Solubility of L-histidine in different aqueous binary solvent mixtures from 283.15 K to 318.15 K with experimental measurement and thermodynamic modelling

doi:10.1016/j.jct.2016.09.039

The Journal of Chemical Thermodynamics

Volume 105, February 2017, Pages 1-14

https://doi.org/10.1016/j.jct.2016.09.039 Get rights and content

Highlights

•
The solubility of L-histidine in three binary solvents was determined.
•
Apelblat, CNIBS/R-K, Jouyban-Acree and NRTL models were used to correlate the data.
•
The mixing thermodynamics were calculated and discussed based on NRTL model.

Abstract

In this study, the solubility of L-histidine in three different binary solvents, including (water + acetone), (water + ethanol) and (water + 2-propanol), was measured over temperatures from 283.15 K to 318.15 K by employing a gravimetric method at atmospheric pressure. It was found that the solubility of L-histidine in the binary mixed solvents increases with the increasing temperature at a given solvent composition, whereas it decreases with the rise of mole fraction of organic solvents. The experimental results were well correlated by the modified Apelblat equation, CNIBS/R-K model, combined version of the Jouyban-Acree model and NRTL model, respectively. This shows that these models can correlate the solubility in three binary mixed solvents accurately. Furthermore, the mixing thermodynamic properties of L-histidine in different binary solvent mixtures were also calculated based on the NRTL model. The result indicates that the mixing process of L-histidine is endothermic and spontaneous.

Introduction

L-histidine (C₆H₉N₃O₂, CAS Registry No. 71-00-1, Fig. 1), also known as (S)-2-Amino-3-(4-imidazolyl) propionic acid, is one of the most essential and naturally occurring amino acids [1]. It serves as a precursor for many chemicals and is extensively used in many fields, such as food, pharmaceutical and feed industries. Furthermore, L-histidine has been widely researched from a nutritional and metabolic point of view. In addition, it has an important implication upon the several biological activities, e.g. transmission of metal elements in biological bases, neuro-transmitting or neuro-modulating in the mammalian central nervous system, including the retina [2]. Amino acids known for their physical and chemical properties have an important effect on numerous industrial and medical applications. However, biologically important and biotechnically produced solutions of L-histidine often appear with salts, organic solvents or other components [3]. In the production activities, crystallization is a basic unit operation. The measurement and correlation of the solubility of drugs will give aid to the design and improvement of their crystallization processes.

Knowledge of physical properties of L-histidine, e.g. purity, size distribution and mobility, is essential for its crystallization [4]. Solubility of L-histidine is one of the most necessary pieces of knowledge for its industrial amplification and manufacturing. However, the solubility of L-histidine is limited to very few solvents. Thus, the measurement and modelling of the thermodynamic values are very important as well as a very challenging task.

Knowledge of the solubility of L-histidine is one of the necessary items for industrial amplification and manufacturing. Through wide research, there are a few literature references on the solubility of L-histidine [5], [6], [7], [8], [9], [10], [11]. M. Kitamura et al. studied the solubility of two crystal forms (stable and metastable polymorphs) of L-histidine in a (water + ethanol) binary mixed solvents as a function of the volume fraction of ethanol x_v,EtOH = 0–0.6 at T = 293 K in 1994 [5]. Then C.M. Roelands et al. [6] determined the solubility of two crystal forms of L-histidine in (water + ethanol) binary mixed solvents (x_v,EtOH = 0–0.8) at T = 298 K in 2006. In addition, A.V. Kustov et al. carried out studies from 2008 to 2012 on the solubility of L-histidine in aqueous urea, aqueous dimethylformamide and aqueous glycerol solutions at 298 K [7], [11]. They also measured the thermal effects of solution of L-histidine in aqueous solutions and binary solvent mixtures. Y. Nozaki et al. [8], [9] studied the solubility of many amino acids in (water + urea) and (water + ethylene) glycol mixtures at 298 K. The solubility of L-basic amino acids in the type of free, monohydro-chloride and dihydrochloride in water was determined at (303.15, 323.15, 343.15) K by K. Hayashi [10]. These references show the solubility values of L-histidine in mixed solvents only at a few temperatures and, but studying the effect of temperature on the solubility. As a result, the solubility values for L-histidine are still limited. Thus, there remains a strong need to determine the solid-liquid equilibrium and associated thermodynamic properties of L-histidine in binary solvent systems within a wide temperature range.

