Journal of Inclusion Phenomena and Macrocyclic Chemistry最新文献

BCS class IV drugs have poor water solubility and permeability, which provide formulation issues due to partial or unpredictable absorption patterns and low bioavailability. This study aims to formulate a ternary solid dispersion of Cefditoren Pivoxil (CFDTPI) with β-cyclodextrin (β-CD) and sugar as carriers, and explore the effect of different types of sugars and sugar alcohols on the solubility, dissolution, and bioavailability of CFDTPI. CFDTPI’s interaction with sugars and β-CD was investigated by molecular docking studies. We conducted phase solubility tests to estimate the stability constant (Ks), complexation efficiency (CE), and Gibbs free energy (ΔG°). Binary and ternary solid dispersions were prepared using the kneading method, and their saturated solubility and in vitro dissolution were evaluated. A pharmacokinetic study was also conducted to determine the bioavailability of the prepared solid dispersions when compared to the pure drug. CFDTPI had a greater and more stable binding affinity with β-CD and sugars. The ternary solid dispersion, specifically the CP: β-CD: Mannitol 0.5% (1:1:0.5%), demonstrated superior dissolution with 99.29% drug release after 75 min, surpassing the pure drug (8.92%) and binary SD (61.63%). Solid-state research indicated that CFDTPI was trapped in the β-CD cavity, resulting in a more hydrophilic environment that improved solubility and dissolution. The pharmacokinetic study showed a 147.77% increase in bioavailability, demonstrating the effectiveness of β-CD and sugars in enhancing CFDTPI’s performance.

A novel dual-ligand Cu MOF material was synthesized with β-cyclodextrin and trimesic acid (H₃BTC) as the ligand of MOF and adsorbing material for plant polyphenol. The Box-Behnken design, a method used in response surface methodology, was applied to improve the extraction of Polygonum hydropiper L. (PL) polyphenols using the as-synthesized MOF. The optimal extraction conditions were determined to be a temperature of 39.4 °C, an ultrasound duration of 16.6 min, and a β-CD solution concentration of 13.4 mM. The resulting extract demonstrated a TPC of 196.34 µg GAE/mL, a DPPH radical scavenging activity of 75.33 µg GAE/mL, a FRAP activity of 68.53 µg GAE/mL, and an ABTS radical scavenging activity of 85.53 µg GAE/mL. The anti-glycosylation experiments demonstrated that the inclusion complex formed by PL polyphenols and β-CD effectively inhibits the production of end products during the later stages of glycosylation, suggesting that PL polyphenols possess strong anti-glycosylation properties. The bioactive activity study show that the copper-based MOFs (Cu-MOFs) possess good antitumor activity which leverages the unique characteristics of Fenton reactions and glutathione depletion capacity of Cu-MOFs. Furthermore, hemolysis test results demonstrated that the as-synthesized MOF possesses excellent biocompatibility, providing important evidence for its potential use in biomedical applications.

Graphical abstract

Schematic representation of β-cyclodextrin-assisted polyphenol extraction from Polygonum hydropiper L. and preparation of ketone-containing metal-organic frameworks.

In the present investigation, the wheel-and-axle compound 1,4-phenylene-bis(di-p-tolylmethanol) (H) was demonstrated to have efficient host ability for the saturated heterocyclic guest solvents dioxane, morpholine and piperidine (DIO, MOR and PIP), known toxins in wastewater. Host: guest (H: G) ratios varied, and from ¹H-NMR experiments, were calculated to be 1:4, 1:1 and 1:2, respectively. Previously, H was reported to form a complex also with the unsaturated heterocyclic solvent pyridine (PYR, H:G 1:3). When H was crystallized from mixtures containing two or more of the four guests, MOR and PYR were found to be favoured solvents, with DIO and PIP being less likely to be selected by the host species. In order to understand these selectivity observations, single crystal X-ray diffraction (SCXRD) experiments were performed on each single solvent inclusion compound, as well as thermogravimetric (TG) and differential scanning calorimetric (DSC) analyses. These latter two analytical techniques provided an understanding for the host selectivity behaviour in mixed guest crystallization experiments in that the MOR- and PYR-containing complexes were significantly more stable than those with DIO and PIP, which were not stable even at ambient conditions. Furthermore, least favoured DIO formed crystals with the lowest density of the four, alluding to a looser molecular packing in the complex, explaining the low host selectivity for this guest species. A brief comparison of these results with earlier reports pertaining to related host compounds 1,4-phenylene-bis(diphenylmethanol) (H1) and 1,4-phenylene-bis(di-p-fluorophenylmethanol) (H2) in the same guest solvents was also undertaken and is reported upon here.

