Conductor-like Screening Model Research Articles

Role of heads and tails on tetrahydrofuran- and dimethyl sulfoxide-water separation by glycerol and sucrose esters

Tetrahydrofuran (THF) and dimethylsulfoxide (DMSO) are miscible in water due to hydrogen (H) bonding. Amphiphilic glycerol and sucrose esters with a different number of tails and heads separate them, depending on the organic solvent concentration. Separation is worse in solutions where amphiphiles are most soluble. Separation occurs due to interactions between the amphiphiles and either organic solvents or water, as shown by attenuated total reflectance-Fourier transform infrared spectroscopy (ATR-FTIR). Separation is best with glycerol esters with more heads and tails. Multiple tails hamper interactions between glycerol ester heads, thereby facilitating interactions with organic solvents or water to promote solvent–water separation. THF interacts with the glycerol ester tails, while water H bonds with the glycerol ester heads, as indicated by activity coefficients estimated with conductor-like screening model for real solvents. In THF, amphiphiles self-assemble into micelles, as shown by small angle x ray scattering (SAXS). Without water, THF is likely both inside and outside the micelles. SAXS shows that micelles shrink with 4% water in THF because water molecules partition inside them and are smaller than THF. With additional water, micelles swell into emulsions. Dissimilar to THF, DMSO preferentially interacts with the glycerol ester heads rather than their tails. ATR-FTIR shows that the proportion of free vs bonded S=O groups of DMSO decreases upon mixing with glycerol esters. DMSO and glycerol esters primarily accept H bonds, as indicated by their sigma profile. This leads to competition for interactions with water, displacing DMSO.

Fatty acid-arginine vesicles with prominent encapsulation efficiency and substantial transdermal delivery of sinomenine hydrochloride

In clinical practice, sinomenine hydrochloride (SH) is a valuable and promising medication for rheumatoid arthritis. However, oral administration of SH is less bioavailable with adverse reactions to the digestive system, blood circulation, and nervous system, among which rash, gastric ulcer, gastric haemorrhage and anaphylactic shock are the most common. Owing to a short half-life in the human body (0.791 h), patient compliance is greatly reduced, resulting in frequent administration for patient treatment. Therefore, SH encapsulated in vesicles with amphiphilic layers would be more stable and have fewer side effects. In this study, a transdermal drug delivery system (TDDS) for SH was designed utilizing fatty acid vesicles as carriers. The physicochemical properties and aggregate morphology of two carriers: arginine-oleic acid ([Arg][Ole]) and arginine-decanoic acid ([Arg][Dec]) were investigated, and the SH encapsulation method by the above materials was optimized and verified by single factor and central composite design (CCD) response surface methods. Notably, the encapsulation efficiency (EE) of SH in [Arg][Dec] vesicles was increased to 83.5 % and the centrifugal stability (CS) to 90.4 %. Moreover, as a result of the Conductor-like screening model for real solvents (COSMO-RS) calculation, it was found that the interaction between [Arg][Dec] and SH was stronger than that of [Arg][Ole], aligning with experimental results. In comparison to the sustained release period in water, the in vitro release experiment showed that the [Arg][Ole] and [Arg][Dec] vesicles could be prolonged to 17 hours. Importantly, the cumulative skin permeability of [Arg][Dec] vesicles reached 1665.59 μg·cm−2 after 48 h, which is much higher than the previous literature value of around 663 μg·cm−2. These results suggest that vesicles provide a viable method for transdermal delivery of SH.

