Comparative analysis of the thermal decomposition kinetics of β-cyclodextrin inclusion complexes with anabasine at different heating rates

The results of analysis of the thermal decomposition kinetics of inclusion complexes of β-cyclodextrin with the alkaloid anabasine at different heating rates are presented. The kinetic characteristics of the processes are determined based on the Friedman, Flynn–Wall–Ozawa and nonparametric kinetics methods.     

Influence of different techniques on formulation and comparative characterization of inclusion complexes of ASA with β-cyclodextrin and inclusion complexes of ASA with PMDA cross-linked β-cyclodextrin nanosponges

Acetyl salicylic acid (ASA), a non-steroidal anti-inflammatory drug, was formulated into inclusion complexes by grinding and precipitation with β-cyclodextrin and freeze drying with pyromellitic dianhydride (PMDA) cross-linked β-cyclodextrin nanosponges. Particle size, zeta potential, encapsulation efficiency, accelerated stability study, in vitro and in vivo release studies were used as characterization parameters. TEM studies showed that the particle sizes of different inclusion complexes of ASA have diameters ranging from 40.12?±?8.79 to 59.53?±?15.55?nm. It also revealed the regular spherical shape and sizes of complexes that are even unaffected after drug encapsulation. Zeta potential was sufficiently high to obtain a stable colloidal formulation. The in vitro and in vivo studies indicated a slow and prolonged ASA release from PMDA cross-linked β-cyclodextrin nanosponges over a long period. XRPD, DSC and FTIR studies confirmed the interactions of ASA with nanosponges. XRPD showed the crystalline nature of ASA decreased after encapsulation. These results indicate that ASA nanosponges formulation can be used for oral delivery.     

Preparation and evaluation of inclusion complexes of diacerein with β-cyclodextrin and hydroxypropyl β-cyclodextrin

The objective of this research was to improve the aqueous solubility, dissolution rate and, consequently, bioavailability of diacerein, along with avoiding its side effect of diarrhea, by complexation with β-cyclodextrin (β-CD) and HP-β-cyclodextrin (HP-β-CD). Phase solubility curve was classified as an A_N type for both the CDs, which indicated formation of complex of diacerein with β-CD and HP-β-CD in 1:1 stoichiometry and demonstrating that both CDs are proportionally less effective at higher concentrations. The complexes were prepared by kneading method and were evaluated to study the effect of complexation on aqueous solubility and rate of dissolution in phosphate buffer (pH 6.8). Based on the dissolution profile HP-β-CD was selected for preparing fast disintegrating tablet of diacerein which was compared with marketed formulation (MF-J). The HP-β-CD complex was probed for Fourier transform infrared spectroscopy, differential scanning calorimetry, and powder X-ray diffraction studies which evidenced stable complex formation and increase in amorphousness of diacerein in complex. In brief, the characterization studies confirmed the inclusion of diacerein within the non-polar cavity of HP-β-CD. HP-β-CD complex showed improved in vitro drug release profile compared to pure drug and similar to that of marketed formulation respectively.     

Excimer fluorescence and structures of the inclusion complexes of β-cyclodextrin with naphthalene and its derivatives

Fluorescence of the inclusion complexes with different compositions formed by naphthalene-h₈, naphthalene-d₈, 2,7-dimethylnaphthalene (DMN), and 2-benzylnaphthalene (BN) with β-cyclodextrin (β-CD) in water was studied. Two types of fluorescence are observed, monomer (MF) and excimer (EF_ fluorescence. The excimer fluorescence of the 2∶2 complex emitted by aggregated light-dispersing crystals forming a precipitate, whereas is the MF is concentrations, EF predominates for the resulting complexes. A proposed structure of the inclusion complexes was derived from MNDO/PM3 semiempirical quantum-chemical calculations. The EF is caused by the structure of the complex, in which both naphthalene molecules are separated by a distance of 4.7 Å: they lie in parallel orientation to each other, whereby one ring is displaced from the other by one-fourth of the length of the naphthalene ring. The complexes of 2,7-DMN and 2-benzylnaphthalene with β-CD do not exhibit EF. For the 2∶2 complex of 2,7-DMN with β-CD, this is due to the fact that the aromatic fragments are removed too far from one another 2-Benzylnaphthalene is unable to form an inclusion complex with β-CD, in whose structure the aromatic fragments inside the cavity could be arranged in parallel planes; instead, it forms a 1∶2 complex with β-CD.     

Study of inclusion complex of β-cyclodextrin and diphenylamine: photophysical and electrochemical behaviors

The photophysical, electrochemical and photoprototropic behaviors of diphenylamine (DPA) in aqueous β-cyclodextrin (β-CD) solution have been investigated using absorption spectroscopy and cyclic voltammetric techniques. Absorption of the neutral and cationic form of DPA is enhanced due to the formation of a 1:1 complex with β-CD. The formation of this complex has been confirmed by Benesi-Hildebrand plot and docking studies by RasMol tool methods. The solid complex of β-CD with DPA is investigated by FT-IR, XRD and AFM methods. The thermodynamic parameters (ΔG, ΔH and ΔS) of inclusion process are also determined. The pK(a) values of neutral-monocation equilibria have been determined with absorption (conjugate acid-base) titrations. A mechanism is proposed to explain the inclusion process.     

