Native Β-cyclodextrin Research Articles

Manifold Fluorescence Enhancement of a Styryl(pyridinium)-chromene Hybrid Dye upon Binding with an Elongated β-Cyclodextrin Cavity.

The interaction of a styryl(pyridinium)-chromene hybrid dye (DSP-C) with the 2-hydroxypropyl-β-cyclodextrin (HPβCD) macrocycle leads to a remarkably large increase (∼310-fold) in its fluorescence intensity, in contrast to the relatively smaller (∼45-fold) enhancement observed with native β-cyclodextrin (βCD). Both macrocycles (βCD and HPβCD) bind with the styryl(pyridinium) as well as the chromene fragments of the hybrid dye, with the simultaneous formation of 1:1 and 2:1 host:guest complexes. However, the binding constant (Keq1) is more than an order of magnitude higher for HPβCD than for βCD. The improved binding affinity of HPβCD is attributed to its elongated and deeper hydrophobic cavity. This is supported well by the optimized geometries of the host-guest complexes. Theoretical calculations also reveal that the energy change due to the release of high-energy water molecules from the host nanocavity is more favorable for HPβCD than βCD, resulting in greater stability of the HPβCD:DSP-C complex. Interestingly, though the fluorescence of DSP-C arises from its styryl(pyridinium) fragment, the complexation of the chromene unit with the host plays a major role in augmenting the fluorescence enhancement of the hybrid dye. The large fluorescence change in the HPβCD:DSP-C system has been utilized for the detection of bile salts by the indicator displacement strategy.

DFT Investigation on the Complexation of β-Cyclodextrin and Hydroxypropyl-β-Cyclodextrin as Recognition Hosts with Trichloroethylene

In this investigation, the potential use of native β-cyclodextrin (β-CD) and hydroxypropyl-β-cyclodextrin (HP-β-CD) as encapsulating agents for trichloroethylene (TCE) was assessed. Various quantum chemical parameters, including HOMO, LUMO, and HOMO–LUMO gap, were calculated. The docking process was examined by considering different initial configurations. The complexation energies were calculated at the molecular level using DFT/BLYP-D4 and PBEh-3c calculations to gain insight into TCE encapsulation within the β-CD and HP-β-CD cavities. We used the independent gradient model (IGM) and extended charge decomposition analysis (ECDA) approaches to examine non-covalent interactions and charge transfer within TCE@β-CD and TCE@HP-β-CD complexes. The calculated thermodynamic data and complexation energies exhibited negative values for both considered complexes, indicating a favorable complexation process. Weak Van der Waals intermolecular interactions were the main driving forces in stabilizing the formed complex. Additionally, Monte Carlo simulations were conducted for a better understanding of the inclusion process. Our results provide evidence for the use of β-CD and HP-β-CD as suitable macrocyclic hosts for complexing trichloroethylene.

A novel approach to supramolecular Aggregation-Induced emission using tetracationic tetraphenylethylene and sulfated β-Cyclodextrin

The combination of aggregation-induced emission-based luminogens (AIEgens) with supramolecular chemistry has gained significant attention due to its ability to produce intense emission even at low concentrations. In this study, we report a supramolecular arrangement characterized by aggregation-induced emission through the integration of tetracationic tetraphenylethylene with a macrocyclic polyanionic derivative of β-cyclodextrin. Despite the exploration of ionic derivatives of cyclodextrins in pharmaceutical and host–guest supramolecular chemistry, the phenomenon of supramolecular aggregation-induced emission based on non-covalent interactions between the ionic derivative of β-cyclodextrin and derivatives of tetraphenylethyelene, a class of AIEgens, has received limited investigation. Our work explores AIE shown by the allylimidazolium derivative of tetracationic tetraphenylethyelene (ALITPE) induced by complexation with polyanionic sulfated β-cyclodextrin (SCD). The effectiveness of the emission intensity of this supramolecular assembly based on AIE is confirmed by steady-state and time-resolved fluorescence measurements, which are supported by ground-state absorption measurements. We also investigate the effect of changes in external environment, such as temperature, pH, and ionic strength, on the supramolecular assembly. Moreover, the aggregation behavior of ALITPE with SCD is comparatively studied with neutral native β-cyclodextrin, highlighting the contribution of high negative charge density on the surface of SCD for efficient aggregation with ALITPE molecules. Additionally, Molecular Docking calculations are employed to provide insights into the aggregation behavior of ALITPE molecules induced by SCD. Overall, our findings demonstrate the potential applicability of the ALITPE/SCD supramolecular assembly as a potential fluorescent sensing probe for various biological applications.