In this paper, the solubility of L-histidine whose polymorph is stable in binary (acetone + water), (ethanol + water) and (2-propanol + water) solvent mixtures was determined using a gravimetric method [4], [6], [8], [9], [12], [13] from 283.15 K to 318.15 K (p = 0.1 MPa). The mole fraction range of ethanol as an anti-solvent is from 0 to 0.7. The anti-solvent (acetone or 2-propanol) content in another two binary solvent mixtures varies from 0 to 0.6. The modified Apelblat equation, CNIBS/R-K model, combined version of the Jouyban-Acree model and NRTL model were used to correlate the experimental results. All of these models show satisfactory correlation results with the experimental values. At the same time, the results can help to understand the relationship between the solubility and temperature as well as solvent composition. Additionally, the dissolution thermodynamic properties of L-histidine (Gibbs energy, enthalpy and entropy), which can help to understand its dissolution behaviour in binary mixed solvents, were calculated by using the Non-Random Two Liquid (NRTL) model.

Section snippets

Materials

L-histidine (M_w = 155.16 g⋅mol⁻¹) whose polymorph is stable, as a white crystalline powder, was purchased from Tokyo Chemical Industry Co., Ltd. (Japan) with stated mass fraction purity higher than 0.99. Organic solvents with analytical grade (acetone, ethanol and 2-propanol) were purchased from Tianjin Jiangtian Chemical Reagent Co. (Tianjin, China) and the mass fraction purity was higher than 0.995. All materials above were used without any further treatment. Distilled-deionized water

Thermodynamic models

The measurement and correlation of solubility of L-histidine plays a critical role in the design and optimization of its crystallization. Various models, such as the modified Apelblat equation, CNIBS/R–K model, λh model, NRTL equation and Jouyban–Acree model, can be used to correlate the solid-liquid equilibrium results. In this study, we adopt the following four models (modified Apelblat equation, CNIBS/R-K model, combined version of the Jouyban−Acree model and NRTL model) to model the

X-ray powder diffraction analysis

The X-ray powder diffraction (PXRD) patterns verified the identity and the high crystallinity of L-histidine used in this study. The patterns also revealed that the forms of both the raw material and residual solids were stable form A. From Fig. 2, Fig. 3, Fig. 4, it was found that all the PXRD patterns of solid phase of L-histidine in equilibrium with its solution have the same characteristic peaks. Therefore, it can be concluded that there was no degradation or crystal transformation during

Conclusions

In this paper, the equilibrium solubility was determined by a gravimetric method for L-histidine in (acetone + water), (ethanol + water) and (isopropanol + water) binary solvent systems over the temperature range of (283.15–318.15) K. The solubility increases with rising temperature and decreases with the initial mole fraction of organic solvent in all binary systems studied.

The experimental solubility results in various binary solvent systems were well correlated based on the modified Apelblat

Notes

The authors declare no competing financial interest.

Acknowledgement

The authors are grateful to the financial support of National Natural Science Foundation of China (81361140344 and 21376164), National 863 Program (2015AA021002) and Major National Scientific Instrument Development Project 21527812.

References (33)

T. Zhang et al.
J. Chem. Thermodyn.
(2016)
M. Kitamura et al.
J. Cryst. Growth
(1994)
Y. Nozaki et al.
J. Biol. Chem.
(1963)
B. Long et al.
Fluid Phase Equilib.
(2010)
Y. Qin et al.
Fluid Phase Equilib.
(2015)
A. Apelblat et al.
J. Chem. Thermodyn.
(1997)
N. Sunsandee et al.
J. Mol. Liq.
(2013)
K. Wang et al.
J. Chem. Thermodyn.
(2012)
W.E. Acree
Thermochim. Acta
(1992)
A. Jouyban-Gharamaleki et al.
Int. J. Pharm.
(1998)

M. Barzegar-Jalali et al.

Int. J. Pharm.

(1997)

A. Jouyban et al.

Thermochim. Acta

(2005)

L.A. Ferreira et al.

Fluid Phase Equilib.

(2008)

L.A. Ferreira et al.

Chem. Eng. Sci.

