Steven Ruellan

Complexation of estragole as pure compound and as main component of basil and tarragon essential oils with cyclodextrins

Inclusion complexes of estragole (ES) as pure compound and as main component of basil and tarragon essential oils (EOs) with α-cyclodextrin (α-CD), β-cyclodextrin (β-CD), hydroxypropyl-β-cyclodextrin (HP-β-CD), randomly methylated-β-cyclodextrin (RAMEB), a low methylated-β-cyclodextrin (CRYSMEB) and γ-cyclodextrin (γ-CD) were characterized. Formation constants (Kf) of the complexes were determined in aqueous solution by nonlinear regression analysis using static headspace gas chromatography (SH-GC) and UV-visible spectroscopy. Solid inclusion complexes were prepared by the freeze-drying method for different CD:ES molar ratios and were characterized by differential scanning calorimetry (DSC) and Fourier transform infrared spectroscopy (FT-IR). Inclusion complexes formation allowed the controlled release of ES. Moreover, increased DPPH radical scavenging activity and photostability of ES and ES containing EOs (ESEOs) were observed in the presence of CDs. These findings suggest that encapsulation with CDs could be an efficient tool to improve the use of ES and ESEOs in aromatherapy, cosmetic and food fields.

Cyclodextrin, an efficient tool for trans-anethole encapsulation: chromatographic, spectroscopic, thermal and structural studies.

Inclusion complexes of trans-anethole (AN) with α-cyclodextrin (α-CD), β-cyclodextrin (β-CD), hydroxypropyl-β-cyclodextrin (HP-β-CD), randomly methylated-β-cyclodextrin (RAMEB) and a low methylated-β-cyclodextrin (CRYSMEB) were investigated in aqueous solution by static headspace gas chromatography (SH-GC), phase solubility study, UV-Visible, (1)H NMR and (2D) ROESY NMR spectroscopies. The obtained results indicated the formation of 1:1 inclusion complex for all the studied CDs. Water solubility of AN was significantly improved upon complexation with CDs as demonstrated by phase solubility and retention studies. Solid inclusion complexes were prepared by the freeze-drying method and the encapsulation of AN was confirmed by Fourier transform infrared spectroscopy (FTIR) and differential scanning calorimetry (DSC) studies. Moreover, the degradation of AN, induced by UVC irradiation, was markedly reduced by the formation of CD inclusion complexes. Results showed that encapsulation in CDs was an efficient way to increase solubility and stability of AN, thereby making it valuable for food or pharmaceutical applications.

Determination of formation constants and structural characterization of cyclodextrin inclusion complexes with two phenolic isomers: carvacrol and thymol

Summary Carvacrol and thymol have been widely studied for their ability to control food spoilage and to extend shelf-life of food products due to their antimicrobial and antioxidant activities. However, they suffer from poor aqueous solubility and pronounced flavoring ability that limit their application in food systems. These drawbacks could be surpassed by encapsulation in cyclodextrins (CDs). Applications of their inclusion complexes with CDs were reported without investigating the inclusion phenomenon in deep. In this study, inclusion complexes were characterized in terms of formation constants (K f), complexation efficiency (CE), CD:guest molar ratio and increase in bulk formulation by using an UV–visible competitive method, phase solubility studies as well as 1H and DOSY 1H NMR titration experiments. For the first time, a new algorithmic treatment that combines the chemical shifts and diffusion coefficients variations for all guest protons was applied to calculate K f. The position of the hydroxy group in carvacrol and thymol did not affect the stoichiometry of the inclusion complexes but led to a different binding stability with CDs. 2D ROESY NMR experiments were also performed to prove the encapsulation and illustrate the stable 3D conformation of the inclusion complexes. The structural investigation was accomplished with molecular modeling studies. Finally, the radical scavenging activity of carvacrol and thymol was evaluated by the ABTS radical scavenging assay. An improvement of this activity was observed upon encapsulation. Taken together, these results evidence that the encapsulation in CDs could be valuable for applications of carvacrol and thymol in food.

Cyclodextrins: A promising drug delivery vehicle for bisphosphonate

Bisphosphonates are well established pharmaceutical drugs with wide applications in medicine. Nevertheless, the side chain and the nature of phosphorous groups could induce a poor aqueous solubility and act on their bioavailability. At the same time, cyclodextrins are cage molecules that facilitate transport of hydrophobic molecules to enhance the intestinal drug absorption of these molecules by forming inclusion complexes. Here we demonstrate that cyclodextrins could be used as a bisphosphonate carrier. The formation of cyclodextrins-bisphosphonate complexes was characterized by 1D and 2D NMR spectroscopy, Isothermal Titration Calorimetry and UV-vis spectroscopy. The results revealed that only the side chain of bisphosphonate was involved in the inclusion phenomenon and its length was a crucial parameter in the control of affinity. Findings from this study suggest that cyclodextrin will be a useful carrier for bisphosphonates.