A promising synthetic citric crosslinked β-cyclodextrin derivative for antifungal drugs: Solubilization, cytotoxicity, and antifungal activity

Effective antifungal therapy for the treatment of fungal keratitis requires a high drug concentration at the corneal surface. However, the use of natural β-cyclodextrin (βCD) in the preparation of aqueous eye drop formulations for treating fungal keratitis is limited by its low aqueous solubility. Here, we synthesized water-soluble anionic βCD derivatives capable of forming water-soluble complexes and evaluated the solubility, cytotoxicity, and antifungal efficacy of drug prepared using the βCD derivative. To achieve this, a citric acid crosslinked βCD (polyCTR-βCD) was successfully synthesized, and the aqueous solubilities of selected antifungal drugs, including voriconazole, miconazole (MCZ), itraconazole, and amphotericin B, in polyCTR-βCD and analogous βCD solutions were evaluated. Among the drugs tested, complexation of MCZ with polyCTR-βCD (MCZ/polyCTR-βCD) increased MCZ aqueous solubility by 95-fold compared with that of MCZ/βCD. The inclusion complex formation of MCZ/βCD and MCZ/polyCTR-βCD was confirmed by spectroscopic techniques. Additionally, the nanoaggregates of saturated MCZ/polyCTR-βCD and MCZ/βCD solutions were observed using dynamic light scattering and transmission electron microscopy. Moreover, MCZ/polyCTR-βCD solution exhibited good mucoadhesion, sustained drug release, and high drug permeation of porcine cornea ex vivo. Hen’s Egg test-chorioallantoic membrane assay and cell viability study using Statens Seruminstitut Rabbit Cornea cell line showed that both MCZ/polyCTR-βCD and MCZ/βCD exhibited no sign of irritation and non-toxic to cell line. Additionally, antifungal activity evaluation demonstrated that all isolated fungi, including Candida albicans, Aspergillus flavus, and Fusarium solani, were susceptible to MCZ/polyCTR-βCD. Overall, the results showed that polyCTR-βCD could be a promising nanocarrier for the ocular delivery of MCZ.

Comparative Analysis of the Effect of Native and Polymeric β-Cyclodextrins on the Solubility and Membrane Permeability of Baricitinib

A study is performed of the effect native and polymeric β-cyclodextrins have on the solubility and membrane permeability of baricitinib, a new generation immunomodulator. It is found that native and polymeric β-cyclodextrins exhibit the same solubilizing effect in relation to baricitinib, while their effect on the membrane permeability of the drug differs. The increased solubility of baricitinib is due to the formation of inclusion complexes that have the same stability but are enthalpy-entropy stabilized in native β-cyclodextrin and enthalpy stabilized in polymeric β-cyclodextrin. The effect cyclodextrins on baricitinib’s coefficients of permeability of through a model membrane is discussed in terms of complexation, changes in the viscosity of the medium, and the state of the water boundary layer near the membrane’s surface.

Amplification of SERS Signal of Methotrexate Using Beta-Cyclodextrin Modified Silver Nanoparticles

The paper describes the use of native β-cyclodextrin (CD) for the modification of silver nanoparticles (AgNPs) in order to improve the determination of the anticancer drug methotrexate (MTX) using surface-enhanced Raman spectroscopy (SERS). A control experiment with unmodified AgNPs showed that the strong SERS signal of MTX can only be achieved in alkaline media. However, competitive interactions and the strong background signal of human body fluid components significantly challenge MTX determination in real samples. While previous reports propose the use of thorough sample pretreatment (e.g., solid phase extraction), the application of CD-modified AgNPs increases the SERS signal of MTX in neutral media by seven times which enables simplifying the analysis and improving its accuracy by reducing the influence of endogenous components of body fluids. A detailed study of the synthesis conditions (CD concentration and reaction time) and SERS registration conditions (pH, NaCl concentration, dilution of urine samples) was performed to maximize the analytical signal and signal-to-noise ratio. The final assay was tested for MTX determination in artificially spiked samples of real human urine. The results demonstrated that MTX can be determined within the concentration range suitable for therapeutic drug monitoring (20–300 μg mL−1) with satisfactory precision (6–15% RSD), accuracy (95–111% apparent recovery), and limit of detection (0.3 μg mL−1).

