Thermodynamics of the Molecular and Chiral Recognition of Cycloalkanols and Camphor by Modified <i>β</i>-Cyclodextrins Possessing Simple Aromatic Tethers

Liu, Yu; Yang, En‐Cui; Yang, Yifei; Zhang, Heng‐Yi; Fan, Zhi; Ding, Fei; Cao, Rui

doi:10.1021/jo035355q

Cited by 31 publications

(19 citation statements)

References 45 publications

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“…66 Cyclodextrins posses a hydrophobic central cavity and a hydrophilic outer surface and can therefore be used to improve the delivery for poorly soluble drugs. 82 Therefore, in addition to hydrogen bonds, non-polar dispersion is also important.…”

Section: The Test Set Complexesmentioning

confidence: 99%

Comprehensive Benchmark of Association (Free) Energies of Realistic Host–Guest Complexes

Sure

Grimme

2015

J. Chem. Theory Comput.

214

352

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The S12L test set for supramolecular Gibbs free energies of association ΔGa (Grimme, S. Chem. Eur. J. 2012, 18, 9955-9964) is extended to 30 complexes (S30L), featuring more diverse interaction motifs, anions, and higher charges (-1 up to +4) as well as larger systems with up to 200 atoms. Various typical noncovalent interactions like hydrogen and halogen bonding, π-π stacking, nonpolar dispersion, and CH-π and cation-dipolar interactions are represented by "real" complexes. The experimental Gibbs free energies of association (ΔGa exp) cover a wide range from -0.7 to -24.7 kcal mol-1. In order to obtain a theoretical best estimate for ΔGa, we test various dispersion corrected density functionals in combination with quadruple-ζ basis sets for calculating the association energies in the gas phase. Further, modern semiempirical methods are employed to obtain the thermostatistical corrections from energy to Gibbs free energy, and the COSMO-RS model with several parametrizations as well as the SMD model are used to include solvation contributions. We investigate the effect of including counterions for the charged systems (S30L-CI), which is found to overall improve the results. Our best method combination consists of PW6B95-D3 (for neutral and charged systems) or ωB97X-D3 (for systems with counterions) energies, HF-3c thermostatistical corrections, and Gibbs free energies of solvation obtained with the COSMO-RS 2012 parameters for nonpolar solvents and 2013-fine for water. This combination gives a mean absolute deviation for ΔGa of only 2.4 kcal mol-1 (S30L) and 2.1 kcal mol-1 (S30L-CI), with a mean deviation of almost zero compared to experiment. Regarding the relative Gibbs free energies of association for the 13 pairs of complexes which share the same host, the correct trend in binding affinities could be reproduced except for two cases. The MAD compared to experiment amounts to 1.2 kcal mol-1, and the MD is almost zero. The best-estimate theoretical corrections are used to back-correct the experimental ΔGa values in order to get an empirical estimate for the "experimental", zero-point vibrational energy exclusive, gas phase binding energies. These are then utilized to benchmark the performance of various "lowcost" quantum chemical methods for noncovalent interactions in large systems. The performance of other common DFT methods as well as the use of semiempirical methods for structure optimizations is discussed.

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Section: The Test Set Complexesmentioning

confidence: 99%

Comprehensive Benchmark of Association (Free) Energies of Realistic Host–Guest Complexes

Sure

Grimme

2015

J. Chem. Theory Comput.

214

352

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“…Although the free‐energy difference δΔ G 0 =Δ G 0 (4‐pentylpyridine)−Δ G 0 (4‐methylpyridine) is −10 kJ mol −1 , the enthalpy difference δΔ H 0 =Δ H 0 (4‐pentylpyridine)−Δ H 0 (4‐methylpyridine) is positive and only 1.7 kJ mol −1 ; δ T Δ S 0 = T Δ S 0 (4‐pentylpyridine)− T Δ S 0 (4‐methylpyridine)=11.8 kJ mol −1 at 298 K. Therefore, the tighter binding of 4‐pentylpyridine relative to 4‐methylpyridine can be attributed to the entropic term. Liu et al 14. reported that chiral recognition of camphor by modified cyclodextrins is driven by entropic change.…”

Section: Resultsmentioning

confidence: 99%

Thermodynamics of Hydrophobic Interactions: Entropic Recognition of a Hydrophobic Moiety by Poly(Ethylene Oxide)–Zinc Porphyrin Conjugates

Iwamoto

Mizutani

Kawasaki

2007

Chemistry An Asian Journal

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The recognition of 4-alkylpyridines by water-soluble poly(ethylene oxide)-zinc porphyrin conjugates was studied with a focus on the thermodynamic parameters of binding. Microcalorimetric studies indicated that binding of the alkyl group of the guest in water is driven by the entropic term (delta DeltaH0 = DeltaH0(4-pentylpyridine) - DeltaH0(4-methylpyridine) = +1.7 kJ mol(-1), deltaT DeltaS0 = TDeltaS0(4-pentylpyridine) - TDeltaS0(4-methylpyridine) = +11.8 kJ mol(-1) at 298 K), thus showing the significance of water reorganization during host-guest interaction. The enthalpy-entropy compensation temperature of binding of 4-alkylpyridines was as low as 38 K; only below this temperature could the enthalpic term be a driving force. The binding affinity was modulated by the addition of cations and by varying the degree of polymerization of poly(ethylene oxide), which suggests that guest binding is coupled with polymer conformation.

