Structure and thermodynamics of alpha-, beta-, and gamma-cyclodextrin dimers. Molecular dynamics studies of the solvent effect and free binding energies

The alpha-, beta-, and gamma-cyclodextrin (CyDs) dimers were studied by molecular dynamics (MD) simulations in water as an explicit solvent. The relative stability of dimers and the involved molecular interactions were determined. Three possible starting orientations were considered for the dimers: head-to-head, head-to-tail, and tail-to-tail. MD simulations were performed over a period of 5 ns to ensure the stability of the system for both the CyD dimers and monomers. The MM-PBSA methodology was used to obtain the free binding energy of the dimers and to determine the most stable arrangement for each solvated CyD. In a vacuum, MD simulations provided the head-to-head orientation as the most stable orientation for the three CyDs, while in aqueous solution the, the head-to-tail orientation was found to be the most stable for the alpha-CyD dimer and the tail-to-tail orientation the most stable for the beta- and gamma-CyD dimers.     

Glucose orientation and dynamics in alpha-, beta-, and gamma-cyclodextrins

We investigate, using molecular dynamics (MD) computer simulations, the conformational behavior of alpha-, beta-, and gamma-cyclodextrins (CDs). Our analysis of a 30 ns trajectory of CD solution dynamics reveals the underlying conformational behaviours of the CDs that explain their relative flexibility. The distributions of the torsion angles related to the glycosidic linkages, P(phi,psi) were calculated for the three CDs. Most noticeable is the limited range in phi torsion rotations compared with psi rotations for all the CDs. This difference between the three CDs is amplified in the motion and dynamics of their glucose monomers when we monitor their orientational and librational positions relative to the macrocyclic mean plane. The relaxation times of the monomers to their equilibrium orientations follow the pattern gamma-CD > alpha-CD > beta-CD. The root-mean-square deviations of the motion of the monomer centers of mass from the mean macrocyclic planes exhibit the same trend.     

Significant differences in the electrochemical behavior of the alpha-, beta-, gamma-, and delta-tocopherols (vitamin E)

Alpha-, beta-, gamma-, and delta-tocopherols can be oxidized in dry CH2Cl2 or CH3CN by one electron to form cation radicals that deprotonate to form the neutral phenoxyl radicals, which are then immediately further oxidized by one electron to the phenoxonium cations (an ECE electrochemical mechanism, where E signifies an electron transfer and C represents a chemical step, with the electrochemical mechanism having been determined by in situ spectroscopic analysis). The principal difference in the electrochemical behavior of the tocopherols relates to the stability of their associated phenoxonium cations. The phenoxonium cation of alpha-tocopherol is stable in solution for at least several hours, the phenoxonium cation of beta-tocopherol is stable for several minutes, and the phenoxonium cations of gamma- and delta-tocopherol are stable for <1 s. In dry CH2Cl2 containing >0.75 M acid (CF3COOH), the deprotonation reaction of the cation radicals can be completely inhibited resulting in the cyclic voltammetric behavior of the tocopherols appearing as chemically reversible one-electron oxidation processes (an E mechanism). In dry acid conditions, the cation radicals can be further oxidized by one electron to form the dications, which are unstable and immediately deprotonate. The high stability of the phenoxonium cation of alpha-tocopherol compared to the other tocopherols (and most other phenols) is a chemically important feature that may shed new light on understanding alpha-tocopherol's unique biological properties.     

Gas-chromatographische Bestimmung von alpha-, beta- und delta-Hexachlorcyclohexan-Spuren in Lindan