The dissolution behavior of 3,4-O-isopropylidene clindamycin in twelve mono-solvents: Solubility, intermolecular interactions, and apparent thermodynamics

The solubility of 3, 4-O-isopropylidene clindamycin (OIC) was determined in twelve solvents at p = 101.3 kPa with the temperature from 273.15 K to 313.15 K. The solubility of OIC increases with the raise temperature. Among the selected solvents, 2-butanol showed the best dissolving ability for OIC, while acetonitrile showed the worst dissolving ability. The obtained data are neatly correlated with five models, including van't Hoff, Yaws, λh, Wilson, and nonrandom two-liquid interaction model (NRTL), with Yaws equation yielding the most accurate predicted results. Moreover, the Conductor-like Screening Model for Real solvents (COSMO-RS) provides better calculated results for the protic solvents than the aprotic ones except for acetonitrile. The dissolving mechanism of OIC was investigated with intermolecular interaction between OIC and solvents, and the analyses indicate that the dissolving process is affected by intermolecular interaction, molecular shape, and size of both solvents and the solute. The apparent thermodynamics analysis shows that the dissolving process of OIC before reaching equilibrium in the twelve solvents is spontaneous, endothermic, and enthalpy driven.

Screening of ionic liquids for the solubility enhancement of quinine using COSMO-RS

Screening of ionic liquids for the solubility enhancement of quinine using COSMO-RS

Lignocellulosic waste biosorbents infused with deep eutectic solvents for biogas desulfurization

This paper introduces an innovative method for treating biogas streams, employing lignocellulosic biosorbents infused with environmentally friendly solvents known as deep eutectic solvents (DES). The primary focus of this study was the elimination of volatile organosulfur compounds (VSCs) from model biogas. Biosorbents, including energetic poplar wood, antipka tree, corncobs, and beech wood, were used, each with varying levels of lignin and hemicellulose content. The selection of the DES with the greatest potential for VSC removal was carried out using COnductor-like Screening MOdel for Realistic Solvents (COSMO-RS) modeling. The chosen DES consisted of quaternary ammonium salts and glycols, specifically, tetrapropylammonium bromide and 1,2-hexanediol (1:3). The physicochemical properties of the new DES, such as the viscosity, density, and melting point, were evaluated. The biosorbents were treated with the selected DES after shredding, purifying, and sieving. Comprehensive analysis techniques, including thermogravimetric analysis, scanning electron microscopy, and X-ray diffraction, were employed on the modified biosorbents both before and after modification. The subsequent step involved the adsorption of VSCs from biogas. The results of this study demonstrated the superior performance of a novel sorbent based on corn cob modified by DES compared to commercially available alternatives. The sorption capacity ranged from 103.8 to 112.1 mg/g for various VSCs. The adsorption process using the new biosorbent can be described by the pseudo second order kinetic model, as well as the Yoon-Nelson and Adams-Bohart models. The high efficacy of the VSCs removal was attributed to the concurrent operation of the absorption and adsorption processes. The resulting sorbent was also characterized by its ability to regenerate repeatedly without significant loss of sorption capacity of the new sorbents.

Molecular engineering of a MOF with an ionic liquid sheath for direct air separation at ambient conditions

Combining ionic liquids (ILs) with metal–organic frameworks (MOFs) offers broad prospects for gas separation applications. However, identifying the best IL-MOF pair for a target gas separation solely based on experimental techniques is impractical. Herein, the promising IL and MOF combination was selected among 35,672 distinct ILs and 5,629 different MOFs by fusing computational methods at different molecular scales, density functional theory, conductor-like screening model for real solvents calculations, and grand canonical Monte Carlo simulations to engineer a MOF with an IL sheath (MOFILS) for direct air separation. The new MOFILS composed of [P6,6,6,14][DCA] and PCN-250(Fe) designed at the atomic level was then experimentally synthesized after fine-tuning the MOF to achieve high-performance air separation. An exceptionally high ideal O2/N2 selectivity of 26 was reached at 1 bar and 25 °C, boosting the benchmark value by four-times. The results of equilibrium and dynamic gas adsorption measurements further indicated a remarkably high selectivity of 382 for the separation of O2/N2:21/79 mixture, demonstrating the broad potential of the MOFILS designed in this work for direct air separation.

