Heterogenous adsorption mechanisms for describing enantioselective retention in normal-phase liquid chromatography.

In this study, the enantioselective retention behaviors of methyl mandelate (MM) and benzoin (B) were investigated using Chiralpak IB as a sorbent and ethanol, 1-propanol, and 1-butanol as solvent modifiers in the normal-phase mode. For both MM and B, similar chiral recognition mechanisms were observed, potentially involving at least two types of chiral adsorption sites. With a retention model describing local retention behaviors, an enantioselectivity model based on a three-site model was proposed to describe the data. Fitted parameters were also used to analyze the contributions of each type of adsorption site to the apparent retention behavior. Combining the local retention model with the three-site model provided a qualitative and quantitative explanation for the correlation between modifier concentration and enantioselectivity. Overall, our results indicated that heterogeneous adsorption mechanisms are a key aspect in understanding enantioselective retention behaviors. Distinct local adsorption sites contribute differently to apparent retention behaviors, with these contributions being influenced by the mobile phase composition to varying degrees. Hence, enantioselectivity changes with variations in modifier concentration.

Effect of mobile-phase modifiers on the enantioselective retention behavior of methyl mandelate with an amylose 3,5-dimethylphenylcarbamate chiral stationary phase under reversed-phase conditions.

In this study, methanol, ethanol, n-propyl alcohol, isopropyl alcohol, acetone, and tert-butanol were used as organic modifiers in reversed-phase mode chiral liquid-chromatography to systematically investigate the effects of mobile phase components on the enantioselective retention behavior of methyl mandelate with immobilized amylose 3,5-dimethylphenylcarbamate-based sorbent called Chiralpak IA. A two-site enantioselective model was used to obtain information on the recognition mechanisms by observing the dependence of the enantioselectivity and retention factor difference on the modifier content. Similar enantioselective retention behaviors were observed for all modifiers, and characteristic modifier concentration points (PL , PM , and PH ) were identified. At modifier concentrations up to PM , the weakened hydrophobic environment resulted in polymer structural relaxation, which changed the recognition mechanisms. By contrast, at concentrations beyond PH , considerably different enantioselectivity behaviors were observed, indicating that the existence of dipole-dipole interaction, which was stronger at higher modifier concentrations, contributed to the retention mechanisms. The concentrations at which these characteristic points occurred were dependent on the carbon number of the modifier molecule. Modifiers with more carbon numbers facilitated the transition in the enantioselective behaviors. These results demonstrated that the proposed method can provide a physically consistent quantitative description of enantioselective retention behavior in reversed-phase mode.

Retention modeling and adsorption mechanisms in reversed-phase liquid chromatography.

To interpret the dependence of solute retention behavior on modifier content in reversed-phase liquid chromatography, a theoretical framework, based on the concentration dependence of solvophobic forces imposed on solutes and the competitive adsorptions of solutes and solvent modifiers, was proposed. The generality of the developed model was demonstrated by comparing the model with conventional retention models. The linear dependence of the Gibbs energy change of solute adsorption with respect to the modifier concentration was assumed, and the model was fitted to the experimental results, with good agreement demonstrated between the experimental data and the model. Retention behaviors were inferred to be determined by two key dimensionless groups that represented the reductions in the retention factors resulting from a weakened solvophobic interaction and modifier competitive adsorption. The retention behaviors were successfully deconvoluted for each contribution as a function of the modifier concentration by using the fitted parameters. The effects of both contributions on the retention behaviors were enhanced for the solutes with aromatic groups. The standard Gibbs energy change SLo of benzene adsorption was found to depend linearly on the number of modifier molecules present but independent of modifier identity. For the solutes associated with hydrogen-bonding groups, the degree of reduction in the solvophobic interactions was considerably reduced. Hence, the relative contributions of both mechanisms to solute retention depend greatly on the solute structure. Perturbation method was performed to investigate the modifier adsorption mechanisms. The results show that the standard Gibbs energy change SLo for the first-layer adsorption of modifiers changed linearly with the carbon number of modifier molecule. These results demonstrated that the proposed model can offer a physically consistent quantitative description of retention when solvent composition is varied.