Zusammenfassung Anstatt des technischen HCH (Hexachlorcyclohexan), das aus mehreren HCH-Stereoisomeren besteht, wird heute fast ausschließlich das im menschlichen Organismus schnell metabolisierte und dann eliminierte gamma-HCH, Lindan als Pflanzenschutzmittel eingesetzt. Trotzdem ist sowohl in der Umwelt, als auch im Organismus immer wieder verhältnismäßig viel beta-HCH zu finden, das im Organismus nicht so leicht abgebaut, sondern angereichert wird. Es schien also notwendig zu sein, die Lindanpräparate auf Verunreinigung durch die anderen Isomeren zu prüfen. Mit den üblichen gas-chromatographischen Untersuchungsverfahren für technisches HCH ist diese Aufgabe nicht zu lösen, weil neben dem die Hauptmenge bildenden gamma-HCH die geringeren Mengen von beta- und delta-HCH in dem Tailing des gamma-HCH verwischt werden. Doch die Retentionszeiten auf den Trennflüssigkeiten Neopentylglykolsuccinat und XF-1112 Resin sind so unterschiedlich, daß die anderen Isomeren sogar in einer Menge um 0,005% zu erfassen sind.

---

Gas chromatographic determination of alpha, beta, and delta benzene hexachloride traces in lindane

Summary Instead of technical BHC (benzene hexachloride) consisting of several stereoisomers, the manufacturers of pesticides today have adopted almost exclusively gamma BHC, lindane, which is rapidly metabolized in the human organism and then eliminated. In spite of this, substantial amounts of beta BHC can be found in the environment as well as in organisms, which is not easily broken down in the organism, but is even cumulative. Thus it appeared necessary to investigate lindane products for contamination by other isomers. The usual gas chromatographic testing procedures for technical BHC are not suitable for this task, since the minute amounts of beta and delta BHC would be obscured in the tailing of the major component gamma BHC. However, when using neopentyl glycol succinate or XF-1112 resin as stationary phases, the retention times differ so markedly that the other isomers can be detected in concentrations as low as 0.005%.

     

Molecular electrostatic potentials and hydrogen bonding in alpha-, beta-, and gamma-cyclodextrins

Cyclodextrins (CDs) are cyclic oligomers of glucose having the toroid of sugars elaborating a central cavity of varying size depending on the number of glucoses. The central hydrophobic cavity of CD shows a binding affinity toward different guest molecules, which include small substituted benzenes to long chain surfactant molecules leading to a variety of inclusion complexes when the size and shape complementarity of host and guest are compatible. Further, interaction of guest molecules with the outer surface of alpha-CD has also been observed. Primarily it is the electrostatic interactions that essentially constitute a driving force for the formation of inclusion complexes. To gain insights for these interactions, the electronic structure and the molecular electrostatic potentials in alpha-, beta-, and gamma-CDs are derived using the hybrid density functional theory employing the three-parameter exchange correlation functional due to Becke, Lee, Yang, and Parr (B3LYP). The present work demonstrates how the topography of the molecular electrostatic potential (MESP) provides a measure of the cavity dimensions and understanding of the hydrogen-bonded interactions involving primary and secondary hydroxyl groups. In alpha-CD, hydrogen-bonded interactions between primary -OH groups engender a "cone-like" structure, while in beta- or gamma-CD the interactions from the primary -OH with ether oxygen in glucose ring facilitates a "barrel-like" structure. Further, the strength of hydrogen-bonded interactions of primary -OH groups follows the rank order alpha-CD > beta-CD > gamma-CD, while the secondary hydrogen-bonded interactions exhibit a reverse trend. Thus weak hydrogen-bonded interactions prevalent in gamma-CD manifest in shallow MESP minima near hydroxyl oxygens compared to those in alpha- or beta-CD. Furthermore, electrostatic potential topography reveals that the guest molecule tends to penetrate inside the cavity forming the inclusion complex in beta- or gamma-CD.     

Extension and compression behavior of rubbery polymer networks

The elastic behavior of different types of rubbery polymers (natural rubber, polybutadiene, silicone, and polyisoprene) networks at various degrees of vulcanization and swelling was examined in extension and compression. The data are represented by the Mooney-Rivlin equation. In compression, although C₂ is zero, C₁ decreases strongly with increasing swelling to a limiting value which, in some cases, may be correlated with the value of C₁ found in extension and hence related to the theoretical modulus for highly swollen networks. A possible explanation is presented in terms of supramolecular order in the amorphous materials.     