Preparation and impregnation of deep eutectic solvents containing zileuton onto adsorbents to elicit the biopharmaceutical attributes

Deep eutectic solvent (DES) is a contemporary and eco-friendly solvent recently exploited to modulate the solubility of drugs. Herein, we developed DESs for an increment of solubility and bioavailability of zileuton (ZLT). ZLT is an anti-inflammatory drug categorized as an inhibitor of the enzyme 5-lipoxygenase commonly prescribed for treating chronic bronchial asthma. However, its therapeutic uses are limited owing to its poor water solubility. Several stable DESs were developed and assessed for viscosity, pH, and solubility. The DES comprising ChCl: EG (1:3) exhibits an excellent ZLT solubility (57.27 ± 0.14 mg/mL). The molecular and electrostatic interaction was assessed through a conductor-like screening model for real solvents (COSMO-RS). Further, 1H NMR analysis, FTIR, and digital microscopy were used to investigate the molecular transition in the chosen DES-ZLT. The DES in a liquid state possesses several drawbacks, such as instability, volatility, and dose precision. Therefore, a wet impregnation approach utilizing inert carriers such as Aerosil-200 and Avicel PH-102 was performed for the solidification of liquid DES. The solidified DES-ZLT was characterized by DSC and PXRD techniques and indicated the existence of ZLT in a highly dissolved state. Furthermore, solid DES-ZLT showed a significant increment in the dissolution studies, resulting in a 2.91 fold rise in oral bioavailability of ZLT. Hence, the presented study proves a well-organized and proficient development of a solid DES system to ameliorate the solubility and stability aspects of ZLT, which could provide the template for promising drugs that lack therapeutic effectiveness owing to solubility issues.

Extraction of ofloxacin from water using hydrophobic eutectic solvents

Wastewater treatment plants do not cope well with emerging micropollutants, such as pharmaceuticals, because they are not effective to remove them. Therefore, this work aims to develop a process for the extraction of ofloxacin (OFX) based on a liquid-liquid extraction using hydrophobic eutectic solvents (HES), coupled with the Conductor-like Screening Model for Real Solvent (COSMO-RS) for solvent screening. First, COSMO-RS was used to predict the partition coefficient of OFX for four HES families: L-menthol: fatty acid, L-menthol: fatty alcohol, fatty acid: fatty acid and fatty acid: fatty alcohols, at three different molar ratios (2:1, 1:1, and 1:2). These results showed that HES formed by fatty acids, especially those with a longer alkyl chain and a higher fatty acid molar ratio, were the most suitable solvents for OFX extraction. Then, the most promising HES to extract OFX was evaluated experimentally. The HES decanoic acid: dodecanoic acid (C10 acid: C12 acid) in a molar ratio of 2:1 being the system with best extraction results of OFX was selected to optimize the extraction conditions of OFX, namely pH, HES: water ratio (v/v), and OFX concentration, using a response surface methodology (RSM). The results obtained showed that at a pH of 5.2, HES-water ratio (v/v) of 1.3, and 2.5 mg/ml of OFX that an extraction efficiency of OFX of (98.8 ± 0.9)% could be achieved. The results show that one-step OFX extraction is possible, but is significantly influenced by both the extraction parameters and the hydrophobic properties of the HES.

Assessing Viscosity in Sustainable Deep Eutectic Solvents and Cosolvent Mixtures: An Artificial Neural Network-Based Molecular Approach.

Deep eutectic solvents (DESs) are gaining recognition as environmentally friendly solvent alternatives for diverse chemical processes. Yet, designing DESs tailored to specific applications is a resource-intensive task, which requires an accurate estimation of their physicochemical properties. Among them, viscosity is crucial, as it often dictates a DES's suitability as a solvent. In this study, an artificial neural network (ANN) is introduced to accurately describe the viscosity of DESs and their mixtures with cosolvents. The ANN utilizes molecular parameters derived from σ-profiles, computed using the conductor-like screening model for the real solvent segment activity coefficient (COSMO-SAC). The data set comprises 1891 experimental viscosity measurements for 48 DESs based on choline chloride, encompassing 279 different compositions, along with 1618 data points of DES mixtures with cosolvents as water, methanol, isopropanol, and dimethyl sulfoxide, covering a wide range of viscosity measurements from 0.3862 to 4722 mPa s. The optimal ANN structure for describing the logarithmic viscosity of DESs is configured as 9-19-16-1, achieving an overall average absolute relative deviation of 1.6031%. More importantly, the ANN shows a remarkable extrapolation capacity, as it is capable of predicting the viscosity of systems including solvents (ethanol) and hydrogen bond donors (2,3-butanediol) not considered in the training. The ANN model also demonstrates an extensive applicability domain, covering 94.17% of the entire database. These achievements represent a significant step forward in developing robust, open source, and highly accurate models for DESs using molecular descriptors.

