Determination and modeling of the solubility of (limonin in methanol or acetone + water) binary solvent mixtures at T = 283.2 K to 318.2 K

https://doi.org/10.1016/j.jct.2016.03.037Get rights and content

Highlights

  • The solubilities of limonin were measured in the binary solvent mixtures methanol + water and acetone + water.

  • The solubility data were correlated by nine models.

  • The solubility of limonin had a maximum point at 0.9 mol fraction of acetone in acetone + water mixtures.

Abstract

The solubility of limonin in the binary solvent mixtures (methanol + water) and (acetone + water) with various initial mole fractions of methanol or acetone was measured by high-performance liquid chromatography (HPLC) at different temperatures ranging from 283.2 K to 318.2 K. The solubility of limonin increased with increasing initial mole fraction of methanol in (methanol + water) mixtures, whereas it had a maximum point at 0.9 mol fraction of acetone in (acetone + water) mixtures. The solubility of limonin increased with increasing temperature in the two binary solvent mixtures. The solubility of limonin was correlated with temperature by the van’t Hoff model and the modified Apelblat model, and the fitting results showed that the modified Apelblat model had better correlation. The CNIBS/Redlich–Kister model and the simplified CNIBS/Redlich–Kister model were used to correlate the solubility data with the initial solvent composition, the results show that the CNIBS/Redlich–Kister model reveals better agreement with the experimental values. Furthermore, to illustrate the effects of both temperature and initial solvent composition on the changes in the solubility of limonin, the solubility values were fitted by the Jouyban–Acree, van’t Hoff–Jouyban–Acree, modified Apelblat–Jouyban–Acree, Ma and Sun models. Among the five models, the Jouyban–Acree model give the best correlation results for (methanol + water) binary solvent mixtures, while the experimental solubility in the (acetone + water) system was most accurately correlated by the van’t Hoff–Jouyban–Acree model.

Introduction

Limonin (C26H30O8, molar mass: 470.51 g mol−1, CAS number 1180-71-8, Fig. 1), a limonoid, is a kind of characteristic secondary metabolite belonging to highly oxygenated triterpenoid derivatives and enriched in citrus fruits [1], [2], [3], for example the fruit of Evodia rutaecarpa (Juss.) Benth, E. rutaecarpa (Juss.) Benth. var. officinalis (Dode) Huang, or E. rutaecarpa (Juss.) Benth. var. bodinieri (Dode) Huang or in seeds of lemon and orange. Limonin shows various biological activities and pharmacological properties [4], [5], [6], [7], [8], [9], including anticancer, antioxidant, anti-inflammatory, antifungal, analgesic and anti-HIV activities.

Limonin often coexists with rutaecarpine and evodiamine in Evodia fructus. To design an optimized separation process, it is essential to understand their solubilities in various solvents. The solubility of rutaecarpine and evodiamine in pure solvents and binary solvent mixtures had been reported in our previous works [10], [11], [12]. Chandler et al. reported the solubility of limonin only in water, and water at pH 6.3 and pH 3.2 [13]. Luo et al. reported the solubility of limonin only at 310.15 K in water, methanol, acetone and other solvents [14]. However, the solubility of Limonin in binary solvent mixtures has not been systematically studied. Therefore, in this work, the solubility of limonin in binary solvent mixtures (methanol + water) and (acetone + water) using various initial mole fractions was measured by high-performance liquid chromatography (HPLC) at different temperatures ranging from 283.2 K to 318.2 K. The measured solubility of limonin was then correlated by several models [15], [16], [17], including the van’t Hoff model, the modified Apelblat model, the CNIBS/Redlich–Kister model, simplified CNIBS/Redlich–Kister model, the Jouyban–Acree model, the van’t Hoff–Jouyban–Acree model, the modified Apelblat–Jouyban–Acree model, Ma and Sun models.

Section snippets

Materials

Limonin (mass-fraction purity  0.98) was isolated from E. fructus previously in our laboratory, its chemical structure was confirmed by 1H NMR (Fig. S1) which was consistent with the data in the literature [18], [19], [20]. Methanol and acetone were analytical reagents and were purchased from Tianjin Hengxin Chemical Preparation Co. Ltd. (Tianjin, China) and Shanghai Rich Joint Chemical Reagents Co. Ltd. (Shanghai, China), respectively. Doubly distilled water was prepared from a SZ-93 automatic

Characterization of limonin

The representative PXRD patterns of limonin standard and precipitates in different solvents were presented in Fig. 2 (Supporting Information). Compared with the PXRD pattern of limonin standard, the PXRD patterns of the precipitates in each solvent exhibited no significant changes, indicating that limonin had no polymorphism throughout the experiments.

Solubility values

The mole fraction solubility of limonin along with the standard uncertainties in methanol aqueous solution and acetone aqueous solution are

Conclusions

The solubility of limonin in the methanol aqueous solution and acetone aqueous solution were measured at different temperatures ranging from 283.2 K to 318.2 K. The solubility of limonin increased with increasing temperature in the two aqueous solutions. The solubility of limonin increased with increasing methanol in the methanol aqueous solution, whereas the maximum point in acetone + water binary solvent mixtures was observed at 0.9 mol fraction of acetone. To correlate the solubility with

Acknowledgments

Financial support from the National Natural Science Foundation of China (Nos. 21366019, 20806037 and 20876131), Jiangxi Province Young Scientists (Jinggang Star) Cultivation Plan (20112BCB23002), Jiangxi Province Higher School Science and Technology Landing Plan Projects (No. KJLD13012), Special Funds for Graduate Student Innovation in Jiangxi Province (No. YC2014-S013), and Jiangxi Province Undergraduate Innovation and Entrepreneurship Training Program (No. 201310403040) are gratefully

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