Effect of 2-propanol content on solute retention mechanisms determined using amylose tris(3,5-dimethylphenylcarbamate) chiral stationary phase under normal- and reversed-phase conditions.

The electrostatic interactions between chiral solutes and polysaccharide (PS)-based chiral selectors are the key to achieving chiral recognition; however, PS-based sorbents, derivatized of phenyl moieties, can exhibit considerably non-polar characteristics, and they are also useful for the separation of enantiomers in the reversed-phase mode. In this study, an immobilized amylose 3,5-dimethylphenylcarbamate-based sorbent was used to investigate the balance between electrostatic interactions and solvophobic interactions, with complementary effects on solute retention behavior when the isopropanol (IPA) concentration was altered. It was proposed that in both normal- and reversed-phase modes, information on the retention mechanisms could be obtained by observing the curvature of the logarithm of the retention factor versus the logarithm of the IPA concentration, and the slope values of the curves were related to the number of displaced IPA molecules upon solute adsorption. Using the proposed model and the two-site adsorption model, the retention behaviors of pantolactone (PL) enantiomers in both normal- and reversed-phase modes were investigated. The PL-sorbent interactions were classified into four types: electrostatic/enantioselective, electrostatic/nonselective, solvophobic/enantioselective, and solvophobic/nonselective. At IPA concentrations below 50 vol.% in n-hexane, the retention behaviors of PL were dominated by electrostatic/enantioselective sites, whereas at IPA concentrations beyond 50 vol.%, the solvophobic interactions of PL-sorbent were strengthened and mostly nonselective. By contrast, in the reversed-phase mode, a reverse in the enantiomeric elution order of PL was observed at 10 vol.% IPA, and considerably different enantioselectivity behaviors were found below and above 20 vol.%, indicating an abrupt change in the sorbent molecular environment. At IPA concentrations beyond 40 vol.%, the presence of PL-sorbent electrostatic interactions enhanced chiral recognition.

Effect of solvents on the chiral recognition mechanisms of immobilized cellulose-based chiral stationary phase.

The effect of solvents on the enantioselectivities of four structurally similar chiral solutes with a cellulose derivative-based chiral stationary phase, Chiralpak IB, were studied using acetone (AC), 2-propanol (IPA), and tert-butanol (TBA) separately as polar modifiers. The enantioselectivities α of benzoin and methyl mandelate decrease with an increase in modifier concentration CM, whereas the enantioselectivity of pantolactone increased with increasing AC concentration. These results were attributed to the heterogeneous adsorption mechanisms of enantiomers. To interpret the dependence of enantioselectivity on modifier content, an enantioselectivity model based on a two-site adsorption model was proposed. The dependence of α on CM was inferred to be mainly due to the distinct modulating effects of modifier concentration on the two adsorption sites: the nonselective type-I site and enantioselective type-II site. The model fitted the benzoin data satisfactorily over a wide TBA concentration range. The retention factors as a function of TBA concentration were successfully deconvoluted for each site. With the use of the proposed model, it was inferred that the chiral recognitions of benzoin and methyl mandelate were mainly achieved by the presence of an aromatic group adjacent to the hydroxyl group. When using IPA and TBA separately as modifiers, the presence of an aromatic group adjacent to the ketone group mainly contributed to the nonselective π interactions and enantioselective steric interactions, respectively. These results, along with those of the modifier adsorption isotherms, determined using the perturbation method, as well as the retention behaviors of various achiral solutes, indicate that the molecular recognition mechanism of IB sorbent is highly sensitive to the adsorbate's molecular geometry. The molecular environment of the sorbent can be controlled using different modifiers, leading to distinct adsorption and retention mechanisms.

Elucidation of retention behaviors in reversed-phase liquid chromatography as a function of mobile phase composition.