Selection of ionic liquid electrolytes for high-performing lithium-sulfur batteries: An experiment-guided high-throughput machine learning analysis

The polysulfide (PS) shuttle mechanism (PSM) is one of the most significant challenges of lithium-sulfur (Li-S) batteries in achieving high capacity and cyclability. One way to minimize the shuttle effect is to limit the PS solubilities in the battery electrolyte. Ionic liquids (IL) are particularly suited as electrolyte solvents because of their tunable physical and chemical properties. In this work, thousands of ILs are screened to narrow down potentially viable candidates to be used as electrolytes in Li-S batteries. To that end, the COnductor-like Screening Model for Realistic Solvents (COSMO-RS) calculations are performed over more than 36,000 ILs. An extensive database containing PS solubilities and other relevant properties is constructed at 25 °C. First, the effectiveness of the COSMO-RS calculations is experimentally tested with six different ILs having a wide range of solubility and viscosity values; a strong correlation between the PS solubility and battery performance is obtained. After specifying the target limits for promising ILs using the experimental battery performance data, machine learning (ML) tools are used to predict and identify the relationship between IL properties and PS solubilities and structural and molecular descriptors of ILs. The extreme gradient boosting (XGBoost) method successfully predicts the solubility and property values. Association rule mining (ARM) and the feature importance analysis show that anion descriptors are more dominant, whereas cations have less impact on the solubilities and properties of ILs. Finally, the imidazolium and pyridinium ILs with bis_imide and borate anion groups are identified as the most promising ones.

Multiscale modeling of CO2 capture in dicationic ionic liquids: Evaluating the influence of hydroxyl groups using DFT-IR, COSMO-RS, and MD simulation methods.

This work employs a combination of density functional theory-infrared (IR), conductor-like screening model for real solvents (COSMO-RS), and molecular dynamic (MD) methods to investigate the impact of hydroxyl functional groups on CO2 capture within dicationic ionic liquids (DILs). The COSMO-RS reveals that hydroxyl groups in DILs reduce the macroscopic solubility of CO2 but improve the selectivity of CO2 over CO, H2, and CH4 gases. Quantum methods in the gas phase and MD simulations in the liquid phase were conducted to delve deeper into the underlying mechanisms. The IR spectrum analysis confirms red shifts in CO2's asymmetric stretching mode and blue shifts in the CR-HR bond of the dication, indicating CO2-DIL interactions and the weakening of the anion-cation interactions caused by the presence of CO2. The results show that the positioning of anions around hydroxyl groups and HR atoms in rings inhibits the proximity of CO2 molecules, causing the hydrogen atoms within methylene groups to accumulate CO2. van der Waals forces were found to dominate the interaction between ions and CO2. The addition of hydroxyl groups strengthens the electrostatic interactions and hydrogen bonds between dications and anions. The stronger interaction energy between ions in [C5(mim)2-(C2)2(OH)2][NTf2]2 limits the displacement of CO2 molecules within this DIL compared to [C5(mim)2-(C4)2][NTf2]2. Compared to [C5(mim)2-(C4)2][NTf2]2, [C5(mim)2-(C2)2(OH)2][NTf2]2 exhibits stronger ion-ion interactions, higher density, and reduced free volume, resulting in a reduction in CO2 capture. These results provide significant insights into the intermolecular interactions and vibrational properties of CO2 in DIL complexes, emphasizing their significance in developing efficient and sustainable strategies for CO2 capture.