(2004)

M. Lenka et al.

Fluid Phase Equilib.

(2016)

D.R. Delgado et al.

J. Mol. Liq.

(2013)

Cited by (38)

Reveal the molecular mechanism of cosolvency behaviors of proline in alcohol + acetone binary mixed solvent
2024, Journal of Industrial and Engineering Chemistry
Cosolvency is a thermodynamic phenomenon of great research significance. But the current theoretical research is still not comprehensive. In this paper, L-proline, (R)-β-proline and (S)-β-proline were used as model materials to reveal the mechanism of cosolvency interaction at the molecular level. By means of spectral analysis and molecular simulation, the effects of aggregates, coordination numbers and interactions on cosolvency were systematically studied. The results show that with the change of solvent composition, the aggregation form and coordination number of solute change, which leads to the change of the interaction between solute and solvent, and finally leads to the cosolvency phenomenon.
Local composition-regular solution theory for analysis of pharmaceutical solubility in mixed-solvents
2024, Journal of Molecular Liquids
Local composition regular solution theory (LC-RST) model was developed by introducing non-equal i–j and j–i parameters into regular solution theory (RST) to account for specific molecular interactions. The LC-RST model was applied to the correlation of solubilities of active pharmaceutical ingredients (API) in hydrogen bond donor (HBD) – hydrogen bond acceptor (HBA) mixed-solvent systems. In the assessment of 32 API-mixed-solvent systems that contained 11 different APIs and 1947 data, it was determined that the LC-RST model had a logarithmic average relative deviation (ARDln) in solubility of 0.028, the Wilson model had an ARDln value of 0.24 and the purely predictive RST model had an ARDln value of 1.29. Partial molar excess enthalpies and entropies of the API in the mixed-solvents determined from the LC-RST model allowed estimation of API solubility regions where specific interactions occur between API and HBD-HBA complex molecules. In the correlation scheme, component numbers were designated as API molecule (1) – HBD molecule (2) - HBA molecule (3) and systems were grouped according to HBD molecule interactions with the API (pro-solvent, anti-solvent, synergistic with HBA molecule). Phenomenological parameter sensitivity analysis of the LC-RST model showed that dominant specific interactions tended to be 1–2 or 2–1 molecules for pro-solvent groupings, 2–3 or 2–3 molecules for anti-solvent groupings and all i–j and j-–i molecular pairs for synergistic HBD-HBA molecule groupings. Based on parameters determined from a given API-mixed-solvent system, the LC-RST model allows qualitative prediction of solubilities for other systems. The LC-RST model is simple to apply and it retains inherent predictive characteristics of regular solution theory.
Solubility and solvation energetics of L-histidine in aqueous NaCl/KCl electrolyte media
2023, Journal of Molecular Liquids
This article describes the solubility etiquette of an important amino acid L-histidine in chloro aqueous solutions of alkali metals (Na, K) under equilibrium saturated conditions through an analytical gravimetric technique at equidistant temperatures. Different thermodynamic parameters along with transfer Gibbs energies under standard conditions were estimated using theoretical methods and experimental solubilities. The way of surrounding by solvent molecules of solute L-histidine in the used media is discussed based on different modes of interactions occurring during solvation. The experimental section describes that the L-histidine solubility enhances in an aqueous KCl solution rather than in NaCl solution. The drop down in L-histidine solubility with moving up electrolyte concentrations at a certain temperature is caused by the salting-out effect. For the studied amino acid, the salting out effect is more pronounced in NaCl electrolyte at any temperature. Amino acid shows higher solubility with rising temperature in both electrolytes’ solutions. The current study suggests that the physical properties of NaCl and KCl and the size of the L-histidine molecules are two crucial factors for the chemical stability of the protein building unit.
Solubility and dissolution thermodynamics of L-histidine and L-tryptophan in aqueous ethanol solution at five equidistant temperatures
2023, Journal of Molecular Liquids