Various retention models have been widely used for understanding the retention mechanisms of solutes in reversed-phase chromatography systems. The models have been used to interpret the often-observed linear plots of the logarithms of retention factor k versus the solvent modifier concentration CM and ln k versus ln⁡CM. In this study, the retention behaviors of nine solutes as a function of acetonitrile (ACN) concentration were systematically investigated using a commercially available C18 column. The thermodynamic properties of solute adsorptions in neat water, determined using van' t Hoff plots, were investigated. Slightly concave upward and downward retention curves were identified for the plots of ln k versus CACN and ln k versus ln CACN, respectively. A three-equilibrium-constant stoichiometric displacement retention model was used to interpret the retention behaviors of the solutes. The model was demonstrated to account for the nonlinearity of the retention curves. The linear fits of the ln k versus ln⁡CACN and ln k versus CACN plots were implied to be more suitably used for high and low ACN concentration ranges, respectively. The model fitted the experimental data satisfactorily over a full range of ACN concentrations; thus, the nonlinearity of ln k versus ln⁡CACN plots was implied to mainly be attributed to the weak ACN-sorbent interactions. U-shaped retention curves were observed for acetone, tetrahydrofuran, tert-butanol, and benzyl alcohol at high ACN concentrations, indicating that the retention behaviors of these solutes may involve two types of interactions, with complementary effects on solute retention factor with increasing ACN concentration.

Solvent effects on the retention mechanisms of an amylose-based sorbent.

The mobile phase, when used in combination with a polysaccharide-based sorbent, often contains hydrocarbons with polar modifiers. Studies have investigated the effect of solvent on the recognition mechanism of polysaccharide-based sorbents, but it remains unclear how these modifier molecules affect solute retention behavior. This study used an amylose 3,5-dichlorophenylcarbamate-based sorbent to systematically investigate the retention behavior of various solutes as a function of the concentration of four polar modifiers: ethanol, isopropanol, methyl tert-butyl ether, and acetone. The thermodynamic properties of adsorption for the four modifiers were thoroughly investigated using retention factor data, van't Hoff plots, and adsorption isotherms of the modifier molecules. The adsorption data of acetone and isopropanol followed the Langmuir isotherm, whereas the bi-Langmuir isotherm more accurately fit the ethanol data. For methyl tert-butyl ether, the Brunauer-Emmett-Teller adsorption isotherm indicated multilayer adsorption with a low saturation capacity of the first adsorption layer. A multivalent retention model interpreted slopes of the plots of the logarithm of the retention factor versus the logarithm of the modifier concentration. Because the molecular polarity of acetone is stronger than that of methyl tert-butyl ether, the limiting absolute slope values of tetrahydrofuran at a very high acetone modifier concentration were smaller than that when methyl tert-butyl ether was used as the polar modifier. The higher absolute value of the slope for tert-butanol suggested the potential of CO groups of acetone molecules to form bifurcated H bonds on a tert-butanol molecule. When alcohol was employed as the polar modifier, the results suggested that the effect of isopropanol self-association on the retention factor was stronger than the effects of solute-IPA complexation and isopropanol adsorption. For alcohol modifiers, U-shaped retention curves were obtained for all aromatic solutes. When acetone or methyl tert-butyl ether was used, the absence of a U-shaped curve indicated the weak polarity of those modifiers.

Effect of solvent composition on the van't Hoff enthalpic curve using amylose 3,5-dichlorophenylcarbamate-based sorbent.