This study aims to improve the photovoltaic properties of phthalacyanines by additives that can be used as DSSC to produce economical materials for renewable energy. Therefore, silver nanoparticles (AgNPs) were successfully synthesized by green chemistry method using green husk of walnut (GHW). Additionally, a new axial silicon phthalocyanine was synthesized. The phytocomponent AgNPs were doped with our newly synthesized phthalocyanine and applied in dye-sensitized solar cells (DSSC) as a sensitizer. The power conversion efficiency of the prepared DSSC was investigated. The formation of AgNPs was confirmed by optical absorption at wavelength between 350 and 540 nm. XRD data confirmed that the average crystallite size of AgNPs was 46.17 nm. FTIR analyses identified the bio-components potentially responsible for silver nanoparticle formation. TEM analysis shows that there are nanoparticles with an average size of 36.15 nm. The success of environmentally friendly green synthesized AgNPs to activate the sensitizer in DSSCs indicates that silver nanoparticles can be effectively used in such applications. The conversion efficiency of the axial phthalocyanine compound was measured as 2.05. However, as a result of doping the phthalocyanine compound with AgNPs, it was measured as 2.63 and 2.81 at 1:1 and 1:2 ratios, respectively. This clearly reveals the effect of AgNPs.

This article presents a novel method for removing and recovering the carcinogenic azo dye Orange II from wastewater using a newly synthesized in this work for the first time, pyridine-functionalized calix [4]arene derivative, clx4. Orange II, widely used in industries, poses significant environmental and health risks due to its toxic and carcinogenic properties. The structure of clx4 was characterized by using ¹H-NMR spectroscopy, FT-IR, mass, and elemental analysis. Solid-liquid and liquid-liquid extraction studies showed high removal efficiencies, with 86% and 99% of Orange II removed within one hour, respectively. Dye adsorption mechanisms were investigated through stability, complexation, and regeneration studies, confirming the effectiveness of clx4. Macrocyclic clx4 compound was also applied in Bulk Liquid Membrane (BLM) systems, demonstrating rapid and efficient transport of Orange II. Kinetic analysis, based on a model of two consecutive irreversible first-order reactions, provided transport rates, with membrane inlet (k₁) and outlet (k₂) rate constants determined through non-linear curve fitting. Maximum flux values for membrane inlet ( (:{J}_{d}^{max})) and outlet ( (:{J}_{a}^{max})) were calculated, highlighting the system’s efficiency. Regeneration studies confirmed the reusability of clx4 over multiple cycles, emphasizing its economic and environmental sustainability. These findings demonstrate clx4 as a promising candidate for the effective removal and recovery of Orange II from industrial wastewater, offering a sustainable solution for environmental remediation.

Porphyrin-based materials are attractive due to their adaptable photochemical and photophysical properties, it is also attainable through strategic organic group modifications. Therefore, the incorporation of porphyrins into inorganic materials yields distinct adsorption, catalytic, and sensing capabilities. This research focuses on modifying ZrO₂ and TiO₂ xerogels using organoalkoxysilanes bearing alkyl and aryl groups, and 5, 10, 15, 20-meso-tetrakis-(para-carboxyphenyl) porphyrin, H₂T(p-COOH)PP, as the active molecule. Near-infrared spectroscopy (NIR) confirmed the attachment of alkyl and aryl groups to the porphyrin via weak interactions. Nitrogen gas adsorption was carried out to characterize pore size and surface areas, while UV-vis and fluorescence spectroscopy monitored changes during the transition from jellifying mixtures to solids, the optimization of fluorescence and textural properties in organo-modified ZrO₂ and TiO₂ xerogels revealed notable trends such as restricted pore accessibility, and a corresponding decrease in specific surface area particularly with large organic groups. In the case of TiO₂ samples modified with alkyl or aryl groups they exhibited increased pore widths, ZrO₂ networks featuring dodecyl groups displayed larger pores. These findings emphasize the significant impact of the oxide network and the presence of large organic groups on the emission process. A comparative analysis with analogous SiO₂ systems provides further insight into material properties and future applications in luminescence, sensors and medical devices.