Continuous flow synthesis of 6-monoamino-6-monodeoxy-β-cyclodextrin.

The first continuous flow method was developed for the synthesis of 6-monoamino-6-monodeoxy-β-cyclodextrin starting from native β-cyclodextrin through three reaction steps, such as monotosylation, azidation and reduction. All reaction steps were studied separately and optimized under continuous flow conditions. After the optimization, the reaction steps were coupled in a semi-continuous flow system, since a solvent exchange had to be performed after the tosylation. However, the azidation and the reduction steps were compatible to be coupled in one flow system obtaining 6-monoamino-6-monodeoxy-β-cyclodextrin in a high yield. Our flow method developed is safer and faster than the batch approaches.

Inclusion complexes of squalene with beta-cyclodextrin and methyl-beta-cyclodextrin: preparation and characterization.

The present work aimed to investigate inclusion complexes of squalene with various cyclodextrins (native β-cyclodextrin and methyl-β-cyclodextrin). The production of squalene-β-cyclodextrin inclusion complex was obtained using Response Surface Methodology and obtained inclusion complexes were studied with FTIR spectroscopy, X-ray diffractometry, thermal analysis, and 1H-NMR spectrometry. At the same time, squalene content was determined by reversed-phase high-performance liquid chromatography. All results confirmed that squalene was successfully involved in the cyclodextrin cavities. Optimizing the condition in preparation for the squalen-β-cyclodextrin inclusion complex yielded 54.3% with squalene content of 9.01%. The essential difference for the inclusion complex of squalene with methylated beta-cyclodextrin was that no precipitate formed in the initial mixture, and the complex was more efficiently dispersed in water. The conclusions of the inclusion complex formation were confirmed by computer simulation by optimizing the complex geometry using the DFT, MM2, and MP3 methods.

Engineered Self-Assembly of Amphiphilic Cyclodextrin Conjugates for Drug Encapsulation.

Cyclodextrins are a group of naturally occurring oligosaccharides that have widely been studied and applied in pharmaceutical formulations forming inclusion complexes with a broad variety of drugs exhibiting different hydrophilicity as well as molecular weights. Grafting aliphatic chains onto native cyclodextrins renders them amphiphilic and enables self-assembly into supramolecular structures that have already been explored for drug delivery. Based on the possibility of controlling the inherent physicochemical properties by modifying their chemical structure, amphiphilic cyclodextrin conjugates hold a great potential to become a drug delivery platform adaptable to the individual needs of specific active drug molecules. In this work, a library of amphiphilic cyclodextrin derivatives was synthesized by conjugating aliphatic chains of different lengths to native β-cyclodextrin via thioether or ester bonds. Upon nanoprecipitation, the synthesized amphiphilic cyclodextrin derivatives spontaneously self-assembled into nanosized supramolecular structures with a monodisperse size distribution. We systematically investigated the relationship between the molecular structure of the amphiphilic cyclodextrin derivatives and the corresponding self-assembly into nanosystems as well as the encapsulation of model drugs with different physicochemical properties. Encapsulation efficiencies up to 97% and pH-dependent release profiles were achieved. We found that both the aliphatic chain length and the linker molecule determine the respective self-assembly and drug encapsulation mechanism of the individual system. The colloidal stability and biocompatibility with human cells of all derivatives were proven. Consequently, amphiphilic cyclodextrin conjugates provide a drug delivery platform with tailor-made control over physicochemical properties and high drug encapsulation efficiency for a broad range of drug molecules, thus offering great potential for the development of future therapeutics with improved therapeutic efficiency.

A Comprehensive Study of Gemfibrozil Complexation with β-Cyclodextrins in Aqueous Solution Using Different Analytical Techniques

Gemfibrozil (GEM) is a hypolipidemic agent, which is effective in reducing serum cholesterol and triglyceride levels. Complexation of GEM with native β-cyclodextrin (β-CD) and with the derivatives hydroxypropyl-β- and randomly methylated β-CD (HPβ-CD and Meβ-CD) was studied in aqueous solution of pH 2.8 and 7.0. The stability constants were determined by spectrofluorimetry, 1H-NMR spectroscopy and solubility assays. Considering the well-known difficulties to obtain similar stability constants by different techniques, the agreement of the values obtained supports the reliability of the results presented. The advantages and drawbacks of each analytical technique for the study of inclusion complexation were discussed as well. In addition, the thermodynamic parameters of complexation, enthalpy (ΔH) and entropy (ΔS), were determined and related to the type of molecular interactions that take place between GEM and the different cyclodextrins. Finally, solid dispersions were prepared by co-evaporation, kneading, vacuum desiccation, and coprecipitation, and complexation was evaluated by X-ray diffraction.

