Sains Malaysiana 49(11)(2020): 2679-2687

http://dx.doi.org/10.17576/jsm-2020-4911-07

Thermal Behavior of Cocrystal: A Case Study of Ketoprofen-Malonic Acid and Ketoprofen-Nicotinamide Cocrystals

(Kelakuan Termal Kokristal: Kajian Kes Kokristal Ketoprofen-Asid Malonik dan Ketoprofen-Nikotinamida)

YUDI WICAKSONO^1,5*, DWI SETYAWAN², ARI SATIA NUGRAHA^3,5 & SISWANDONO⁴

¹Department of Pharmaceutics, Faculty of Pharmacy, University of Jember, 68121 Jember, Indonesia

²Department of Pharmaceutics, Faculty of Pharmacy, Airlangga University, 60286 Surabaya, Indonesia

³Drug Utilisation and Discovery Research Group, Faculty of Pharmacy, University of Jember

68121 Jember, Indonesia

⁴Department of Pharmaceutical Chemistry, Faculty of Pharmacy, Airlangga University, 60286 Surabaya, Indonesia

⁵Center for Development of Advanced Science and Technology, University of Jember, 68121 Jember, Indonesia

Received: 30 November 2019/Accepted: 25 May 2020

ABSTRACT

Thermal properties are essential parameters in transformations of solid state. It is useful for estimating physical-chemical interactions that occur specifically in a multicomponent system as cocrystal. However, there is still minimum information about determining the thermal properties of cocrystal in literature. In this study, the investigation of thermal behavior of cocrystal was determined in non-isothermal conditions based on the Kissinger method. The ketoprofen-malonic acid (KMA) and ketoprofen-nicotinamide (KN) cocrystal used as model were prepared using solvent evaporation method, while the characterization was performed by powder x-ray diffraction (PXRD), differential scanning calorimetry (DSC), and Fourier-transform infrared (FTIR). From the experimental results, the activation energy (E_a) of pure ketoprofen, KMA cocrystal, and KN cocrystal are 264.38, 384.77, and 116.64 kJ mol^-1, while the enthalpy of activation (ΔH*) are 261.31, 381.78, and 113.76 kJ mol^-1, respectively. The calculated values of entropy of activation (ΔS*) for pure ketoprofen, KMA cocrystal, and KN cocrystal are 465.22, 809.77, and 84.34 J K^-1 mol^-1 and the free energy of activation (ΔG*) of pure ketoprofen, KMA cocrystal, and KN cocrystal obtained by general thermodynamic equation are 89.53, 90.87, and 84.62 kJ mol^-1, respectively. Experimental results of the thermodynamic parameters showed cocrystals to have a positive value of ΔS*, indicating the formation of cocrystals was a non-spontaneous process. Also, the KMA cocrystal had greater free energy of activation (ΔG*) than the KN cocrystal which indicated the formation of the crystal lattice involving greater binding energy than KN cocrystal.

Keywords: Cocrystal; ketoprofen; Kissinger method; thermal properties

ABSTRAK

Sifat terma adalah parameter penting dalam transformasi keadaan pepejal. Ia berguna untuk menganggar interaksi fizikal-kimia yang berlaku secara khusus dalam sistem multikomponen sebagai kokristal. Walau bagaimanapun, maklumat berkenaan penentuan sifat terma kokristal dalam kajian kepustakaan masih kurang. Dalam penyelidikan ini, kajian terhadap sifat terma kokristal ditentukan dalam keadaan bukan isotermal berdasarkan kaedah Kissinger. Ketoprofen-asid malonik (KMA) dan ketoprofen-nikotinamida (KN) yang digunakan sebagai model disediakan menggunakan kaedah penyejatan pelarut, sementara pencirian dilakukan dengan pembelauan sinar-x serbuk (PXRD), kalorimetri pengimbasan pembezaan (DSC) dan transformasi Fourier inframerah (FTIR). Daripada keputusan kajian, tenaga pengaktifan (E_a) ketoprofen tulen, kokristal KMA, dan kokristal KN adalah 264.38, 384.77 dan 116.64 kJ mol^-1, sementara entalpi pengaktifan (ΔH*) masing-masing adalah 261.31, 381.78 dan 113.76 kJ mol^-1. Nilai pengiraan entropi pengaktifan (ΔS*) untuk ketoprofen tulen, kokristal KMA dan kokristal KN adalah 465.22, 809.77 dan 84.34 J K^-1 mol^-1 dan tenaga pengaktifan bebas (ΔG *) ketoprofen tulen, kokristal KMA dan kokristal KN yang diperoleh oleh persamaan termodinamik am masing-masing adalah 89.53, 90.87 dan 84.62 kJ mol^-1. Hasil uji kaji parameter termodinamik menunjukkan kokristal yang terbentuk mempunyai nilai ΔS * yang positif, menunjukkan pembentukan kokristal tersebut adalah melalui proses yang tidak spontan. Selain itu, kokristal KMA juga mempunyai tenaga pengaktifan bebas (ΔG*) yang lebih besar daripada kokristal KN yang menunjukkan pembentukan kisi kristal kokristal KMA menggunakan tenaga pengikatan yang lebih besar daripada kokristal KN.

Kata kunci: Kaedah Kissinger; ketoprofen; kokristal; sifat terma

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*Corresponding author; email: yudi.farmasi@unej.ac.id