Synthesis, binding and self-assembly properties of a well-defined pillar[5]arene end functionalised polydimethylacrylamide

The synthesis, binding and self-assembly properties of a well-defined pillar[5]arene end-functionalised poly(dimethylacrylamide)(MePilla-PDMAC) are reported. In order to synthesise MePilla-PDMAC, a new trithiocarbonate type RAFT agent MePilla-CTA was developed incorporting a partially methylated pillar[5]arene moiety. Kinetic studies clearly indicated the propensity of MePilla-CTA to control the polymerisation of DMAC. Interestingly, as PDMAC type chains display good solubilty both in organic and aqueous media, MePilla-PDMAC was able of specifically bind electron deficient guest molecules at the α-chain-end both in chloroform and water. Complex formation was found to be reversible upon addition of chloride anions or heating in organic and aqueous media, respectively. Furthermore, cryo-TEM, VT-NMR (1H) and VT-DLS investigations also indicated the ability of MePilla-PDMAC to self-assemble into micelle-like aggregates in water showing reversible recognition properties.

Nootkatone encapsulation by cyclodextrins: Effect on water solubility and photostability

Nootkatone (NO) is a sesquiterpenoid volatile flavor, used in foods, cosmetics and pharmaceuticals, possessing also insect repellent activity. Its application is limited because of its low aqueous solubility and stability; this could be resolved by encapsulation in cyclodextrins (CDs). This study evaluated the encapsulation of NO by CDs using phase solubility studies, Isothermal Titration Calorimetry, Nuclear Magnetic Resonance spectroscopy and molecular modeling. Solid CD/NO inclusion complex was prepared and characterized for encapsulation efficiency and loading capacity using UV-Visible. Thermal properties were investigated by thermogravimetric-differential thermal analysis and release studies were performed using multiple headspace extraction. Formation constants (Kf) proved the formation of stable inclusion complexes. NO aqueous solubility, photo- and thermal stability were enhanced and the release could be insured from solid complex in aqueous solution. This suggests that CDs are promising carrier to improve NO properties and, consequently, to enlarge its use in foods, cosmetics, pharmaceuticals and agrochemicals preparations.

Cyclodextrin-intercalated layered double hydroxides for fragrance release

In order to attain the controlled release of fragrance, the intercalation of cyclodextrins (CDs) and fragrance in layered double hydroxides (LDHs) was examined. Carboxymethyl-β-CDs (CMCDs) of various degrees of substitution as well as Mg–Al support were synthesized. CMCDs were intercalated into LDH by the reconstruction method. Powder X-ray diffraction, thermal gravimetric analyses and Fourier transform infrared indicated a successful intercalation of CMCDs into the LDH gallery. The retention capacities of the hybrid materials were investigated in aqueous phase and in gaseous solution by static headspace gas chromatography and multiple headspace extraction. The functionalization of the LDH with CMCD allowed the encapsulation of various organic guests and could prolong the fragrance release time in comparison to that from LDH without CMCD, which can be attributed to the inclusion of the fragrance compound in the CMCD cavity.

The effect of cyclodextrin complexation on the solubility and photostability of nerolidol as pure compound and as main constituent of cabreuva essential oil

Nerolidol (Ner), a major component of many plant essential oils, is known for its various biological properties. However, the low solubility of Ner in water and its susceptibility to degradation limit its application. The aim of our study was to improve the solubility and photostability of Ner through its encapsulation in different cyclodextrins (CDs). The formation constants of cis-, trans-Ner and their commercial mixture with various CDs (α-CD, β-CD, γ-CD, HP-β-CD, RAMEB, CRYSMEB and SBE-β-CD) were determined by phase solubility studies and confirmed by the spectral displacement UV-visible method. The solubility of cabreuva essential oil (EO) rich in trans-Ner was also evaluated by total organic carbon (TOC) analysis. The encapsulation efficiency (EE %) of Ner in HP-β-CD solid complexes was assessed by HPLC. The structural characterization of CD/trans-Ner inclusion complex was then conducted by NMR spectroscopy followed by molecular modelling studies. The effect of encapsulation on the Ner photostability was also carried out over time under UVB irradiation. AL-type phase-solubility diagrams were obtained, suggesting the formation of 1:1 CD/Ner inclusion complexes. The solubility of Ner was enhanced by approximately 70-fold in the presence of 10 mM HP-β-CD. Moreover, high EE % values were obtained for 5:1 and 10:1 HP-β-CD:Ner molar ratios. NMR and molecular modelling studies revealed the most stable structure for trans-Ner inside the CD cavity with the OH group oriented towards the wider rim of the CD. Finally, CD encapsulation of Ner as pure compound or as main component of the cabreuva EO, protected it from degradation. This effect was more pronounced as the concentration of CD increased. These findings suggested that CDs are promising encapsulating carriers for Ner by enhancing its solubility and stability and thereby its application in food industry.