Structural Studies of Piperine Inclusion Complexes in Native and Derivative β-Cyclodextrins.

Piperine (PN), the primary pungent alkaloid in black pepper shows several biological activities such as antioxidant, antimicrobial and anti-cancerogenic effects. Similar to other alkaloids, PN is characterized by poor water solubility. One way to improve its solubility and thus its biological activities is by forming inclusion complexes with suitable cyclodextrins. In this work PN inclusion complexes in native β-cyclodextrin (β-CD), its methylated (randomly methylated (RM-β-CD), heptakis-(2,6-di-O-methyl)-β-CD (DM-β-CD) and heptakis-(2,3,6-tri-O-methyl)-β-CD (TM-β-CD)) and 2-hydroxypropylated (HP-β-CD) derivatives are investigated using physicochemical methods, such as phase solubility study and X-ray crystallography complemented by theoretical (molecular dynamics simulations) studies. The determination of the crystal structure of the PN inclusion complexes in β-CD, DM-β-CD and TM-β-CD, reveals the formation of 1:2 guest:host inclusion complexes in the crystalline state. The guest PN molecule threads the hydrophobic cavities of the hosts which are arranged as couples in a tail-to-tail mode in the case of PN/β-CD and in a head-to-tail mode in the cases of PN/DM-β-CD and PN/TM-β-CD. MD studies based on the crystallographically determined structures and docked models show the stability of the examined complexes in an aqueous environment whereas the binding affinity of PN for the host molecules is calculated by the MM/GBSA method. Finally, phase-solubility studies of PN with β-CD, RM-β-CD and HP-β-CD are presented, indicating a Bs-type for the PN/β-CD complex and an AL-type for the PN/RM-β-CD and PN/HP-β-CD complexes with 1:1 guest:host stoichiometry.

Design, Preparation and Evaluation of Supramolecular Complexes with Curcumin for Enhanced Cytotoxicity in Breast Cancer Cell Lines.

Curcumin is one of the most researched phytochemicals by pharmacologists and formulation scientists to unleash its potential therapeutic benefits and tackle inherent biopharmaceutic problems. In this study, the native β-cyclodextrin (CD) and three derivatives, namely, Captisol (sulfobutyl ether β-CD), hydroxypropyl β-cyclodextrin, and hydroxyethyl β-cyclodextrin were investigated for inclusion complexes with curcumin using two preparation methods (physical mixing and solvent evaporation). The prepared complexes were studied for docking, solubility, FTIR, DSC, XRD, and dissolution rates. The best-fitting curcumin: cyclodextrins (the latter of the two CDs) were evaluated for cytotoxicity using human breast cell lines (MCF-7). Dose-dependent cytotoxicity was recorded as IC50% for curcumin, curcumin: hydroxyethyl β-cyclodextrin, and curcumin: hydroxypropyl β-cyclodextrin were 7.33, 7.28, and 19.05 µg/mL, respectively. These research findings indicate a protective role for the curcumin: hydroxypropyl β-cyclodextrin complex on the direct cell lines of MCF-7.

Alternative Methotrexate Oral Formulation: Enhanced Aqueous Solubility, Bioavailability, Photostability, and Permeability.

