Comment on “Structural Study of a Eutectic Solvent Reveals Hydrophobic Segregation and Lack of Hydrogen Bonding between the Components”

Schaeffer, Nicolas; Silva, Liliana P.; Coutinho, João A. P.

doi:10.1021/acssuschemeng.2c02985

Cited by 6 publications

(5 citation statements)

References 8 publications

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“…All six systems appear to present pseudobinary eutectic behavior where two eutectic points are observed. Elevated MPs between the eutectic points are suggestive of the presence of a cocrystal composition, 102 which in these cases occurs for compositions that may correspond to 2:3, 1:1, or 3:2 cocrystal compositions. Indeed, for the NPe 4 I 3 /m-F 4 DIB system, we were able to isolate crystals of the 1:1 cocrystal by recrystallizing the 5:5 asground material in methanol in a freezer.…”

Section: Experimental Development Of New Halogen Bonding-based Des Fo...mentioning

confidence: 99%

eutXG: A Machine-Learning Model to Understand and Predict the Melting Point of Novel X-Bonded Deep Eutectic Solvents

Ayres,

Bandara,

McMillen

et al. 2024

ACS Sustainable Chem. Eng.

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We present the application of an extreme gradient boosting model (eutXG) to predict the melting point (MP) of deep eutectic solvents (DES). The model is based on XGBoost, a decision tree ensemble based on gradient boosting designed to be highly scalable that enables superior training speed and prediction accuracy. The selected model�trained with molecular fingerprints, molar ratios, and selected chemical descriptors�enabled the prediction of the MPs of DES with an average accuracy of 97.6%, which represents a difference of just ±2.4% with respect to the values reported in the literature. Using SHapley Additive exPlanations (SHAP), further insights into the relative importance of different inputs used to train the machine learning model were identified. Moreover, the generalization ability of the eutXG model was critically assessed by comparing the predicted vs the experimentally determined MP of a series of novel DES based on halogen bonding, developed by mixing tetraalkylammonium triiodide salts (NPe 4 I 3 or NHex 4 I 3 ) with organoiodines, such as 1,2diiodotetrafluorobenzene (o-F 4 DIB), 1,3-diiodotetrafluorobenzene (m-F 4 DIB), or 2,5-diiodothiophene (2,5-DIT), demonstrating its ability to predict the actual melting with a difference of only 2 K. Our results not only reinforce the importance of having (at least some) representative data for the training step to increase the accuracy of the model's predictions but also demonstrate the ability of eutXG to accelerate the development of novel applications for this entirely new class of hydrophobic DES, potentially impacting a wide range of fields from pharmaceuticals to agrochemicals.

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Section: Experimental Development Of New Halogen Bonding-based Des Fo...mentioning

confidence: 99%

eutXG: A Machine-Learning Model to Understand and Predict the Melting Point of Novel X-Bonded Deep Eutectic Solvents

Ayres,

Bandara,

McMillen

et al. 2024

ACS Sustainable Chem. Eng.

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“…In their Comment to our paper entitled “Structural Study of a Eutectic Solvent Reveals Hydrophobic Segregation and Lack of Hydrogen Bonding between the Components”, Schaeffer et al disagree with our statement that the obtained results may “challenge the fundamental definition of DESs”, since the system formed by butylated hydroxytoluene (BHT) and l -menthol (MEN) cannot be classified as a deep eutectic solvent (DES). We agree with the authors that some misconceptions persist in the present literature, since this system has been designated as a “type V DES” in a recent publication .…”

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confidence: 95%

“…As a second point in their Comment, Schaeffer et al 2 assert that the results extrapolated for one mixture point (BHT:MEN 1:3 or, equivalently, x BHT = 0.25) across the whole compositional range can lead to erroneous or spurious results. This composition is very close to one of the eutectic points found by the authors (x BHT = 0.24) from their phase diagram.…”

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confidence: 99%

Response to Comment on “Structural Study of a Eutectic Solvent Reveals Hydrophobic Segregation and Lack of Hydrogen Bonding between the Components”

Busato

Mannucci

Lisio

et al. 2022

ACS Sustainable Chem. Eng.

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“…It was recently demonstrated that mixing of BHT and MEN at a 1:3 molar ratio (or, equivalently, at BHT molar fraction x BHT = 0.25) provides a liquid phase at room temperature suitable for liquid–liquid microextractions of pesticides and fat-soluble micronutrients from food matrices. , This system is very intriguing as the molecular structure of BHT shows an evidently encumbered hydroxyl group because of two adjacent tert -butyl substituents (Figure ). − Given that the hydroxyl group should be the main thing responsible for the H-bond interaction, we decided to study also MEN mixtures with TBC and PC counterparts, which are analogues of BHT but with respectively one and no tert -butyl groups in ortho -position to the hydroxyl. Note that the PC compound possesses acute toxicity, so that the PC/MEN mixtures are far from meeting the requirements of sustainable solvents, but it was selected to solve the scientific case as it is the structural analogue species to the BHT and TBC ones but with no steric hindrance around the hydroxyl group.…”

Section: Introductionmentioning

confidence: 99%

The Complex Story Behind a Deep Eutectic Solvent Formation as Revealed by l-Menthol Mixtures with Butylated Hydroxytoluene Derivatives

Busato,

Mannucci,

Rocchi

et al. 2023

ACS Sustainable Chem. Eng.

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An in-depth study of the hydrophobic eutectic mixtures formed by l-menthol (MEN) with the butylated hydroxytoluene (BHT), 2-tert-butyl-p-cresol (TBC), and p-cresol (PC) compounds has been carried out, where TBC and PC are analogous to the BHT species but with a different degree of steric hindrance around the hydroxyl group. Thermal characterization evidenced that the BHT/MEN system can be classified as an ideal eutectic, while the TBC/MEN and PC/MEN mixtures behave as type V deep eutectic solvents (DESs) for a wide range of compositions around the eutectic point. As shown by an array of experimental and theoretical methods, in the BHT/MEN mixtures the establishment of hydrogen-bond (H-bond) interactions between the components is dramatically hampered because of the steric hindrance in the BHT molecule, so that the achievement of a liquid phase at room temperature for the eutectic composition is driven by apolar–apolar attractions among the alkyl functional groups of the constituents. Differently, the TBC-MEN donor–receptor H-bond is the main driving force for the formation of a type V DES and derives from a concurrence of electronic and steric factors characterizing the TBC molecule. Finally, the absence of steric hindrance around the hydroxyl group allows the self-association among PC molecules through H-bonded networks already in the pristine compound, but the replacement with the more favorable PC-MEN H-bond provides a type V DES upon mixing of these components. Our combined approach, together with the peculiarity of the inspected systems, delivered an archetypal study able to shed light onto the various contributions ruling the structure–properties relationship in DESs and possibly deepening the currently accepted view of these inherently complex media.

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Comment on “Structural Study of a Eutectic Solvent Reveals Hydrophobic Segregation and Lack of Hydrogen Bonding between the Components”

Cited by 6 publications

References 8 publications

eutXG: A Machine-Learning Model to Understand and Predict the Melting Point of Novel X-Bonded Deep Eutectic Solvents

eutXG: A Machine-Learning Model to Understand and Predict the Melting Point of Novel X-Bonded Deep Eutectic Solvents

Response to Comment on “Structural Study of a Eutectic Solvent Reveals Hydrophobic Segregation and Lack of Hydrogen Bonding between the Components”

The Complex Story Behind a Deep Eutectic Solvent Formation as Revealed by l-Menthol Mixtures with Butylated Hydroxytoluene Derivatives

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