The structure-dependent unique host-guest chemistry of the bowl-shaped inorganic vanadium-oxygen cluster anion, [V₁₂O₃₂]^4– (V12), is reviewed. The half-spherically ordered square-pyramidal VO₅ units form the relatively positively charged concave inside. It stabilizes anionic moiety at the concave, even though the host itself possesses negative charge. Unusual anions such as nitroxyl anion, NO^–, and deprotonated nitromethane anion, CH₂NO₂^–, are also stabilized in V12. The guest-exchange, -removal and -inclusion of the V12 host are demonstrated. The removal of a guest causes a flip of one of the VO₅ pyramidal units, and the inclusion retrieves the structure. The incorporation of a bromine molecule induces the polarization of bromine molecule, and it provides brominated products of alkanes with unique selectivity. The lid effect of a cation above the concave controls the depth and orientation of a guest. An inert tetraethylammonium cation acts as a lid. Azide, N₃^–, is forced to be laid down in the concave with elliptically distorting the V12 host. The lid cation also affects the oxidation catalytic property of V12.

Water contaminants represent a significant global challenge that impacts the environment. The dispersal of production waste significantly impacts this problem. By in-situ polymerizing pyrrole on CoFe₂O₄ nanoparticles, a polypyrrole-coated cobalt ferrite (PPy@CoFe₂O₄) magnetic nanosorbent is synthesized to achieve effective removal of As(III). XRD data corroborated the findings of the SEM examination, which showed spherical nanoparticles with diameters of about 50 nm. Spinel ferrite production was suggested by the FTIR spectra, which showed clear peaks in the 400–600 cm^− 1 region, confirming the evidence of M–O bonds. The optimal removal of As(III) (99%) occurred at a pH of 6.0 to 7.0, with an adsorbent dosage of 40 mg. PPy/CoFe₂O₄ demonstrates a maximal monolayer adsorption capacity of 201.4 mg g^⁻1 under optimum conditions (330 K temperature, 40.0 mg adsorbent dose, and pH 6.0). Adsorption followed a pseudo-second-order kinetic model with an equilibrium time of 210 min. The adsorption isotherms were accurately represented by the Langmuir model. The removal efficiency was still higher than 94% following the five adsorption-desorption cycles. The adsorption of As(III) by PPy@CoFe₂O₄ is strongly influenced by pH of the medium. Electrostatic interaction is likely the main mechanism of As(III) adsorption onto PPy/CoFe₂O₄. The adsorption of As(III) onto PPy/CoFe₂O₄ takes place spontaneously, as indicated by a negative ΔG°. The results indicate that the PPy/CoFe₂O₄ composite functions as a highly efficient adsorbent, showcasing extensive applicability in the treatment of wastewater contaminated with heavy metal ions.

Recently, boron neutron capture therapy (BNCT) has attracted attention as a new cancer therapy. We have previously developed a fluorophenyl boronic acid-modified polyrotaxane (FPBA-PRX), as a novel supramolecular boron compund for BNCT. FPBA in FPBA-PRX binds to sialic acid, which is highly expressed on the surface of tumor cells, and functions not only as a tumor-targeting ligand but also as a boron compound because it has boron in the molecule. In this study, to enhance cancer-accumulating properties of FPBA-PRX, we prepared two targeting materials; namely, (1) polyethylene glycol-modified dopamine (PEG-Dopamine), which prevents FPBA-PRX from binding to sialic acid onto normal cells under normal tissue pH conditions, and (2) a folate-modified β-cyclodextrin (FA7-β-CyD), which is selectively taken up by cells with high expression of folate receptors (FR-α). As a result, FPBA in FPBA-PRX bound to PEG-Dopamine at pH 7.4, resulting in decreased uptake by sialic acid highly expressing cells, but dissociated PEG-Dopamine at pH 6.5 in tumor microenvironment, resulting in restored cellular uptake. FA7-β-CyD interacted with adamantane present at both ends of FPBA-PRX. In addition, FPBA-PRX/FA7-β-CyD was taken up into cells more efficiently than FPBA-PRX alone in FR-α-over expressing tumor cells. These results suggest that FPBA-PRX/PEG-Dopamine and FPBA-PRX/FA7-β-CyD have potential as boron compounds by improving the tumor selectivity of FPBA-PRX.

A water-soluble tetrasulfonatomethylcalix[4]resorcinarene[WSC4R]was synthesized using microwave irradiation, achieving high yields. The structural characterization of the synthesized macrocycle was performed through elemental analysis, Fourier-transform infrared (FT-IR) spectroscopy, proton nuclear magnetic resonance (¹H NMR), carbon-13 nuclear magnetic resonance (¹³C NMR), and electrospray ionization mass spectrometry (ESI-MS). The interactions of the macrocycle with various cationic surfactants—differing in hydrophobic tail length, polar head group composition, and counterion identity—were systematically investigated using turbidimetry, tensiometry, and dynamic light scattering (DLS). Furthermore, the antimicrobial activity of the compound was evaluated against bacterial strains, including Escherichia coli, Bacillus subtilis, Staphylococcus aureus, and Bacillus megaterium, to explore its potential biological applications.