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“…Synthesis of mono(6-phenolic-6-deoxy)-β-CD 1 [18] To a solution of phenol (0.4 g, 4 mmol) in DMF (10 mL) is added anhydrous K 2 CO 3 (0.56 g, 4 mmol). The mixture is stirred for 2 h at room temperature under nitrogen, after which 6-OTs-β-CD (1.9 g, 1.5 mmol) in dry DMF (20 mL) is added dropwise with stirring, and then the whole solution is heated at 80℃ for 24 h. The resultant solution is evaporated under reduced pressure to give a yellow powder, which is dissolved in a minimum amount of hot water, and then the solution is poured into acetone (200 mL).…”

Section: 2mentioning

confidence: 99%

Self-assembly behavior of phenyl modified β-cyclodextrins

Zhao

Liu

2006

SCI CHINA SER B

Self Cite

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The self-assembly behavior of mono(6-phenolic-6-deoxy)-β-cyclodextrin (1) both in solution and the solid state is comparatively studied by X-ray crystallography and 1 H NMR spectroscopy. The results obtained show that the phenolic groups in the crystal 1 can successively penetrate into the adjacent β-cyclodextrin cavities from the secondary side to form head-to-tail linear polymeric supramolecule with a 2-fold screw axis. The self-assembly behavior also can be determined in D 2 O solution, giving a self-association constant of 240 mol −1 ⋅L. Using the present and previous structures reported for the relevant β-cyclodextrin derivatives, i.e., mono(6-anilino-6-deoxy)-β-cyclodextrin (2), mono(6-phenylselenyl-6-deoxy)-β-cyclodextrin (3), and mono(6-phenylthio-6-deoxy)-β-cyclodextrin (4), we further reveal the factors governing the formations of supramolecular assemblies.Cyclodextrins(CDs), a cyclic oligosaccharide composed of 6, 7, or 8 α-1,4-linked D-glucopyranose units, are able to form supramolecular complexes with a wide range of guest molecules by the inclusion complexation within the hydrophobic cavities, and therefore have received much attention in the fields of molecular recognition and molecular assembly [1][2][3][4] . The conformations of many modified CDs have been carefully studied both in solution and the solid state, and most studies show that the formation of selfinclusion complexes or supramolecular assemblies mainly depend on the spatial size-fit and/or geometric complementarity between the substituents and CD cavities [5][6][7][8][9][10][11][12][13][14][15][16] . We have recently reported systematical studies on the binding behaviors of mono-modified β-CDs both in solution and the solid state. The obtained results indicated that the assembly modes of polymeric supramolecules might be gov erned through the precise control of structures and chemical properties of substituents [10] . In the present study, we wish to report the self-assembly behavior of mono(6-phenolic-6-deoxy)-β-cyclodextrin (1) both in solution and the solid state by means of X-ray crystallography and 1 H NMR. Using the present and previous structures reported for the relevant β-CD derivatives (Fig. 1), i.e., mono(6-anilino-6-deoxy)-β-CD (2) [11] , mono(6-phenylselenyl-6-deoxy)-β-CD (3) [10] , and mono(6-phenylthio-6-deoxy)-β-CD (4) [16] , the factors governing the formations of supramolecular assemblies are further discussed. It is of our particular interest to investigate how the slight difference of pivot heteroatoms, through which the aromatic substituent is tethered to β-CD, affects the binding behavior of modified β-CDs with phenyl substituents both in solution and the solid state.

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Thermodynamics of the Molecular and Chiral Recognition of Cycloalkanols and Camphor by Modified β-Cyclodextrins Possessing Simple Aromatic Tethers

Cited by 31 publications

References 45 publications

Comprehensive Benchmark of Association (Free) Energies of Realistic Host–Guest Complexes

Comprehensive Benchmark of Association (Free) Energies of Realistic Host–Guest Complexes

Thermodynamics of Hydrophobic Interactions: Entropic Recognition of a Hydrophobic Moiety by Poly(Ethylene Oxide)–Zinc Porphyrin Conjugates

Self-assembly behavior of phenyl modified β-cyclodextrins

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