in acidic media concentrated on amine and amide group in the drug compound the surface contain amide group that protonated in acidic media so repulsion charge between similar charge then the hydrogel will swelling, the surface also have carboxyl group that ionization with increase pH to became carry negative charge until reached pH = 6 occurred electrostatic attraction between different charge, the hydrogen ions play important role in adsorption process because compete with drug molecules on surface adsorbent and when continues increase in pH value the drug converted to neural molecule and less electrostatic forces so decrease amounts of drug [18]

 

 

Fig (5) Effect of pH values on adsorption of atenolol on hydrogels at 15^oC

3-1-6. effect of ionic strength on adsorption process:

Found many factors effect on swelling behavior so determine some salts have different character (charge / radius) as (Nacl, KCl and CaCO₃). the fig ( 6) show result that get it, its notice the quantity of adsorbate less with increase concentration salts and observed the (CaCO₃) highly effector we can interpreting the result according electrostatic attraction and repulsion when the bonding forces have been attraction between adsorbate and adsorbent that mean added positive ions will done compete on active site in surface hydrogel the swelling effecting largely by radius and charge salt whomsoever small radius not effect on capable to absorption water when penetration so sodium ions less effector from potassium ions while calcium ion have divalent it was operating a complex on surface polymer to worked on reinforcement entanglement then not easily on hydrogel to swelling and overlapping with drug molecules so decrease in amount of adsorbate because sharking and contraction in hydrogel addition cations compete with positive charge group on drug molecule [19,20].

 

Fig (6) Effect of ionic strength on adsorption of ciprofloxacin on adsorbent surface at 15^oC

 

4. CONCLUSION:

From during this study was determined optimum condition to adsorption atenolol drug on (AAM-CO-MA) hydrogel to use in controlled release system the study appeared in 15^oc, pH=6, 50/L, and 120 min can removal 94.2 from drug in aqueous solution, The study shown adsorption process was exothermic and non-spontaneously reaction and highly regular molecules, The adsorption applied on pseudo second order, also appeared negative effect on adsorbate amount with increase temperature and ionic strength, The quantity of adsorbate depend on (charge /radius)cation ad follow sequence Na<K<Ca⁺² .

 

5. REFERENCES:

1.      Pakdel, P.M. and Peighambardoust, S.J., 2018. A review on acrylic based hydrogels and their applications in wastewater treatment. Journal of Environmental Management, 217, pp.123-143.

2.      Deen, G.R. and Loh, X.J., 2018. Stimuli-Responsive Cationic Hydrogels in Drug Delivery Applications. Gels, 4(1), p.13.

3.      León, O., Muñoz-Bonilla, A., Soto, D., Ramirez, J., Marquez, Y., Colina, M. and Fernández-García, M., 2018. Preparation of oxidized and grafted chitosan superabsorbents for urea delivery. Journal of Polymers and the Environment, 26(2), pp.728-739.

4.      Yahia, L., Chirani, N., Gritsch, L., Motta, F.L. and Fare, S., 2015. History and applications of hydrogels. Journal of Biomedical Sciences, 4(2), pp(1-23).

5.      N Caló, E. and Khutoryanskiy, V.V., 2015. Biomedical applications of hydrogels: A review of patents and commercial products. European Polymer Journal, 65, pp.252-267.

6.      Ahmed, E.M., 2015. Hydrogel: Preparation, characterization, and applications: A review. Journal of Advanced Research, 6(2), pp.105-121.

7.      Gabb, G.M., Mangoni, A., Anderson, C.S., Cowley, D., Dowden, J.S., Golledge, J., Hankey, G.J., Howes, F.S., Leckie, L., Perkovic, V. and Schlaich, M., 2016. Guideline for the diagnosis and management of hypertension in adults—2016. mortality, 3, p.4.

8.      Tahseen, F. and Gangurde, A.B., 2014. Formulation Development and In-vitro Evaluation of Sustained Release Tablets of Carvedilol Solid Dispersion. International Journal, 3(4), pp.52-61.

9.      Haro, N.K., Del Vecchio, P., Marcilio, N.R. and Féris, L.A., 2017. Removal of atenolol by adsorption–Study of kinetics and equilibrium. Journal of Cleaner Production, 154, pp.214-219.

10.   Lal, S. and Datta, M., 2015. In vitro prolonged gastric residence and sustained release of atenolol using novel clay polymer nanocomposite. Applied Clay Science, 114, pp.412-421.

11.   Kyzas, G.Z., Koltsakidou, A., Nanaki, S.G., Bikiaris, D.N. and Lambropoulou, D.A., 2015. Removal of beta-blockers from aqueous media by adsorption onto graphene oxide. Science of the Total Environment, 537, pp.411-420.

12.   Deshmukhe, A. Shetty, S., 2017.Resealed erythrocytes: A novel and promising drug carrier. International Journal of Pharmaceutical Sciences and Research, 8(8),PP.3242-3251

13.   Khan, S., Dan, Z., Mengling, Y., Yang, Y., Haiyan, H. and Hao, J., 2018. Isotherms, kinetics and thermodynamic studies of adsorption of Ni and Cu by modification of Al2O3 nanoparticles with natural organic matter. Fullerenes, Nanotubes and Carbon Nanostructures, 26(3), pp.158-167.

14.   Altaa, S.H.A., Alshamsi, H.A.H. and Al-Hayder, L.S.J., 2017. Rhodamine B Removal on A-rGO/Cobalt Oxide Nanoparticles Composite by Adsorption from Contaminated Water. Journal of Molecular Structure. 1161, pp. 356-365.

15.   Yuvaraja, G., Prasad, C., Vijaya, Y. and Subbaiah, M.V., 2018. Application of ZnO nanorods as an adsorbent material for the removal of As (III) from aqueous solution: kinetics, isotherms and thermodynamic studies. International Journal of Industrial Chemistry, pp.1-9.

16.   Dehdashti, B., Amin, M.M., Pourzamani, H., Rafati, L. and Mokhtari, M., 2018. Removal of atenolol from aqueous solutions by multiwalled carbon nanotubes modified with ozone: kinetic and equilibrium study. Water Science and Technology,2018, pp.1-13.

17.   Tang, R., Dai, C., Li, C., Liu, W., Gao, S. and Wang, C., 2017. Removal of Methylene Blue from Aqueous Solution Using Agricultural Residue Walnut Shell: Equilibrium, Kinetic, and Thermodynamic Studies. Journal of Chemistry, 2017,pp.1-10

18.   Haro, N.K., Del Vecchio, P., Marcilio, N.R. and Féris, L.A., 2017. Removal of atenolol by adsorption–Study of kinetics and equilibrium. Journal of Cleaner Production, 154, pp.214-219.

19.   Mouni, L., Belkhiri, L., Bollinger, J.C., Bouzaza, A., Assadi, A., Tirri, A., Dahmoune, F., Madani, K. and Remini, H., 2018. Removal of Methylene Blue from aqueous solutions by adsorption on Kaolin: Kinetic and equilibrium studies. Applied Clay Science, 153, pp.38-45

20.   Ilgin, P. and Ozay, O., 2017. Novel stimuli-responsive hydrogels derived from morpholine: synthesis, characterization and absorption uptake of textile azo dye. Iranian Polymer Journal, 26(6), pp.391-404.

 

 

 

 

 

 

Received on 15.02.2019           Modified on 20.03.2019

Accepted on 28.04.2019         © RJPT All right reserved