Oil extraction desulfurization based on ionic liquid: Back-extractant screening, experiment and process simulation

A comprehensive back-extractant screening method was first developed for regenerating ionic liquids (ILs) after oil extraction desulfurization (EDS). Statistical analysis was performed using the Technique for Order Preference by Similarity to an Ideal Solution (TOPSIS) with the Entropy Weighting Method (EWM) on screening indices obtained based on the COnductor-like Screening MOdel for Realistic Solvents (COSMO-RS) and the Quantitative Structure Activity Relationship (QSAR) models. CCl4 was selected as the optimal back-extractant among 196 candidates for regenerating the IL, 1-butyl-3-methylpyridinium dicyanamide ([BMPy][DCA]), targeting the simultaneous removal of thiophene (TS), benzothiophene (BT), dibenzothiophene (DBT), and 4,6-dimethyldibenzothiophene (4,6-DMDBT). The experimentally measured hexary liquid–liquid equilibrium (LLE) confirmed the satisfactory selectivities and distribution coefficients of CCl4. Based on the NRTL parameters correlated from the LLE data, a complete EDS process including IL-extraction and IL-regeneration was established and evaluated economically based on the total annual cost (TAC). The results demonstrated that this process significantly decreased the sulfur content from 500 ppm to less than 10 ppm. The study results verified the feasibility and effectiveness of the proposed method and showed the excellent industrial performance of the selected IL and back-extractant.

Application of ionic liquid extractant in enhanced separation of 2-propanol-n-hexane azeotrope system

2-Propanol and n-hexane are widely used (as) chemical reagents in electronic, pharmaceutical, and chemical industries. An efficient separation of the azeotropic system of 2-propanol-n-hexane is of profound practical significance. By using the conductor-like screening model for real solve (COSMO-RS) predictive model, ionic liquids as extractants for separating the azeotropic system of 2-propanol-n-hexane were evaluated with selectivity coefficients (S) and capacity (C) as the evaluation indexes. Based on the evaluation results, one high-performance extractants named hydroxylamine Cl (C8A19) was selected from 435 kinds of ionic liquids designed by combining 29 kinds of anions and 15 kinds of cations. Moreover, the reliability of the model in predicting the vapor–liquid phase equilibrium behavior of 2-propanol-n-hexane system was verified. Then, the effect of C8A19 on the vapor–liquid phase equilibrium of the 2-propanol-n-hexane system was investigated theoretically and experimentally. The results show that the azeotrope of the system can be broken when the molar fraction of C8A19 is 0.02, denoting that C8A19 can be used for enhanced separation of 2-propanol-n-hexane system. On the basis of the aforementioned study, the selectivity mechanism of the extractant was analyzed from the perspective of microscopic molecular interactions by using the descriptor (σ-profiles) of COSMO-RS. This study provides both theoretical and data support for further designing high-performance ionic liquid extractants and extraction process.

Consistent Analytical Second Derivatives of the Kohn-Sham DFT Energy in the Framework of the Conductor-Like Screening Model through Gaussian Charge Distributions.

The use of implicit solvation models such as the conductor-like screening model (COSMO) in quantum chemical calculations is very common, as both a rough estimate of solvation effects as well as a general tool for stabilizing ionic molecular structures. In order to generate a smooth potential energy surface as well as consistent gradients, it is necessary to apply the Gaussian charge model (GCM) for the COSMO charges. This work introduces an efficient implementation for consistent analytical second derivatives of the electronic energy with COSMO-GCM in the framework of the Kohn-Sham density functional theory. This is used to investigate the infrared spectroscopy of amino acids in aqueous solution, where the impact of pH on the molecular structure and vibrational spectra is examined. Furthermore, the structure and stability of selected all-metal aromatic cluster ions are assessed.