This study highlights the saturated solubilities and dissolution thermodynamical properties of two very important amino acids viz. L-histidine and L-tryptophan having various roles in many field in pure aqueous and aqua-ethanol medium at particular as well as range of temperature employing static gravimetric method which is very systematic and error free. Finding confirms that L-histidine shows more solubility in water rich region and L-tryptophan shows more solubility in organic rich region. L-tryptophan has an extra benzene ring which makes L-tryptophan more covalent than L-histidine moiety. Consequently, solubility of former in water rich region becomes low. In connection with those mentioned properties other various physiochemical parameters like co-solvent diameter, apparent dipole moment, apparent molar volume, solvent diameter etc. are also estimated. All observations are explained clearly on the ground of several solution related interactions namely cavity forming, solvent-solvent, solvent-solute interactions etc. Both total and chemical transfer Gibbs energies as well as entropies are calculated and explained to give support to stability and variation of solubility in both aqueous and aqua-ethanol media.
Solubility measurement and thermodynamic correlation of (2,4-dichlorophenoxy)acetic acid in fifteen pure solvents
2021, Journal of Chemical Thermodynamics
The solid-liquid equilibrium behavior of (2,4-dichlorophenoxy)acetic acid (2,4-D) was investigated. The solubility of 2,4-D in fifteen pure solvents were measured using the gravimetric method from 278.15 K to 323.15 K. The Hirshfeld surface analysis provided quantitative information about intermolecular interactions in 2,4-D crystal structure. The MEPs analysis showed that the carboxyl group of 2,4-D molecule was the main site for hydrogen bond formation. Besides, four thermodynamic models including the modified Apelblat equation, van’t Hoff equation, λh equation, and NRTL model were used to correlate the solubility data, and the results showed that the modified Apelblat equation has the best fitting. The calculation results of thermodynamic properties such as mixing enthalpy, mixing entropy and mixing Gibbs free energy showed that the dissolution process of 2,4-D was spontaneous. KAT-LSER model was used to investigate the solvent effect. The results revealed that solvent-solvent interaction had a significant unfavorable effect to the solubility of 2,4-D. Finally, solvation free energy analysis was performed to quantitatively explain the differences in solubility of 2,4-D in different solvents.
Effect of emulsification techniques on the distribution of components on the surface of microparticles obtained by spray drying
2021, Food and Bioproducts Processing
Citation Excerpt :
The high pressures generated during emulsification could expose the protein fraction of GA without breaking the protein structure. This is observed through the increase in the concentration of hydrophilic amino acids, such as histidine (Liu et al., 2017), on the surface of microparticles, in spite of being a smaller proportion with respect to the other amino acids in GA (hydroxyproline). The chemical structure of the proteins in the emulsion is not modified during the spray drying process (Gaiani et al., 2011b).
The number of studies on the surface composition of microparticles obtained by spray drying has increased due to the interest in understanding the relationship between the characteristics of these microparticles and the oxidation stability of encapsulated bioactive compounds. The aim of this study was to evaluate the effect of emulsification techniques on the distribution of components on the surface, microstructure, and physicochemical properties of encapsulated β-carotene microparticles obtained by spray drying. Emulsions created by microfluidization and observed by XPS showed a greater presence (11.35–16.82%) of hydrophilic amino acids (histidine, glycine, serine, threonine) on the surface. Emulsions obtained by rotor/stator system exhibited low encapsulation efficiency (9.1–46.0%), and the microparticles presented a high number of surface irregularities (shrinkage and dents) compared to the microfluidization samples. In contrast, emulsions obtained by microfluidization showed shorter wetting (12.37–14.47 min) and solubility times (25.66–30.22 min), attributed to the percentage of protein on the surface of microparticles. The characteristics of the microparticles provided by the microfluidizer could help in the design of fast-hydration and dispersion powder products by spray drying.

View all citing articles on Scopus

View full text

Solubility of L-histidine in different aqueous binary solvent mixtures from 283.15 K to 318.15 K with experimental measurement and thermodynamic modelling

Highlights

Abstract

Introduction

Section snippets

Materials

Thermodynamic models

X-ray powder diffraction analysis

Conclusions

Notes

Acknowledgement

J. Chem. Thermodyn.

J. Cryst. Growth

J. Biol. Chem.

Fluid Phase Equilib.

Fluid Phase Equilib.

J. Chem. Thermodyn.

J. Mol. Liq.

J. Chem. Thermodyn.

Thermochim. Acta

Int. J. Pharm.

Int. J. Pharm.

Thermochim. Acta

Fluid Phase Equilib.

Chem. Eng. Sci.

Fluid Phase Equilib.

J. Mol. Liq.