Van't Hoff plots have been widely used for investigating the thermodynamic properties of adsorption processes in various chromatography systems. By measuring the retention factor k over a certain temperature range, the plot of ln k versus 1/T often yields a straight line with a slope of -ΔHvH0/R. Although this method provides information on adsorption enthalpy changes, its theoretical basis does not account for the effect of the solvent. In this paper, the relationship between apparent enthalpy changes determined directly from van't Hoff plots and solvent modifier concentrations is systematically investigated using three simple solutes-tetrahydrofuran, acetone, and tert-butanol-in an n-hexane-methyl tert-butyl ether (MTBE) mobile phase with an amylose 3,5-dichlorophenylcarbamate-based sorbent. The apparent enthalpy changes of solutes are strongly dependent on MTBE concentration, increasing rapidly with MTBE content at low concentrations but leveling off after ΔH0 reaches approximately -15kJ/mol. These data cannot be explained by the thermodynamic model currently used in the literature. A new three-equilibrium-constant thermodynamic model is developed herein to account for solute-sorbent, solvent-sorbent, and solute-solvent interactions. The thermodynamic parameters of the model are estimated from the apparent enthalpy changes at different MTBE concentrations. The results reveal that two key dimensionless groups control the van't Hoff enthalpic curves: the fractions of solute molecules bound to modifier molecules and adsorption sites occupied by modifier molecules. As a result, the shapes of van't Hoff enthalpic curves reflect the adsorption isotherm of MTBE without complexation or information regarding solute-MTBE complexation without MTBE competitive adsorption. The new model is thus demonstrated to be more reliable than the current model for examining the thermodynamic properties of retention mechanisms.

Retention models and interaction mechanisms of benzene and other aromatic molecules with an amylose-based sorbent.

Stoichiometric displacement models have been widely used for understanding the adsorption mechanisms of solutes in chromatography systems. Such models are used for interpreting plots of solute retention factor versus concentrations of polar modifier in an inert solvent. However, these models often assume that dispersion forces are negligible and they are unable to account for solutes with significant aromatic interactions. In this study, a systematic investigation of the relationship between retention behavior and aromatic groups was performed using five simple aromatic molecules-benzene, naphthalene, mesitylene, durene, and toluene-with a commercially available amylose tris(3,5-dimethylphenylcarbamate)-based sorbent. The enthalpy changes of adsorption, determined from van't Hoff plots, were obtained separately in pure n-hexane and in pure isopropanol (IPA). In pure n-hexane, the solute adsorptions were driven by electrostatic interactions, favoring a T-shaped binding configuration (edge-to-face π-π interaction). The order of enthalpy change indicated the amount of effective T-shaped π-interactions. In pure IPA, solute adsorption was dominated by dispersion forces, favoring a sandwich binding configuration (face-to-face π-π interaction). The adsorption isotherms of toluene revealed that in pure IPA and in pure n-hexane, the isotherms were linear. The results suggested that the high solvent strength of IPA weakened the interactions between aromatic molecules. The retention behavior of the benzene, naphthalene, mesitylene, and durene as a function of IPA concentration was investigated. U-shaped retention curves were found for all aromatic solutes. A new retention model for monovalent aromatic solutes was developed for describing the U-shaped curves. Three key dimensionless groups were revealed to control the retention behavior. The models suggested that solvophobic interactions should be accounted for in the retention models used to investigate the retention behaviors of solutes associated with aromatic groups.

Elucidation of adsorption mechanisms of solvent molecules with distinct functional groups on amylose tris(3,5-dimethylphenylcarbamate)-based sorbent.

Although polysaccharide derivative-based sorbents have been widely used for chiral separation, for a long time it remained unclear how these CSPs interact with the molecules associated with different functional groups. In this study, six molecules were chosen for retention behavior studies: acetone (AC), tetrahydrofuran (THF), methanol (MET), isopropanol (IPA), tert-butanol (TBA), and benzene (BZN). An immobilized amylose carbamate stationary phase, amylose tris(3,5-dimethylphenylcarbamate)-based sorbent, or Chiralpak IA, was used. Van't Hoff plots of ln k versus 1/T showed that alcohol molecules may simultaneously form two H-bonds with the IA sorbent. The results of density functional theory simulations and IR spectra support this inference showing that alcohol may bind with amide groups in three possible configurations. Frontal tests of AC and IPA were performed to estimate adsorbed solute concentration. Langmuir isotherm for IPA adsorption and mass action model for IPA self-aggregation were used for analyzing the IPA frontal results. Average IPA aggregation numbers range from 1.4 to 2.3. More than fifty percent of IPA molecules were found to be in aggregate form. From the frontal test results, thermodynamic properties of the adsorptions were determined. Retention behaviors of the five solutes as a function of IPA concentration were investigated. The absolute values B of the slopes from plots of the logarithms of the retention factor versus the logarithms of the IPA concentration increase in the order THF

Insights into chromatographic enantiomeric separation of allenes on cellulose carbamate stationary phase.

