Effects of molecular shape on alcohol aggregation and water hydrogen bond network behavior in butanol isomer solutions

Choi, Seungeui; Saravanan, P.; Choi, Junho

doi:10.1039/d1cp00634g

Cited by 22 publications

(11 citation statements)

References 78 publications

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“…These findings are consistent with the previous predictions of the architecture of H-bonded clusters for butanol isomers. For example, based on the calculated cluster size distributions, the average number of molecules contained in the aggregates was around 13, 11, 11, and 4 for n -, sec -, iso -, and tert -butanol, respectively . In other computational works, , the probability of finding monomers and pentamers in n -butanol was the highest.…”

Section: Results and Discussionmentioning

confidence: 87%

“…For example, based on the calculated cluster size distributions, the average number of molecules contained in the aggregates was around 13, 11, 11, and 4 for n-, sec-, iso-, and tert-butanol, respectively. 15 In other computational works, 7,8 the probability of finding monomers and pentamers in n-butanol was the highest. In the case of tert-butanol, it was predicted to form either cyclic tetramers 13 or hexamers.…”

Section: Resultsmentioning

confidence: 88%

“…In fact, the discussions on the steric hindrance effect of molecular shape, the impact of the alkyl chain length, and the position of the OH group on the supramolecular structure in various alcohols are abundant in the literature. − However, the information on the associating phenomena of alcohols with the steric hindrance in the form of the attached phenyl group is based practically only on the dielectric and infrared spectroscopy studies and many contradictions have arisen on this topic. − First, Kalinovskaya et al and Johari et al postulated that the phenyl group in 1-phenyl-1-propanol reduces the extent of intermolecular H-bonding as the Debye-type relaxation process vanishes. Subsequently, Böhmer et al concluded that the aromatic ring only affects the supramolecular architecture of phenyl-propanols, while the structure formation through HBs is not generally suppressed by the increased steric hindrance.…”

Section: Introductionmentioning

confidence: 99%

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Supramolecular Structure of Phenyl Derivatives of Butanol Isomers

et al. 2022

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Wide-angle X-ray scattering patterns were recorded for a series of aliphatic butanol isomers ( n -, iso -, sec -, tert -butanol) and their phenyl derivatives (4-phenyl-1-butanol, 2-methyl-3-phenyl-1-propanol, 4-phenyl-2-butanol, and 2-methyl-1-phenyl-2-propanol, respectively) to determine their atomic-scale structure with particular emphasis on the formation of supramolecular clusters. In addition, molecular dynamics simulations were carried out and yielded good agreement with experimental data. The combination of experimental and theoretical results allowed clarification of the origin of the pre-peak appearing at low scattering angles for the aliphatic butanols and its absence for their phenyl counterparts. It was demonstrated that the location of the hydroxyl group in the molecule of alkyl butanol, its geometry, and rigidity determine the morphology of the supramolecular clusters, while the addition of the aromatic moiety causes more disordered organization of molecules. The phenyl group significantly decreases the number of hydrogen bonds and size of the supramolecular clusters formed via the O–H···O scheme. The lower association ability of phenyl alcohols via H-bonds is additionally attenuated by the appearance of competing π–π configurations evidenced by the structural models.

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Section: Results and Discussionmentioning

confidence: 87%

Section: Resultsmentioning

confidence: 88%

Section: Introductionmentioning

confidence: 99%

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Supramolecular Structure of Phenyl Derivatives of Butanol Isomers

et al. 2022

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“…n-Butanol is the shortest linear alcohol that is able to form a separate phase when mixed with water at ambient conditions. [16] It is therefore suitable for liquid-liquid extraction from water. However, due to the mutual solubility of n-butanol and water, the n-butanol phase during extraction is not pure, but saturated with water.…”

Section: The Structure Of Wet N-butanolmentioning

confidence: 99%

n‐Butanol: An Ecologically and Economically Viable Extraction Solvent for Isolating Polar Products from Aqueous Solutions

Reetz

König

2021

Eur J Org Chem

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In memory of Klaus HafnerWater is the solvent of choice in terms of greenness and sustainability. However, it can be difficult to isolate very polar products from water. Here, we discuss the use of n-butanol as a solvent to extract polar compounds from aqueous solution. n-Butanol produces high yields and can also be sourced sustainably from biomass, which makes it attractive from a climate perspective. The reason for its high efficiency is that the wet n-butanol phase is a nanomaterial that incorporates little pockets of water that can stabilize the polar solute. Thus, the environment remains very water-like, and the presence of hydrophobic groups can tip the equilibrium towards the nbutanol phase. We also discuss a simple estimate whether nbutanol will be an efficient extraction solvent for the compound of interest based on common public databases. This should help to guide practicing organic chemists during the solvent selection process.

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“…Meanwhile, by employing the combination of MD simulation and graph theory, the aggregation behavior of solute and water molecules has been examined with the calculation of network properties of molecular aggregates in a wide range of binary mixtures of water including salts, − osmolytes, ,, alcohols, − and so on. − Sundar et al conducted a detailed analysis, calculating the radial distribution function (RDF) and graph theoretical properties of the H-bond network of solution in various osmolyte–water mixtures . The results indicate that the local solvation structure and overall H-bond network properties in urea and glycerol solutions are similar regardless of the nature of the osmolyte, whether it is a denaturant or stabilizer.…”

Section: Introductionmentioning

confidence: 99%

Molecular Aggregation Behavior and Microscopic Heterogeneity in Binary Osmolyte–Water Solutions

Seo,

Singh,

Ryu

et al. 2023

J. Chem. Inf. Model.

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Osmolytes, small organic compounds, play a key role in modulating the protein stability in aqueous solutions, but the operating mechanism of the osmolyte remains inconclusive. Here, we attempt to clarify the mode of osmolyte action by quantitatively estimating the microheterogeneity of osmolyte−water mixtures with the aid of molecular dynamics simulation, graph theoretical analysis, and spatial distribution measurement in the four osmolyte solutions of trimethylamine-N-oxide (TMAO), tetramethylurea (TMU), dimethyl sulfoxide, and urea. TMAO, acting as a protecting osmolyte, tends to remain isolated with no formation of osmolyte aggregates while preferentially interacting with water, but there is a strong aggregation propensity in the denaturant TMU solution, characterized by favored hydrophobic interactions between TMU molecules. Taken together, the mechanism of osmolyte action on protein stability is proposed as a comprehensive one that encompasses the direct interactions between osmolytes and proteins and indirect interactions through the regulation of water properties in the osmolyte− water mixtures.

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Effects of molecular shape on alcohol aggregation and water hydrogen bond network behavior in butanol isomer solutions

Abstract: Despite that butanol isomers such as n-butanol, sec-butanol, isobutanol and tert-butanol have the same chemical formula, their liquid-liquid phase diagram is distinct. That is, the tert-butanol is miscible in water...

Cited by 22 publications

References 78 publications

Supramolecular Structure of Phenyl Derivatives of Butanol Isomers

Supramolecular Structure of Phenyl Derivatives of Butanol Isomers

n‐Butanol: An Ecologically and Economically Viable Extraction Solvent for Isolating Polar Products from Aqueous Solutions

Molecular Aggregation Behavior and Microscopic Heterogeneity in Binary Osmolyte–Water Solutions

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