The poor aqueous solubility and/or permeability and thereby limited bioavailability largely restricts the pharmaco-therapeutic implications of potent anticancer drugs such as methotrexate (MTX). Furthermore, MTX’s inherently unstable nature makes it difficult to develop a viable oral formulation. In this study we developed the spray-dried amorphous inclusion complexes of MTX with native β-cyclodextrin (β-CD) and its derivatives, namely HP-β-CD, M-β-CD, and DM-β-CD to enhance the aqueous solubility, photostability, permeability, and oral bioavailability of MTX in rats. Our findings show that the 1:1 stoichiometry ratio of MTX and CDs improves the aqueous solubility, stability, and pharmacokinetic profiles of the drug, the better results being obtained particularly with DM-β-CD as a host, which has a higher complexation ability with the drug compared to other β-CDs. Specifically, the pharmacokinetic analysis demonstrated 2.20- and 3.29-fold increments in AUC and Cmax, respectively, in comparison to free MTX. Even though the absorptive permeability of MTX and MTX/DM-β-CD inclusion complexes was similar, the efflux of the absorbed MTX from ICs was significantly lower compared to the free MTX (4.6- vs. 8.0-fold). Furthermore, the physicochemical characterization employing SEM, DSC, and PXRD confirmed the transformation of crystalline MTX to its amorphous state. In solution, 1H NMR studies revealed that MTX embedded into the DM-β-CD cavity resulting in both H-3 and H-5 chemical shifts implied the presence of intermolecular interaction between the drug and CD moiety. It was, therefore, evident that an MTX IC could be a successful oral formulation technique, preventing MTX degradation and enhancing its pharmacologically relevant properties.

PdNP@Cyclodextrin on Cu/Al LDH-containing nanocomposites: Cage effect, crystallite size tuning and composite topology towards cross-couplings

A series of Cu/Al layered double hydroxides and Pd(0/II) composites containing native and modified cyclodextrins were prepared under different conditions of solvent (water or N,N-dimethylformamide), Pd precursors (Na2PdCl4 or Pd2dba3) and cyclodextrin/Pd ratios for the catalytic evaluation in Pd/Cu catalyzed cross-couplings aiming for the preparation of aryl thiophenes and N-arylamines. According to XPS measurements, the nanocomposites prepared in water presented a higher Pd(II)/Pd(0) ratio and subtle evidence of [PdCl4]2− intercalation by analyses of X-ray diffractograms. On the other hand, those prepared in N,N-dimethylformamide showed a higher content of Pd(0), probably dispersed on layered double hydroxides surface. SEM-FEG analyses combined with particle size distribution revealed that cyclodextrins were able to tune the size distribution, especially the β-form (15 nm in the presence of cyclodextrins). Powder X-rays diffraction data refinement using Rietveld method revealed that controlled palladium crystallite sizes of 11.53 nm and 10.22 nm were obtained in the presence of hydroxypropylated cyclodextrins (β and γ forms). Notably, the Rietveld refinement of the Pd nanocomposites revealed the presence of malachite, gibbsite, and sperniite phases in 23.05%, 23.05%, 15.23% contents. It suggests that Pd introduces a distortion in the initial LDH lattice. The catalytic activities of these nanocomposites were evaluated in Suzuki-Miyaura reaction in water/ethanol mixture, under low Pd loadings and room-temperature. Noteworthy, the nanocomposite prepared in N,N-dimethylformamide with native β-cyclodextrin showed higher catalytic activity (turnover number up to 7379) in Suzuki-Miyaura and Buchwald-Hartwig reactions for the synthesis of 2-aryl thiophenes, a component of several classes of functional organic electronic materials, and N-(4-nitrophenyl)-1,2-ethanediamine, respectively. This same nanocomposite was recycled up to three runs without loss in catalytic activity. A tentative test envisaging a one-pot borylation-Suzuki-Miyaura strategy indicated that the Miyaura borylation was conceivably affected by the coexisting malachite and spertiniite phases in the nanocomposite. However, control experiments in the presence of Cu(OH)2, Al(OH)3 and malachite indicate a lack of catalytic activity for these phases in Suzuki-Miyaura reactions. Thus, the catalytic activity is mostly attributed to the nanocomposite Cu–Al LDHs containing CDs. The enhancement in catalytic activity is suggested to occur as a result of deprotonation/adsorption of phenylboronic acid, transmetallation facilitated by a relatively high surface hydroxyl sites, improved substrate complexation by β-CDs and potential soluble Cu(II) active species from the layered matrix.

The Influence of the Hydroxyl Type on Crosslinking Process in Cyclodextrin Based Polyurethane Networks.