Allenes are cumulenes with three contiguous carbons linked together through double bonds. 1,3-disubstituted allenes are not superimposable on their mirror image; as a consequence they are chiral. Chiral allenes are increasingly important in organic synthesis due to their interesting reactivity. Because of their applications in the field of asymmetric catalysis and in the pharmaceutical industry their optical purity is always a parameter which needs to be determined. In this article, we report the enantiomeric separation of hexa-3,4-diene-3-ylbenzene, an aromatic allene, on a cellulose carbamate (Chiralcel OD-3) stationary phase, using heptane as the mobile phase. Spectroscopic studies using infrared (IR) and vibrational circular dichroism revealed that, in the presence of heptane, the stationary phase undergoes a conformational change due to intermolecular H-bonding between the CO and NH of the neighboring polymer chains. Van't Hoff plots for the retention factor, k, showed that the retention of the two enantiomers is dominated by the enthalpy, while the plot for the selectivity, α, is entropy driven. This suggests that the enantioselectivity is a result of inclusion of the enantiomers in the cavities of the chrial stationary phase. VCD spectra, along with density functional theory calculation (DFT) of the interaction between each enantiomer and the chiral stationary phase, supported the chromatographic elution order findings.

Effect of alcohol aggregation on the retention factors of chiral solutes with an amylose-based sorbent: modeling and implications for the adsorption mechanism.

Various displacement models in the literature have been widely used for understanding the adsorption mechanisms of solutes in various chromatography systems. The models were used for describing the often-observed linear plots of the logarithms of the retention factor versus the logarithms of the polar modifier concentration CI(0). The slopes of such a plot was inferred to be equal to the number of the displaced modifier molecules upon adsorption of one solute molecule, and were generally found to be greater than 1. In this study, the retention factors of four structurally related chiral solutes, ethyl lactate (EL), methyl mandelate (MM), benzoin (B), and pantolactone (PL), were measured for the amylose tris[(S)-α-methylbenzylcarbamate] sorbent, or AS, as a function of the concentration of isopropanol (IPA) in n-hexane. With increasing IPA concentration CI(0), the slopes increase from less than 1, at a concentration range from 0.13 to 1.3M, to slightly more than 1 at higher concentrations. Such slopes cannot be explained by the conventional retention models. It was found previously for monovalent solutes that such slopes can only be explained when the aggregation of the mobile phase modifier, isopropyl alcohol, was accounted for. A new retention model is presented here, accounting for alcohol aggregation, multivalent solute adsorption, multivalent solute-alcohol complexation, alcohol adsorption, and solute intra hydrogen-bonding, which occur in these four solutes. The slope is found to be controlled by three key dimensionless groups, the fraction of the sorbent binding sites covered by IPA, the fraction of the solute molecules in complex form, and the fraction of the IPA molecules in aggregate form. The limiting slope at a very high IPA concentration is equal to the value of (x+y)/n, where x is the number of the solute-sorbent binding sites and y is the number of the alcohol molecules in the solute-alcohol complex, and n is the alcohol aggregation number. The model was tested with the HPLC data of two sets of chiral solutes, one set of new data presented here and of one set of literature data by Gyimesi-Forrás et al. (2009), for which there is no known intramolecular H-bonding. For the first set of solutes, the values of the equilibrium constants for intramolecular hydrogen bonding were calculated from our previous IR data. The value of the parameter y was fixed on the basis of the number of the solute functional groups, IR data, and the results of DFT and MD simulations. The retention factors in pure hexane (k0) were found experimentally for EL, MM, and B; for PL they were estimated from the data. Then the values of x and the complexation equilibrium constants were estimated. The model fits fairly well our new data, and less well the more-limited literature data, for which the k0 values were unavailable, and the retention factors were obtained over a narrow range of IPA concentrations. For EL and PL, results of infrared spectroscopy, density functional theory, and molecular dynamics simulations indicated strong solute-IPA complexation, and multiple solute-sorbent binding sites, which are consistent with the fitting results. Hence, the new model has been shown to be more reliable than the previous models for estimating the numbers of the potential binding sites of multivalent solutes.

