A spectral displacement study of cyclodextrin/naphthenic acids inclusion complexes

2009 ◽  
Vol 87 (12) ◽  
pp. 1747-1756 ◽  
Author(s):  
Mohamed H. Mohamed ◽  
Lee D. Wilson ◽  
John V. Headley ◽  
Kerry M. Peru
Keyword(s):  
Guest Molecule ◽  
Hydrophobic Effect ◽  
Relative Size ◽  
Binding Constants ◽  
Naphthenic Acids ◽  
Single Component ◽  
Complex Mixtures ◽  
Complex Stability ◽  
Guest Molecules ◽  
Equilibrium Binding

The spectral displacement technique has been used to obtain 1:1 β-cyclodextrin (β-CD)/carboxylate anion equilibrium binding constants (K2) for some complex mixtures of naphthenic acids (NAs) and some examples of single-component NAs in aqueous solution. Three specific examples of single-component NAs were chosen with variable Z values as follows: 2-hexyldecanoic acid (Z = 0; S1), trans-4-pentylcyclohexanecarboxylic acid (Z = –2; S2), and dicyclohexylacetic acid (Z = –4; S3). The estimated K2 values for S1, S2, and S3 are as follows: 1.42 × 103 M–1, 52.2 × 104 M–1, and 13.1 × 104 M–1, respectively. The corresponding K2 values are 2.34 × 104 M–1 and 1.27 × 104 M–1 for commercial (Fluka) and industrial (Syncrude) sourced NAs, respectively. The magnitude of K2 for 1:1 complexes formed between β-CD and S1, S2, or S3 did not correlate with the degree of hydrogen deficiency (Z-series) but there was a correlation with the size of the guest molecules (n) examined in this study. The correlation between complex stability and the relative size of the lipophilic fragments of the guest molecule are related to the importance of the hydrophobic effect for inclusion of such carboxylic acid guest molecules within β-CD.

Tuning of the Cavity of Water-Soluble Thiacalix[4]arene for the Control of Inclusion Ability Toward Water-Miscible Organic Molecules

2004 ◽  
Vol 69 (5) ◽  
pp. 1080-1096 ◽  
Author(s):  
Noriyoshi Kon ◽  
Nobuhiko Iki ◽  
Yuichiro Sano ◽  
Satoshi Ogawa ◽  
Chizuko Kabuto ◽  
...  
Keyword(s):  
Guest Molecule ◽  
Organic Molecules ◽  
Hydrophobic Effect ◽  
Binding Constants ◽  
Water Soluble ◽  
Main Role ◽  
Diethyl Ketone ◽  
Guest Molecules ◽  
X Ray ◽  
H Nmr

Inclusion abilities of water-soluble thiacalix[4]arenetetrasulfonate (3) and mono-O-carboxymethylated derivatives 5 and 6 toward water-miscible organic molecules such as alcohols, ketones, and nitriles in water were investigated by 1H NMR. The limit chemical shift change of the guest upon inclusion in the host suggested that the hosts regioselectively encapsulate the guests from the side of aliphatic moiety. Large guests such as pentan-1-ol showed folding of the alkyl chain to be included inside the cavity. On the other hand, mono-O-substituted 6 included a guest molecule less deep in the cavity than 3 did. Binding constants (K) of 3 toward guest molecules increased with hydrophobicity of the guest, suggesting that hydrophobic effect plays a main role for the complexation. On the contrary, mono-O-carboxymethyl derivatives 5 and 6 showed the opposite dependency of stability on hydrophobicity; higher affinities toward less hydrophobic guests. Among the guests examined, the smallest entities such as CH3OH and CH3CN were best included in 5 with the highest binding constant ever reported (K > 102 M-1). It was concluded that introduction of the carboxymethyl group into one of the phenolic OH of thiacalix[4]arene led to tuning of the cavity shape for stereospecific inclusion of small guests. The tuning of cavity by the O-alkylation was actually confirmed by X-ray crystal analysis of a complex of 5 with diethyl ketone.

scholarly journals Hydrogen Inter-Cage Hopping and Cage Occupancies inside Hydrogen Hydrate: Molecular-Dynamics Analysis

2020 ◽  
Vol 11 (1) ◽  
pp. 282
Author(s):  
Yogeshwaran Krishnan ◽  
Mohammad Reza Ghaani ◽  
Arnaud Desmedt ◽  
Niall J. English
Keyword(s):  
Molecular Dynamics ◽  
Energy Barrier ◽  
Guest Molecule ◽  
Arrhenius Equation ◽  
Dynamics Simulation ◽  
Type Ii ◽  
Large Cage ◽  
Guest Molecules ◽  
Simulation Time ◽  
Average Occupancy

The inter-cage hopping in a type II clathrate hydrate with different numbers of H2 and D2 molecules, from 1 to 4 molecules per large cage, was studied using a classical molecular dynamics simulation at temperatures of 80 to 240 K. We present the results for the diffusion of these guest molecules (H2 or D2) at all of the different occupations and temperatures, and we also calculated the activation energy as the energy barrier for the diffusion using the Arrhenius equation. The average occupancy number over the simulation time showed that the structures with double and triple large-cage H2 occupancy appeared to be the most stable, while the small cages remained with only one guest molecule. A Markov model was also calculated based on the number of transitions between the different cage types.