Study on preparation and inclusion behavior of inclusion complexes between β-cyclodextrin derivatives with benzophenone

In the paper, the two chemically modified β-cyclodextrin derivatives of 4,4´-diaminodiphenyl ether-bridged-bis-β-cyclodextrins (ODA-bis-β-CD) and p-aminobenzenesulfonic acid-β-cyclodextrin (ABS-β-CD) were synthesized, and then these two β-cyclodextrin derivatives were respectively formed into inclusion complexes with benzophenone (BP) by co-precipitation method. The structure of the inclusion complexes were characterized by UV/vis spectroscopy, FT-IR spectroscopy, elemental analysis, ¹H NMR spectroscopy and XRD. Spectral titration was performed to study the inclusion behavior of the inclusion complexes. These experiments indicated that two inclusion complexes were formed at a stoichiometric ratio of 1:1 and the inclusion stability constants at different temperatures were calculated using the Benesi–Hildebrand (B–H) equation. The thermodynamic parameters (ΔG°, ΔH°, ΔS°) were obtained. As a result, it was found that the two chemically modified β-cyclodextrins containing BP were exothermic and spontaneous process (ΔG°?<?0), and the processes of inclusion complexation were mainly enthalpy driven with negative or minor negative entropic contribution.     

Electrochemical and associated techniques for the study of the inclusion complexes of thymol and β-cyclodextrin and its interaction with DNA

Journal of Solid State Electrochemistry - Thymol, a potent agent for microbial, fungal, and bacterial disease, has low aqueous solubility and it is genotoxic, i.e., is capable of damaging...     

Long-lived phosphorescence of aqueous solutions of β-cyclodextrin complexes with naphthalene and its derivatives at room temperature

A long-lived phosphorescence at room temperature (lifetime>1 s) of aqueous solutions of β-cyclodextrin complexes with naphthalene and its derivatives was found. The phosphorescence isobserved for aggregated complexes that form in water a light-scattering suspension, and its low intensity is due to predomination of 2∶2 complexes with efficient excimer fluorescence. Complexes containing isolated aromatic molecules are assumed to be the centers of fluorescence. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 10, pp. 2022–2024, October, 1999.     

Carotenoids and β-cyclodextrin inclusion complexes: Raman spectroscopy and theoretical investigation

In the present study, the inclusion processes of β-carotene, astaxanthin, lycopene, and norbixin (NOR) into the β-cyclodextrin (β-CD) cavity were investigated by means of Raman spectroscopy and quantum mechanics calculations. The Raman ν(1) band assigned to C═C stretching was sensitive to the host-guest interaction and in general undergoes a blue shift (3-13 cm(-1)) after inclusion takes place, which is the consequence of the localization of single and double bonds. This is supported by the molecular modeling prediction, which inclusion complexes show the ν(1) band blue shifted by 1-8 cm(-1). The calculated complexation energies was small for most of derivatives and was found to be -11.1 kcal mol(-1) for inclusion of AST and +0.27 kcal mol(-1) for NOR. The stability order was qualitatively correlated to topological parameters accounting for the opening angle of the chain. This means that after inclusion the guest molecules assume a slightly more extended conformation, which enhances the host-guest contact, improving the interaction energy. The results discussed here clearly demonstrate the matrix effect on the carotenes' spectroscopic profile and should contribute to fully characterize the raw samples.     

Investigation of inclusion complexes of citronella oil, citronellal and citronellol with β-cyclodextrin for mosquito repellent

The aim of this study was to prepare the inclusion complexes of citronella oil, citronellal or citronellol with β-cyclodextrin and evaluate their physicochemical properties using scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FTIR) and differential scanning calorimetry (DSC). A kneading method was employed to prepare the inclusion complexes and weight ratios of each of the active substance to β-cyclodextrin were 1:1 (1:1 CPX) and 1:2 (1:2 CPX). For comparison purposes, physical mixtures of these active compounds and β-cyclodextrin were also prepared and investigated. Unlike the physical mixtures, the SEM technique revealed drastic changes in the shapes and morphologies of the particles for the inclusion complexes. Furthermore, the FTIR and DSC results seemed to reveal some interactions between the active substance and β-cyclodextrin. The o/w lotions, which contained 10% w/w citronella oil (normal citronella oil; 1:1 CPX or 1:2 CPX), were formulated using Cremophors as emulsifiers. With modified Franz diffusion cell and synthetic membrane, the release rates of citronella oil from the lotions containing the inclusion complexes were significantly lower than that from the prepared lotion containing normal citronella oil. The mosquito (Aedes aegypti) repellent efficacy of the lotions containing citronella oil, citronellal or citronellol (both normal and inclusion complexes) was further evaluated by human-bait technique. The highest mosquito repellent activity was observed in the formulation which contained citronella oil–β-cyclodextrin inclusion complex at weight ratio of 1:1.     