Recognizing alpha-, beta- or gamma-substitution in pyridines by mass spectrometry

A general mass spectrometric method able to recognize the site of substitution of monosubstituted pyridines is described. The method requires that the molecule under investigation forms, upon ionization and dissociation, the respective alpha-, beta- or gamma- pyridinium ion of m/z 78. Pyridinium ions are stable and common fragments of ionized and protonated pyridines and are found to function as appropriate structurally diagnostic fragment ions. They can be identified by their characteristic and nearly identical collision-induced dissociation behavior and distinguished by the combined use of two structurally diagnostic ion/molecule reactions with acetonitrile and 2-methyl-1,3-dioxolane. alpha-, beta- or gamma-substitution in pyridines can, therefore, be securely recognized via an MS-only method based on structurally diagnostic ions and by the inspection of a single molecule (no need for intracomparisons within the whole set of isomers).     

Micellar behavior of aqueous solutions of dodecyldimethylethylammonium bromide, dodecyltrimethylammonium chloride and tetradecyltrimethylammonium chloride in the presence of alpha-, beta-, HPbeta- and gamma-cyclodextrins

Conductivity, static fluorescence and (1)H NMR measurements have been carried out to study the micellar behavior of aqueous solutions of dodecyldimethylethylammonium bromide (DDAB), dodecyltrimethylammonium chloride (DTAC) and tetradecyltrimethylammonium chloride (TDAC) in absence and presence of alpha-cyclodextrin (alpha-CD), beta-cyclodextrin (beta-CD), hydroxypropyl-beta-cyclodextrin (HPbeta-CD) and gamma-cyclodextrin (gamma-CD). The conductivity measurements were carried out at 298.15 K. The influence of cyclodextrins on the micellar parameters, such as cmc* (apparent critical micellar concentration), beta (degree of ionization) have been analyzed. Thermodynamics of the systems was discussed in terms of the change in standard free energy of micellization, DeltaG(m)(0). Micellization was found to be less spontaneous in presence of cyclodextrins. The fluorescence intensity of the surfactant solutions is enhanced by the addition of cyclodextrins. The association constants obtained from conductivity and fluorescence data suggest the binding of gamma-CD with the surfactants to be strongest among all the cyclodextrins used. (1)H NMR chemical shift changes provide powerful means for probing the cyclodextrin-micellar interactions and inclusion of surfactant is shown by the change in the chemical shift of some of the guest and host protons in comparison with the chemical shifts of the same protons in the free compounds.     

Stress relaxation in polymer networks: equilibrium behavior and dynamics

The elastic and relaxational properties of a polymer network have been calculated using a stress based formulation based on the Rouse mode expansion [W. L. Vandoolaeghe and E. M. Terentjev, J. Chem. Phys. 123, 34902 (2005)]. In this article, we propose an improved Rouse mode expansion incorporating appropriate boundary conditions. In contrast to the previous work, this improved formulation provides a smooth crossover from the classical equilibrium result of rubber elasticity to the shorter-time-scale Rouse relaxation of a polymer melt. Our results are compared with the classical phantom network approach in equilibrium, as well as both equilibrium and dynamic elongation experiments. The model captures the qualitative features of the data well and some of the quantitative aspects, such as the exponents seen in the dynamic modulus G(omega).     

Complexation and chiral recognition thermodynamics of gamma-cyclodextrin with N-acetyl- and N-carbobenzyloxy-dipeptides possessing two aromatic rings

The stability constants (K) and the standard free energy (deltaG degrees ), enthalpy (deltaH degrees ), and entropy changes (deltaS degrees ) for the complexation of gamma-cyclodextrin with 34 enantiomeric and diastereomeric N-acetyl- and N-carbobenzyloxy-d/l-dipeptides with two aromatic moieties were determined in aqueous buffer solution at 298.15 K by titration microcalorimetry. Chiral recognition of the enantiomeric dipeptide pairs by gamma-cyclodextrin was found to be fairly poor, exhibiting only small percentage differences in K, while the diastereomeric dipeptides were discriminated to much greater extent with affinity differences of up to 6-7 times. The complex structures of several selected pairs were elucidated by NMR techniques. Combining the microcalorimetric and NMR data, the complexation and chiral recognition behavior of gamma-cyclodextrin is discussed in particular in terms of the length, bulkiness, and flexibility of the tether connecting the two aromatic moieties in a guest.     