A Fluorescence Quenching Analysis of the Binding of Fluoroquinolones to Humic Acid

2017 ◽  
Vol 71 (11) ◽  
pp. 2512-2518 ◽  
Author(s):  
Ryan P. Ferrie ◽  
Gregory E. Hewitt ◽  
Bruce D. Anderson
Keyword(s):  
Humic Acid ◽  
Fluorescence Quenching ◽  
Water Solubility ◽  
Binding Constants ◽  
High Water ◽  
Static Quenching ◽  
Temperature Range ◽  
Equilibrium Binding ◽  
Quenching Analysis ◽  
High Water Solubility

Fluorescence quenching was used to investigate the interaction of six fluoroquinolones with humic acid. Static quenching was observed for the binding of ciprofloxacin, enoxacin, fleroxacin, levofloxacin, norfloxacin, and ofloxacin to humic acid. The equilibrium binding constants were found from Stern–Volmer plots of the data. The quenching experiments were repeated over a temperature range of 25–45 ℃ and van’t Hoff plots were generated. From these linear plots, thermodynamic values were calculated for Δ H, Δ G, and Δ S for each of the fluoroquinolones. The equilibrium binding constants were found to be <1 for all the antibiotics studied. The calculated ΔH values were all negative and ranged from −9.5 to −27.6 kJ/mol. The high water solubility of the antibiotics and low ΔH of binding suggests that the antibiotics will be transported easily through the environment. Finally, whether the fluoroquinolones are in a protonated, deprotonated, or partially protonated state is found to correlate to the strength of binding to humic acid.

Inclusion compounds of plant growth regulators in cyclodextrins. V. 4-Chlorophenoxyacetic acid encapsulated in β-cyclodextrin and heptakis(2,3,6-tri-O-methyl)-β-cyclodextrin

2005 ◽  
Vol 61 (2) ◽  
pp. 207-217 ◽  
Author(s):  
Frantzeska Tsorteki ◽  
Kostas Bethanis ◽  
Nikos Pinotsis ◽  
Petros Giastas ◽  
Dimitris Mentzafos
Keyword(s):  
Guest Molecule ◽  
Crystal Packing ◽  
Host Molecule ◽  
X Ray Diffraction ◽  
Guest Molecules ◽  
Space Group ◽  
X Ray ◽  
Dimeric Complexes ◽  
The Mean ◽  
Chlorophenoxyacetic Acid

The crystal structures of 4-chlorophenoxyacetic acid (4CPA) included in β-cyclodextrin (β-CD) and heptakis(2,3,6-tri-O-methyl)-β-cyclodextrin (TMβCD) have been studied by X-ray diffraction. The 4CPA/β-CD complex crystallizes as a head-to-head dimer in the space group C2 in the Tetrad packing mode. The packing modes of some β-CD dimeric complexes, having unique stackings, are also discussed. The 4CPA/TMβCD inclusion complex crystallizes in the space group P21 and its asymmetric unit contains two crystallographically independent complexes, complex A and complex B, exhibiting different conformations. The host molecule of complex A is significantly distorted, as a glucosidic residue rotated about the O4′—C1 and C4—O4 bonds forms an aperture where the guest molecule is accommodated. The phenyl moiety of the guest molecule of complex B is nearly perpendicular to the mean plane of the O4n atoms. The conformations of the guest molecules of the two complexes are similar. The crystal packing consists of antiparallel columns as in the majority of the TMβCD complexes published so far.

Colloidal properties of single component naphthenic acids and complex naphthenic acid mixtures

2013 ◽  
Vol 395 ◽  
pp. 104-110 ◽  
Author(s):  
Mohamed H. Mohamed ◽  
Lee D. Wilson ◽  
Kerry M. Peru ◽  
John V. Headley
Keyword(s):  
Naphthenic Acid ◽  
Naphthenic Acids ◽  
Single Component ◽  
Colloidal Properties

Investigation of the disorder of dibromo- and dichloromethane in their tri-ortho-thymotide clathrates using X-ray diffraction and solid-state 2H NMR spectroscopy