Formation of inclusion complexes and controlled release of atrazine using free or silica-anchored β-cyclodextrin

Immobilization of cyclodextrin on the surface of silica was performed using citric acid as the bonding agent. Inclusion complexes of atrazine with free (CD) or anchored (CDSI) β-cyclodextrin were prepared and then characterized using infrared spectroscopy, X-ray diffraction and differential scanning calorimetry. The complexation reaction showed first order kinetics, with a rate constant (k) of 8.72?×?10^?3 min^?1. There was a rapid increase of absorbance in the first 40?min, followed by attainment of equilibrium after ~2?h. The stoichiometry of the reaction was 1:1, with both free and anchored β-cyclodextrin increasing the solubilization of atrazine in an aqueous medium (by around 1.5 and 3.4 times, respectively). The association constant (K _a) of the complex was 28.93?L?mol^?1 using CD and 130.68?L?mol^?1 using CDSI. In release tests, 62% of the atrazine complexed with CDSI or β-CD was released after 40?h, while 83% of free atrazine was released during the same period.     

Modeling and conformation analysis of β-cyclodextrin complexes

Summary A series of -cyclodextrin complexes containing various guest molecules was studied using computer-aided molecular modeling and conformation analysis techniques. The geometry of each complex was studied using crystallographic data. The positions of the glycosidic O4 atoms indicate that the -cyclodextrin molecules are elliptically distorted. This distortion can be related to the van der Waals volume of the guest molecules. This correlation is different for aromatic and non-aromatic guest compounds. Rigid body docking experiments demonstrated that in crystal structures the guest molecule occupies a position in the cavity of nearly minimum interaction energy when there are no other molecules having interactions with the guest molecule. From the crystallographic data several rules could be deduced which seem to determine the conformation of -cyclodextrin molecules in complexes. A procedure was developed to construct -cyclodextrin molecules that are able to encompass guest molecules having a given van der Waals volume.     

Solubility and molecular modeling of triflumizole-β-cyclodextrin inclusion complexes

Solubility enhancement of the fungicide triflumicole by-cyclodextrin is explained using a thermodynamic approach. The influence of organic cosolvents on the overall equilibrium constants of triflumizole complexation with-cyclodextrin in aqueous solutions has been investigated. Their variance in mixed solvents is only partly explained by a competitive inclusion of substrate and cosolvent molecules in-cyclodextrin. The geometries of host-guest complexes have been estimated by molecular mechanics calculations. Their broad structural variety caused by the flexibility of host and guest molecules and different association possibilities of triflumizole have been analysed by a dynamic Monte Carlo docking method. The hydrophobic effect has been simulated by cominimization of the hydrophobic contributions to the solvation energy, calculated from the solvent accessible surface area of the complex and the conformational (potential) energy.     

A study on the inclusion complexation of 3,4,5-trihydroxybenzoic acid with β-cyclodextrin at different pH

Effect of β-cyclodextrin (β-CD) on the absorption and fluorescence spectra of 3,4,5-trihydroxybenzoic acid (THB) have been studied buffer solutions of different pHs (pH ~1, pH ~7 and pH ~10). The study reveals that in all the above pHs THB forms 1:1 inclusion complex. The hydroxyl groups are present in the interior part of the β-CD cavity and carboxyl group is present in the hydrophilic part of the β-CD cavity. Dual luminescence is observed at pH ~1 and pH ~7 solutions which shows that intramolecular charge transfer present at these pH. The broad spectral maximum at pH ~10 indicates that intramolecular proton transfer is present in THB.     

Volumetric study on the inclusion complex formation of α- and β-cyclodextrin with 1-alkanols at different temperatures

The partial molar volumes (V_a) of 1-alkanols (carbon number, m=5, 6, 7) in - and -cyclodextrin (CD) solutions at 5.00 mmol kg^–1 have been determined as a function of alkanol concentration (C_a) between 293.2 and 308.2 K by using a dilatometer. It has been observed that with an increase in C_a, V_a increased in -CD solution but decreased in -CD solution, asymptotically to a value of V_a in CD-free water. The dependence of V_a on C_a provided the binding constant (K) of 1:1 complex, the volume change in complex formation, and the partial molar volume of complex itself. The complex formation mechanism has been discussed on the basis of these values and their carbon number dependences in the respect of geometric behavior, hydrophobic interaction, and van der Waals interaction. It is concluded that the CD cavity in water is not rigid but flexible for fitting in nicely with guest molecule.