Solubility Of Organic Molecules Research Articles

SOMAS: a platform for data-driven material discovery in redox flow battery development

Aqueous organic redox flow batteries offer an environmentally benign, tunable, and safe route to large-scale energy storage. The energy density is one of the key performance parameters of organic redox flow batteries, which critically depends on the solubility of the redox-active molecule in water. Prediction of aqueous solubility remains a challenge in chemistry. Recently, machine learning models have been developed for molecular properties prediction in chemistry and material science. The fidelity of a machine learning model critically depends on the diversity, accuracy, and abundancy of the training datasets. We build a comprehensive open access organic molecular database “Solubility of Organic Molecules in Aqueous Solution” (SOMAS) containing about 12,000 molecules that covers wider chemical and solubility regimes suitable for aqueous organic redox flow battery development efforts. In addition to experimental solubility, we also provide eight distinctive quantum descriptors including optimized geometry derived from high-throughput density functional theory calculations along with six molecular descriptors for each molecule. SOMAS builds a critical foundation for future efforts in artificial intelligence-based solubility prediction models.

Predicting Solubility Limits of Organic Solutes for a Wide Range of Solvents and Temperatures.

The solubility of organic molecules is crucial in organic synthesis and industrial chemistry; it is important in the design of many phase separation and purification units, and it controls the migration of many species into the environment. To decide which solvents and temperatures can be used in the design of new processes, trial and error is often used, as the choice is restricted by unknown solid solubility limits. Here, we present a fast and convenient computational method for estimating the solubility of solid neutral organic molecules in water and many organic solvents for a broad range of temperatures. The model is developed by combining fundamental thermodynamic equations with machine learning models for solvation free energy, solvation enthalpy, Abraham solute parameters, and aqueous solid solubility at 298 K. We provide free open-source and online tools for the prediction of solid solubility limits and a curated data collection (SolProp) that includes more than 5000 experimental solid solubility values for validation of the model. The model predictions are accurate for aqueous systems and for a huge range of organic solvents up to 550 K or higher. Methods to further improve solid solubility predictions by providing experimental data on the solute of interest in another solvent, or on the solute's sublimation enthalpy, are also presented.

Absolute Organic Crystal Thermodynamics: Growth of the Asymmetric Unit into a Crystal via Alchemy.

The solubility of organic molecules is of critical importance to the pharmaceutical industry; however, robust computational methods to predict this quantity from first-principles are lacking. Solubility can be computed from a thermodynamic cycle that decomposes standard state solubility into the sum of solid–vapor sublimation and vapor–liquid solvation free energies ΔGsolubility° = ΔGsub° + ΔGsolv°. Over the past few decades, alchemical simulation methods to compute solvation free energy using classical force fields have become widely used. However, analogous methods for determining the free energy of the sublimation/deposition phase transition are currently limited by the necessity of a priori knowledge of the atomic coordinates of the crystal. Here, we describe progress toward an alternative scheme based on growth of the asymmetric unit into a crystal via alchemy (GAUCHE). GAUCHE computes deposition free energy ΔGdep° = −ΔGsub° = −kBT ln(Vc/Vg) + ΔGAU + ΔGAU→UC as the sum of an entropic term to account ...

Organic molecules on the surface of water droplets – an energetic perspective

The solubility of organic molecules is a well established property, founded on decades of measurements, the results of which have been tabulated in handbooks. Under atmospheric conditions water droplets may form containing small amounts of other molecules. Such droplets typically have a very large area to volume ratio, which may shift the solvation equilibrium towards molecules residing on the droplet surface. The presence of organic molecules on droplet surfaces is extremely important for reactivity--it is well established that certain chemical reactions are more prevalent under atmospheric conditions than in bulk. Here we present a thermodynamic rationalization of the surface solvation properties of methanol, ethanol, propanoic acid, n-butylamine, diethyl ether, and neopentane based on potential of mean force (PMF) calculations--we have previously demonstrated that an energetic description is a very powerful means of disentangling the factors governing solvation (Caleman et al., Proc. Natl. Acad. Sci. U. S. A., 2011, 108, 6838-6842). All organic molecules investigated here are preferentially solvated on the surface of the droplets rather than in the inside, yet the magnitude of surface preference may differ by orders of magnitude. In order to dissect the energetic contributions that govern surface preference, we decompose the PMF into enthalpic and entropic components, and, in a second step, into contributions from water-water and solute-water interactions. The analysis demonstrates that surface preference is primarily an enthalpic effect, but the magnitude of surface preference of solutes containing large apolar groups is enhanced due to entropy. We introduce an analysis of the droplet PMFs that allows one to extrapolate the results to larger droplets. From this we can estimate the solubility of the solutes in water droplets, demonstrating that the solubility in droplets can be orders of magnitude larger than in bulk water. Our findings have implications for understanding the process of electrospray ionization, an important technique in biological mass spectrometry, since our work strongly suggests that in equilibrium biomolecules would be adsorbed on the droplet surface as well.

NIR-investigations on the H-bond state in H 2)–solvent mixtures

The formation of H-bonds of H 2O with H-bond acceptors in dilute solutions has been shown by IR-spectroscopy in several systems [1, 2]. In comparison to these solutions the H-bonds in systems enriched in H 2O seem to be poorly understood [3]. The H 2O combination band (ν 3 + ν 2) is a useful tool for investigations of interactions of H 2O–organic molecules. with this method the strength and amount of H-bonds can be determined. At mole fractions of H 2O between 0.8 and 0.98 in acetone, tetrahydrofuran, etc. the spectra show the presence of H-bonds between H 2O and the organic acceptors similar to those in dilute solutions; in addition the spectra indicate the presence of less free OH-groups and more H-bonds of intermediate strength in comparison to pure water. The relation between these observations and the solubility of organic molecules in H 2O as well as the two phase formation after addition of salts or sugars for example to these binary solvents is studied and will be discussed.