The influence of the hydroxyl groups (OH) type on the polyaddition processes of isocyanates represents a critical approach for the design of multicomponent polyurethane systems. Herein, to prove the effect of hydroxyl nature on both the isocyanate-OH polyaddition reactions and the structure/properties of the resulting networks, two structurally different cyclodextrins in terms of the primary and secondary groups’ ratio were analyzed, namely native β-cyclodextrin (CD) and its derivative esterified to the primary hydroxyl groups with oligolactide chains (CDLA). Thus, polyurethane hydrogels were prepared via the polyaddition of CD or CDLA to isophorone diisocyanate polyethylene glycol-based prepolymers (PEG-(NCO)2). The degradable character of the materials was induced by intercalating oligolactide short sequences into the polymer chains composing the polymer network. In order to establish the influence of the OH type, the synthesis of polyurethane hydrogels was analyzed by a rheological investigation of the overall system reactivity. Materials properties such as swelling behavior, thermal properties and hydrolytic degradation were influenced by the reaction feed. Specifically, the presence of primary OH groups leads to more compact networks with similar water uptake, disregarding the CD content, while the predominance of secondary OH groups together with the presence of oligolactide spacers leads to the fine tuning of the water swelling properties.

Tetraethylenepentamine-Coated β Cyclodextrin Nanoparticles for Dual DNA and siRNA Delivery.

Nucleic acid reagents, including plasmid-encoded genes and small interfering RNA (siRNA), are promising tools for validating gene function and for the development of therapeutic agents. Native β-cyclodextrins (BCDs) have limited efficiency in gene delivery due to their instable complexes with nucleic acid. We hypothesized that cationic BCD nanoparticles could be an efficient carrier for both DNA and siRNA. Tetraethylenepentamine-coated β-cyclodextrin (TEPA-BCD) nanoparticles were synthesized, characterized, and evaluated for targeted cell delivery of plasmid DNA and siRNA. The cationic TEPA coating provided ideal zeta potential and effective nucleic acid binding ability. When transfecting plasmid encoding green fluorescent protein (GFP) by TEPA-BCD, excellent GFP expression could be achieved in multiple cell lines. In addition, siRNA transfected by TEPA-BCD suppressed target GFP gene expression. We showed that TEPA-BCD internalization was mediated by energy-dependent endocytosis via both clathrin-dependent and caveolin-dependent endocytic pathways. TEPA-BCD nanoparticles provide an effective means of nucleic acid delivery and can act as potential carriers in future pharmaceutical application.

Assessment of sulfobutylether-beta-cyclodextrin as a promising Fluorometholone molecule container: DFT, Docking, Molecular dynamics and MM-PBSA free energy calculations

ABSTRACT In the present work, the preferential binding mode of Fluorometholone (FLU) drug into the nanopores of two cyclodexterins, b-cyclodextrin (b-CD) and sulfobutylether-b-cyclodextrin (SEB-b-CD), are theoretically investigated using density functional theory (DFT), Docking, the molecular dynamics (MD) simulation and MM-PBSA free energy calculations. The computational results reveal that hydrogen bonds (HBs) and van der Waals (vdW) interactions have the significant roles in the stability of FLU into the cavity of b-CD and SBE-b-CD structures in the aqueous phase. It is found that the complexing ability of FLU is significantly increased from -62.245 kJ/mol in native b-CD to -89.677 kJ/mol in SEB-b-CD by introducing sulfobutylether groups to the hydroxyl groups of the macromolecule. In addition, a remarkable enhancement of the solubility of SBE-β-CD, compared to the native β-cyclodextrin, is observed. The inclusion process of FLU drug into SEB-β-CD improves the polarity of FLU@SBE-β-CD complex and enhances its solubility. Furthermore, the conformational stability of the top-scored FLU@β-CD and FLU@SEB-β-CD docked models is analysed by molecular dynamics simulation. The MM-PBSA freeenergy approach approves more binding affinity of FLU drug into the SEB-β-CD cavity. The obtained data aim to explore the potential application of SEB-β-CD macromolecule for designing and developing pharmacological formulations.

One-Step Extraction of Olive Phenols from Aqueous Solution Using β-Cyclodextrin in the Solid State, a Simple Eco-Friendly Method Providing Photochemical Stability to the Extracts.