Chiral recognition mechanism of acyloin-containing chiral solutes by amylose tris[(S)-α-methylbenzylcarbamate].

Although polysaccharide sorbents have been widely used for chiral separations, the recognition mechanisms have not been fully elucidated. In this study, we focus on one important commercial sorbent, amylose tris[(S)-α-methylbenzylcarbamate] (AS) sorbent. Four solutes containing acyloin, O═C-C-OH, which has a hydroxyl group in the α-position of a carbonyl group, were studied: ethyl lactate (EL), methyl mandelate (MM), benzoin (B), and pantolactone (PL). The observed retention factors (kR and kS) and enantioselectivities (α = kR/ kS) were determined in n-hexane and in hexane-isopropanol (IPA) solutions. Infrared (IR) spectroscopy and density functional theory (DFT) simulations of the interactions of these solutes with the side chains of the polymer led to a general hypothesis for the chiral recognition mechanism for these solutes: A strong H-bond forms as the primary (or "leading") nonenantioselective interaction (or "anchor" point) between the solute OH group of each enantiomer and the sorbent C═O group. A weaker H-bond forms preferably for the R enantiomer between the solute C═O groups and the sorbent NH groups. The S enantiomer is prevented from forming such a bond for steric restrictions. A third interaction might involve the O groups of the phenyl groups of the solutes. IR spectroscopy shows evidence of an intramolecular H-bond for all four solutes. The retention factors were found to increase with increasing strength of the intermolecular H-bond and with decreasing strength of the intramolecular H-bond. The enantioselectivities were found to correlate with the molecular rigidity or flexibility, as determined from the distribution of the torsion angles of the acyloin group. The enantioselectivity was higher for the more rigid molecules. Simulations of left-handed AS with 200 n-hexane molecules indicated no effect of hexane on the H-bonds in AS. Monte Carlo (MC) and molecular dynamics (MD) "docking" simulations of AS with these solutes revealed certain chiral cavities that can lead to chiral discrimination. The results support the proposed mechanism.

Retention models and interaction mechanisms of acetone and other carbonyl-containing molecules with amylose tris[(S)-α-methylbenzylcarbamate] sorbent.

The stoichiometric displacement models developed in the literature have been widely used for understanding the adsorption mechanisms of solutes in various chromatography systems. The models were used to explain the linear plots of the logarithms of the solute retention factor versus the molar concentration of a competitive modifier in an inert solvent. The slope of the linear plot was inferred to be the total number of modifier molecules displaced from the sorbent and from the solute-modifier complex upon adsorption of a solute molecule. The slopes reported in the literature were generally greater than 1. In this study, we determined the retention factors of five monovalent solutes, acetone, cyclo hexanone, benzaldehyde, phenylacetaldehyde, and hydrocinnamaldehyde, on a derivatized polysaccharide sorbent, amylose tris[(S)-α-methylbenzylcarbamate], or AS, as a function of the concentration of a polar modifier isopropanol (IPA) in n-hexane (an inert solvent). Each solute has one CO functional group, which can form an H-bond with a sorbent NH group and the OH group of IPA. The slopes, from 0.25 to 0.45, of the log-log plots are less than 1, which cannot be explained by the literature displacement models. The results of Infrared Spectroscopy and Density Functional Theory simulations show clear evidence of acetone-IPA complexation and IPA aggregation with average aggregation number n=3. A new thermodynamic retention model is developed to take into account IPA aggregation, IPA-solute complexation, and competitive adsorption. Dimensionless group analysis indicates that aggregation of IPA can lead to slopes B below 1, even at high IPA concentrations. The model parameters (IPA aggregation number and equilibrium constants) are estimated from the retention factors at different IPA concentrations. The retention model and the parameters are further validated with dynamic chromatography simulations. The results show that the aggregation leads to a significant reduction in the IPA monomer concentration, which affects the IPA-sorbent binding and the IPA-solute complexation. As a result, the slope of the log-log plot at a high IPA concentration approaches 1/n without complexation, or 2/n with complexation. The variations of B between the five achiral solutes can be due to different strengths of solute-IPA complexation. Hence, the complexation and aggregation of the polar modifier in the mobile phase must be accounted for in the retention models used in the interpretation of the retention factors and the adsorption mechanisms.