Improving creep resistance while maintaining reversibility of covalent adaptive networks via constructing reversibly interlocked polymer networks

Thermoresponsive covalent adaptive networks (CANs) have attracted increasing research attention because of their temperature-dependent reversibility, which endows the materials with versatile smart functionalities including intrinsic self-healability not available for traditional thermosets. Nevertheless, the associated reduction in creep resistance of this type of CANs limits their practical application. Here in this work, we demonstrate that the reversibility and dimensional stability can be combined via interlocking the thermoresponsive network with an ultraviolet-responsive network. The two types of networks are, respectively, crosslinked by orthogonal reversible Diels-Alder (DA) bonds and coumarin. Owing to the interlocked architecture, the latter single network can be uniformly distributed in the former, restricting the chain movement and enhancing the creep resistance even when the former is decrosslinked at elevated temperature as a result of retro-DA reaction. Meanwhile, the ultraviolet-responsive network plays the role of a photo-reversible switch. Its decrosslinking on exposure to 254 nm ultraviolet (UV) light and recrosslinking under a UV irradiation of 350 nm lead to repeated releasing and reimposing of the restraints on the neighboring thermoresponsive network. By using this smart habit, the material can either be conditionally self-healed with moderate healing efficiency or completely self-healed depending on whether only DA bonds or both DA bonds and coumarin are triggered. More importantly, the conflicting properties, that is, creep resistance and reversibility of the CANs are thus united. The proposed strategy provides a facile way for overcoming the weaknesses of CANs while maintaining the advantage.     

Binding of dimethyl 2,3-naphthalenedicarboxylate with alpha-, beta- and gamma-cyclodextrins in aqueous solution

Fluorescence has been used to investigate the complexes of 2,3-dimethyl naphthalenedicarboxylate with naturally occurring alpha-, beta- and gamma-cyclodextrins. Emission spectra upon excitation of the naphthoate group show two peaks whose ratio of intensities R is the sensitive to the medium polarity. The change of R with cyclodextrin concentration and temperature allows us to obtain the stoichiometry, the formation constants and the changes of enthalpy and entropy upon inclusion. Complexes show 1:1 stoichiometry. R extrapolated at [CD]-->infinity and the analysis of quenching and polarization measurements, as well as, molecular mechanics calculations in the presence of water, permit us to explain the geometry of the complexes, the possible location of the guest in conformity with thermodynamics parameters and the forces responsible for the complexation.     

Applications of biocatalysis in fragrance chemistry: the enantiomers of alpha-, beta-, and gamma-irones

The history of iris extracts, and of the isolation and enzyme-mediated synthesis of their odoriferous principle, the "irones", will be used to describe the improvement brought about by chemistry and biocatalysis in the development of natural fragrances. In particular, this tutorial review will discuss how the progress in the field of enzyme chemistry allowed the optimisation of accelerated procedures for the preparation of natural irone extracts, and the synthesis of all the ten isomers of irone, starting from commercial irone alpha.     

Enantioseparation of chiral organochlorines on permethylated beta- and gamma-cyclodextrin, as well as 1:1 mixtures of them