Development of ionic-liquid-impregnated activated carbon for sorptive removal of PFAS in drinking water treatment

Adsorption of per- and poly-fluoroalkyl substances (PFAS) on activated carbon (AC) is considerably hindered by the surface water constituents, degrading the ability of the AC adsorption process to remove PFAS in drinking water treatment. Herein, we developed ionic-liquid-impregnated AC (IL/AC) as an alternative to AC for PFAS sorption and demonstrated its performance with real surface water for the first time. Ionic liquids (ILs) of 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide (IL(C2)) and 1-hexyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide (IL(C6)) were selected from among 272 different ILs using the conductor-like screening model for realistic solvents (COSMO-RS) simulation. Impregnation of the ILs in AC was verified using various analytical techniques. Although the synthesized IL/ACs were less effective than pristine AC in treating PFAS in deionized water, their performances were less impacted by the surface water constituents, resulting in comparable or sometimes better performances than pristine AC for treating PFAS in surface water. The removal efficiencies of 10 wt% IL(C6)/AC for six PFAS were 1.40–1.96 times higher than those of pristine AC in a surface water sample containing 2.6 mg/L dissolved organic carbon and millimolar-level divalent cation concentration. PFAS partitioning from the surface water to ILs was not hindered by dissolved organic matter and was enhanced by the divalent cations, indicating the advantages of IL/ACs for treating significant amounts of PFAS in water. The synthesized IL/ACs were effective at treating coexisting pharmaceutical and personal-care products in surface water, showcasing their versatility for treating a broad range of water micropollutants.

Thermophysical insights and COSMO-RS study of triethylenetetramine-based protic ionic liquids with alkyl carboxylic acids

Protic ionic liquids (PILs) have increasing interest due to their potential application compared to conventional organic solvents. In the present study, new class of protic ionic liquids were developed by combining triethylenetetramine as cation and distinct carboxylic acids, specifically formic acid, butanoic acid, hexanoic acid, and octanoic acid employed as the anions. The products structures and purity were verified using 1H and 13C NMR as well as ESI-MS analysis. The structural variations effects on the thermophysical characteristics such as refractive index (nD), viscosity (η), density (ρ), and speed of sound (u) were evaluated throughout a broad temperature range. Temperatures between 293.15 and 333.15 K were used to calculate the viscosity and density values. It was also determined the thermal decomposition temperature (Td) and quantified the amount of water in the synthetic protic ionic liquids. Additional parameters such the expansion coefficient (α), standard entropy (S0), volume (V), lattice potential energy (UPOT), isentropic compressibility (βs), Intermolecular free length (Lf) of PILs were calculated using experimental values for sound speed and density. Furthermore, computation of activation energy employed the experimental viscosity values. In order to calculate the electronic polarizability and free volume present inside the ionic liquids, refractive indices of PILs were measured between the temperatures of 293.15 and 323.15 K. The study also explored the Conductor-like Screening Model for Real Solvents (COSMO-RS) computational approach to gain insights into the structural variation of TETA-based ionic liquids. The prepared PILs derived properties and linked with their structural moieties.

Inhibition of asphaltene aggregation using deep eutectic solvents: COSMO-RS calculations and experimental validation

Asphaltene precipitation/deposition adversely affects various oil and gas processes, such as oil recovery, transportation, and petroleum processing. The resulting increase in viscosity of crude oil decreases distillate yields creating unstable phase separation. Deep eutectic solvents (DESs) have recently gained interest as inhibitors of asphaltene aggregation. The goal of the present study is to derive the mechanism of inhibition of petroleum asphaltene aggregation by a novel screening of DESs. An archipelago-based chemical structure of asphaltene was adopted for performing quantum chemical calculations. The structure was used in the conductor-like screening model for real solvents (COSMO-RS) model to screen potential DESs for asphaltene precipitation. It was found that DESs containing thymol were the most promising of the 153 DES combinations screened. The COSMO-RS predictions were validated experimentally using solubility data of asphaltene in DESs. Among the studied DESs, thymol-diphenyl ether provided the highest solubility for asphaltene, which was further validated using the experimental and the COSMO-RS predicted data. In addition, to characterize the structural interactions between asphaltene and DESs, Fourier transform infrared (FTIR) spectroscopy and nuclear magnetic resonance (NMR) measurements were performed. It was found that strong interaction between asphaltene and the DESs is responsible for the higher asphaltene dispersion. The present approach opens pathways to rationally design and understand the impact of structural variation of DESs based on their interactions with asphaltene.