The extraction of phenolic compounds from olive mill wastes is important, not only to avoid environmental damages, but also because of the intrinsic value of those biophenols, well-known for their high antioxidant potential and health benefits. This study focuses on tyrosol (Tyr) and hydroxytyrosol (HT), two of the main phenolic compounds found in olive mill wastes. A new, simple, and eco-friendly extraction process for the removal of phenolic compounds from aqueous solutions using native β-cyclodextrin (β-CD) in the solid state has been developed. Several β-CD/biophenol molar ratios and biophenol concentrations were investigated, in order to maintain β-CD mostly in the solid state while optimizing the extraction yield and the loading capacity of the sorbent. The extraction efficiencies of Tyr and HT were up to 61%, with a total solid recovery higher than 90% using an initial concentration of 100 mM biophenol and 10 molar equivalents of β-CD. The photochemical stability of the complexes thus obtained was estimated from ∆E*ab curve vs. illumination time. The results obtained showed that the phenols encapsulated into solid β-CD are protected against photodegradation. The powder obtained could be directly developed as a safe-grade food supplement. This simple eco-friendly process could be used for extracting valuable biophenols from olive mill wastewater.

Unexpected Encapsulation of Selected Polycyclic Aromatic Hydrocarbons by β-Cyclodextrin Studied Using UV-Vis Spectrophotometry, Micro-Planar Chromatography and Temperature Dependent Inclusion Chromatography

This research communication significantly extends our previous studies focusing on the temperature effects related to the unexpected chromatographic behavior of 1-acenaphthenol in the presence of native β-cyclodextrin (β-CD) additive, working under thin-layer chromatographic (TLC) conditions. We have applied complementary and orthogonal techniques including (i) temperature-controlled ultraviolet-visible (UV-VIS) spectroscopy, (ii) thermostated microplanar high-performance chromatography (micro-HPTLC) and (iii) temperature-dependent inclusion chromatography based on high-performance liquid chromatography (HPLC) to investigate the retention behavior of related host molecules. Particularly, various symmetric and asymmetric molecules were tested, such as: naphthalene and its derivatives including acenaphthylene, acenaphthene and selected dimethynaphthalenes: 1,8-DMN, 1,5-DMN, 2,3-DMN and 2,6-DMN. Reported raw experimental data, particularly performed in liquid phase and detected by UV-Vis spectrophotometry, may suggest that solubility changes of the supramolecular complexes studied and differences in total analysis time between TLC and HPLC separation can trigger strong retention of target components in planar chromatographic systems. This was also supported by principal component analysis (PCA) of the multi-source data obtained. It is hoped that the reported analyses enable the adjustment of phenomenological models describing liquid chromatography retention and the solubility behavior of low-molecular mass guest molecules, controlled by supramolecular interactions with selected macrocycles. It should be noted that the reported phenomenon, specifically supramolecular complexes precipitation, may have a number of practical applications. This can be used to improve the efficiency and selectivity of planar and/or microfluidic systems. On the other hand, precipitation via host-guest interactions may be applied for highly selective water purification technological processes that will be designed for the removal of given organic micropollutants.

Evaluation of Enantioselective Capillary Electrophoretic Approach for the Enantiomeric Separation of Abscisic Acid

Background: The application of enantioselective capillary electrophoresis approach for the assessment of the enantiomeric purity of chiral molecules is receiving increased attention. Abscisic acid is one of the chiral sesquiterpenic plant growth regulators that regulate various ecological and physiological roles in higher plants. Enantiomeric determination of ABA is of great concern because of the different biological activity of its enantiomers. Materials and Methods: In this study, we investigated the enantioseparation selectivity of ABA by incorporating native β-cyclodextrins (β-CD) and its derivatives as chiral modifiers in the background electrolyte of an enantioselective capillary zone electrophoresis system. Electrophoretic aspects that affect the enantiomeric separation, such as pH, types of β-CD and its concentration, applied voltage, injection pressure and time, were studied and optimised. Results and Discussions: An enhancement in enantioseparation was achieved in a bare fused-silica capillary (64.5 cm × 50 mm i.d.) using a background electrolyte solution consisting of (2-hydroxypropyl)- β-CD (80 mM) solubilised in 100 mM phosphate buffer adjusted to pH 5.9 with NaOH, operated under normal polarity mode (25 kV) at 25°C, and using hydrodynamic injection (75 mbar for 10s). Relative standard deviations of (intra- and inter-day) ≤ 3.23% and ≤ 1.39% for migration times and enantiomeric fractions (EF) were achieved using the proposed method. Conclusion: The proposed chiral capillary electrophoretic method offers advantages in terms of enantioselectivity and analysis times, which can serve as a reliable platform for the stereoisomeric analysis of ABA.