2011 ◽  
Vol 89 (7) ◽  
pp. 854-862
Author(s):  
Glenn A. Facey ◽  
Ilia Korobkov
Keyword(s):  
Solid State ◽  
Nmr Spectroscopy ◽  
Guest Molecule ◽  
Type B ◽  
X Ray Diffraction ◽  
Guest Molecules ◽  
X Ray ◽  
Twofold Axis ◽  
H Nmr ◽  
Heavy Atoms

The tri-ortho-thymotide (TOT) clathrates of dibromo- and dichloromethane were characterized by single crystal X-ray diffraction at 200 K and solid-state 2H NMR spectroscopy as a function of temperature. The host structure was found to be typical of other cage-type TOT clathrates. The X-ray results showed a substantial amount of disorder among the guest molecules. In both clathrates, multiple guest molecule positions could be modeled. The heavy atoms of all the guest molecule positions lie approximately in the same plane, with some out-of-plane distortion. The guest molecules were of two different types in positions symmetric about the crystallographic twofold rotation axis: type A guests, with carbon atoms well removed from the crystallographic twofold axis, and type B guests, with carbon atoms very close to the twofold axis. The 2H NMR spectra for the guests confirmed that the disorder was dynamic. The experimental results could be accounted for by the presence of three simultaneous types of molecular motion, all fast with respect to the 2H quadrupolar interaction: (i) twofold molecular flips about the molecular C2 symmetry axis, (ii) exchange between the type A and type B sites in a single plane, and (iii) a two-site libration of the plane containing the heavy atoms of the A and B guest sites with a temperature-dependent amplitude.

Determination of Relative Stability of Urea Complexes from X-Ray Powder Diffraction Data

1960 ◽  
Vol 4 ◽  
pp. 140-150 ◽  
Author(s):  
Jack Radell ◽  
J.W. Connolly
Keyword(s):  
Dissociation Constant ◽  
Guest Molecule ◽  
Interplanar Spacing ◽  
Dynamic Equilibrium ◽  
Crystalline Complex ◽  
Guest Molecules ◽  
X Ray ◽  
Host Molecules ◽  
The Stability

AbstractUrea complexes consist of a channel made up of hydrogen-bonded urea host molecules into which a variety of guest molecules can fit to form a crystalline complex. The urea host can accommodate, one at a time, a variety of guests having the requisite size and shape. The stability of the resulting complex is a function of the properties of the guest molecule. A procedure has been devised which produces pure complex free of any uncomplexed urea or host molecules in solution. The insoluble crystalline complexes formed from the solution of urea and guest molecule in methanol established a dynamic equilibrium. When the crystals of complex are removed from the solution, dissociation to urea and guest occurs to an extent, depending upon the dissociation constant of the complex. If the dissociation constant, KD, is very low, undetectable quantities of uncomplexed urea form along with complex. If the dlissoclation constant is high, extensive amounts of urea form in the presence of complex. Characteristic interplanar spacing s are obtained for a urea complex irrespective of the guest molecule present. The pattern obtained for the hexagonal complex is completely different from the pattern obtained for tetragonal urea. X-ray examination of a homologous series of compounds gives, for each partially dissociated complex, spacings for both urea and complex. The relative intensities of urea and complex spacings permit the estimation of the stability of such a complex compared to that of other homologues.

Inclusion complexation involving sugar-containing species: β-cyclodextrin and sugar surfactants

2004 ◽  
Vol 82 (1) ◽  
pp. 45-49 ◽  
Author(s):  
Vincent C Reinsborough ◽  
Vanessa C Stephenson
Keyword(s):  
Surface Tension ◽  
Critical Micelle Concentration ◽  
Inclusion Complex ◽  
Computer Modeling ◽  
Inclusion Complexation ◽  
Binding Constants ◽  
Guest Molecules ◽  
Sugar Moiety ◽  
G 12 ◽  
Concentration Surface

Surface tension, proton NMR, and computer modeling studies were undertaken in nonionic alkylpolyglycoside (APG) solutions containing β-cyclodextrin (β-CD) with a view to characterize the inclusion complexes formed and to determine if the sugar entities of the host and guest molecules played a significant role in the process. The APGs investigated were four glucopyranosides (octyl G8, decyl G10, dodecyl G12, tetradecyl G14) and two maltosides (decyl M10, dodecyl M12). Critical micelle concentrations (CMC) were obtained in the surfactant–β-CD systems, which in all cases increased with increasing β-CD concentration. The 1:1 APG–β-CD inclusion complex was principally formed with binding constants of 425 (mol L–1)–1 for the G12 complex, 340 (mol L–1)–1 for the G10 complex, and 125 (mol L–1)–1 for the M12 complex. The preferred configuration of the G-12–β-CD complex has the surfactant tail coiled in the CD cavity with the surfactant sugar moiety sealing off the narrower opening of the CD torus.Key words: alkylpolyglycoside, β-cyclodextrin, NMR, critical micelle concentration, surface tension.

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