Gas chromatography columns coated with 10% permethylated beta- and gamma-cyclodextrin in 85% dimethyl-15% diphenyl polysiloxane (beta- and gamma-PMCD, respectively) and 1:1 mixures are prepared and tested with regard to the enantioseparation of chiral chloropesticides. On the columns with the individual O-methylated cyclodextrins (O-tCDs), the enantiomers of aaeeee-hexachlorocyclohexane (alpha-HCH), e-aeee-1,3,4,5,6-pentachlorocyclohex-1-ene (beta-PCCH), and e-aaee-1,3,4,5,6-pentachlorocyclohex-1-ene (gamma-PCCH), cis- and trans-chlordane, and cis-heptachlor epoxide are separated on both columns, with the exception of the latter being separated only on beta-PMCD. On the column coated with 5% beta- and 5% gamma-PMCD, the resulting separation factor (a) is virtually 1/2 of the arithmetric mean of the elution-dependent separation factors on the individual O-tCDs. In case of reversed elution order on beta- and gamma-PMCD, the enantiomers are not resolved on the mixed columns as is the case with cis-chlordane. Likewise, the lower resolution of the gamma-PCCH enantiomers on the mixed columns prove the reversed elution order on beta- and gamma-PMCD without having enantioenriched standards available. On the column coated with 5% beta- and 5% gamma-PMCD, similar retention times to those observed on both 10% beta-PMCD and 10% gamma-PMCD are obtained. On the column coated with 10% beta- and 10% gamma-PMCD, significantly longer retention times are obtained compared with the columns that contain a total of 10% chiral stationary phase (CSP). This indicates that a relevant part of the interaction of the analytes with the chiral selector is non-enantioselective and, thus, only delays the elution of both enantiomers. Moreover, these non-enantioselective interactions prevent a direct comparison of CSPs with different amounts of the chiral selector. However, this is possible by using mixed phases of two CSPs with similar properties. Using this system, it is demonstrated that for the organochlorine compounds studied, no higher separation factor is observed on the mixed CSPs than on the individual O-tCD with the higher separation factor. Estimations allow a prediction that enantioseparations of organohalogen compounds can be achieved on columns coated with as little as 1% of the CSP.     

Phase behavior and photocrosslinking kinetics of semi-interpenetrating polymer networks prepared from miscible polymer blends

Mixtures of polystyrene derivatives (PSCS) and poly(vinyl methyl ether) (PVME) were made photocrosslinkable by chemically labeling PSCS chains with photoreactive anthracene. Miscibility of these anthracene-labeled PSCS/PVME blends was examined by light scattering under several crosslinking conditions in the one-phase region via photodimerization of anthracenes. As the reaction proceeds, the coexistence curve of PSCS/PVME blends shifts toward the low temperature side. By following the changes in concentration of anthracenes with irradiation time, it was found that the crosslinking reaction of PSCS chains in the blends does not follow the mean-field kinetics. However, it can be well expressed by the Kohlrausch–Williams–Watts (KWW) relaxation mechanism, indicating that the crosslinking reaction proceeds inhomogeneously in the blends. By scaling the reaction time with the average reaction rate obtained from the KWW equation modified for the reaction kinetics, all the crosslinking data obtained in the miscible region of the reacted blends fall on a single master curve. These experimental results suggest the universal behavior of the photocrosslinking kinetics obtained under the “shallow quench” conditions in the region far away from the coexistence curve of the reacting blends. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 455–462, 1998     

Comparison of nanotube structures constructed from alpha-, beta-, and gamma-cyclodextrins by potential-controlled adsorption

"Nanotube" structures of the alpha-, beta-, and gamma-cyclodextrins (CyD's), which are similar to that of CyD-polyrotaxane, were constructed by potential-controlled adsorption onto Au(111) surfaces in sodium perchlorate solution without a threaded polymer. CyD molecules adsorbed randomly on bare Au(111) surfaces without potential control and the desorption of CyD's from Au surfaces was observed at a negative potential of less than -0.60 V versus SCE. On the other hand, in the specific range between these potentials, ordered molecular arrays with "nanotube" structures of the CyD's (alpha-, beta-, and gamma-CyD) were observed on Au(111). The range of potentials for formation of the "nanotube" structures of alpha-, beta-, and gamma-CyD was from -0.15 to -0.20 V, from -0.25 to -0.45 V, and from -0.22 to -0.45 V, respectively. beta- and gamma-CyD require a more negative potential for adsorption-induced self-organization (AISO) than alpha-CyD in order to weaken adsorption and induce self-organization. Furthermore, we have succeeded in the visualization of the dynamic process in solution, such as the self-ordering, and the destruction of the nanotube structure. These results indicate that control of the electrode potential facilitates management of the delicate balance of various interactions, resulting in the formation of two-dimensional supramolecular structures on the substrates.