Infrared spectroscopy and molecular simulations of a polymeric sorbent and its enantioselective interactions with benzoin enantiomers.

Retention factors, k(R) and k(S), and enantioselectivities, S ≡ k(R)/k(S), of amylose tris[(S)-α-methylbenzylcarbamate] (AS) sorbent for benzoin (B) enantiomers were measured for various isopropyl alcohol (IPA)/n-hexane compositions of the high-performance liquid chromatography (HPLC) mobile phase. Novel data for pure n-hexane show that k(R) = 106, k(S) = 49.6, and S = 2.13. With some IPA from 0.5 to 10 vol %, with S = 1.8-1.4, the retention factors were smaller. Infrared spectra showed evidence of substantial hydrogen bonding (H-bonding) interactions in the pure polymer phase and additional H-bonding interactions between AS and benzoin. Density functional theory (DFT) was used to model the chain-chain and chain-benzoin H-bonding and other interactions. DFT was also used to predict fairly well the IR wavenumber shifts caused by the H-bonds. DFT simulations of IR bands of NH and C═O allowed for the first time the predictions of relative intensities and relative populations of H-bonding strengths. Molecular dynamics (MD) simulations were used to model a single 12-mer polymer chain. MD simulations predicted the existence of various potentially enantioselective cavities, two of which are sufficiently large to accommodate a benzoin molecule. Then "docking" studies of benzoin in AS with MD, Monte Carlo (MC), and MC/MD simulations were done to probe the AS-B interactions. The observed enantioselectivities are predicted to be primarily due to two H-bonds, of the kind AS CO···HO (R)-benzoin and AS NH···OC (R)-benzoin, and two π-π (phenyl-phenyl) interactions for (R)-benzoin and one H-bond, of type AS CO···HO (S)-benzoin, and one π-π interaction for (S)-benzoin. The MC/MD predictions are consistent with the HPLC and IR results.

Novel behavior of heat of micellization of pluronics F68 and F88 in aqueous solutions.

It is well understood that the heat of micellization for surfactants is monotonically decreased along with an increase in temperature. However, this behavior for polymeric surfactants has never been carefully examined. In this study, the heat of micellization of poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide) (PEO-PPO-PEO) triblock copolymers (Pluronics F68 and F88) in water as a function of temperature is carefully examined by using a high-sensitivity differential scanning calorimeter (HSDSC). The critical micelle temperature (CMT) decreases along with an increase in the concentration of Pluronic F68 (or F88). The heat of micellization decreases along with an increase in the temperature, as expected, when the CMT is higher than 55 and 42 degrees C for Pluronics F68 and F88, respectively. It is interesting to observe that the heat of micellization increases along with the temperature while the temperature is below 55 and 42 degrees C for Pluronics F68 and F88, respectively. The enthalpy-entropy compensation phenomenon for the micellization of Pluronics F68 and F88 in connection with the hydrophobicity is discussed.