Excited state dipole moments of two dicyanobenzene isomers from thermochromic shifts and ab initio calculations

The excited state dipole moments of two positional isomers of dicyanobenzene have been determined from thermochromic shifts of the absorption and fluorescence emission spectra in ethyl acetate solution and compared to the results of ab initio calculations. We found that the dipole moments of excited states from thermochromic shifts closely resemble the ab initio values of the isolated molecule, while the results of conductor-like screening model (COSMO) using the same wave function model as for the isolated molecule, shows considerable deviations from the experimental values. It is shown that the dipole moments of the two cyano groups add up vectorially for both the ground and excited states.

Environmental impact of PFAS: Filling data gaps using theoretical quantum chemistry and QSPR modeling

Per- and polyfluorinated alkyl substances (PFAS), known for their widespread environmental presence and slow degradation, pose significant concerns. Of the approximately 10,000 known PFAS, only a few have undergone comprehensive testing, resulting in limited experimental data. In this study, we employed a combination of physics-based methods and data-driven models to address gaps in PFAS bioaccumulation potential. Using the COnductor-like Screening MOdel for Realistic Solvents (COSMO-RS) method, we predicted n-octanol/water partition coefficients (logKOW), crucial for PFAS bioaccumulation. Our developed Quantitative Structure-Property Relationship (QSPR) model exhibited high accuracy (R2 = 0.95, RMSEC = 0.75) and strong predictive ability (Q2LOO = 0.93, RMSECV = 0.83). Leveraging the extensive NORMAN, we predicted logKOW for over 4,000 compounds, identifying 244 outliers out of 4519. Further categorizing the database into eight Organisation for Economic Co-operation and Development (OECD) categories, we confirmed fluorine atoms role in enhanced bioaccumulation. Utilizing predicted logKOW, water solubility logSW, and vapor pressure logVP values, we calculated additional physicochemical properties that are responsible for the transport and dispersion of PFAS in the environment. Parameters such as Henry’s Law (kH), air–water partition coefficient (KAW), octanol–air coefficient (KOA), and soil adsorption coefficient (KOC) exhibited favorable correlations with literature data (R2 > 0.66). Our study successfully filled data gaps, contributing to the understanding of ubiquitous PFAS in the environment and estimating missing physicochemical data for these compounds.

Extraction of 5-Hydroxymethylfurfural and Furfural in Aqueous Biphasic Systems: A COSMO-RS Guided Approach to Greener Solvent Selection.

5-Hydroxymethylfurfural (HMF) and furfural (Fur) are promising biobased platform chemicals, derived from the dehydration of carbohydrate feedstocks, normally conducted in an aqueous phase. Plagued by side-reactions in such phase, such as the rehydration to levulinic acid (LA) and formic acid (FA) or self-condensation to humins, HMF and Fur necessitates diversification from monophasic aqueous reaction systems toward biphasic systems to mitigate undesired side-reactions. Here, a methodology based on the COnductor-like Screening MOdel for Real Solvents (COSMO-RS) method was used to screen solvent candidates based on the predicted partition coefficients (Ki). Hansen solubility parameters in conjunction with excess thermodynamic quantities determined by COSMO-RS were employed to assess solvent compatibility. Experimental validation of the COSMO-RS values highlighted only minor deviations from the predictions with root-mean-square-error (RMSE) values of HMF and Fur at 0.76 and 5.32, respectively, at 298 K. The combined effort suggested cyclohexanone, isophorone, and methyl isobutyl ketone (MIBK) as the best candidates. Finally, extraction solvent reuse demonstrated cyclohexanone suitability for HMF extraction with KHMF of 3.66 and MIBK for Fur with KFur 7.80 with consistent partitioning across four total runs. Both solvents are classified as recommended by the CHEM21 solvent selection guide, hence adding to the sustainability of the process.