DFT study the interaction of β‐cyclodextrin with benzyl azide and phenyl acetylene in synthesis of 1,2,3‐triazoles

The phenyl acetylene and benzyl azide cycloaddition reaction in water in the presence of β‐cyclodextrin (β‐CD) as a phase transfer catalyst (PTC) can get a better yield in a shorter time. The interaction between β‐CD and phenyl acetylene or benzyl azide plays an important role in this reaction. This paper studies the complexes of β‐CD with phenyl acetylene and benzyl azide using density functional theory (DFT) method. In order to find out the orientations of guests in the cavity of β‐CD, binding energy and deformation energy are investigated, and the calculated results are confirmed by ¹H nuclear magnetic resonance (¹HNMR). The data from single point energy indicate that the inclusion complexes can improve the solubilities of phenyl acetylene and benzyl azide in water. The ¹³C and ¹⁵N spectra show that the most obvious variation concentrates on C₆ and C₈ of phenyl acetylene and N₁₅ of benzyl azide in complexes. Mulliken charge and frontier orbital are employed for revealing the charge distribution. The effect of β‐CD is discussed in terms of the calculated parameters. Copyright © 2014 John Wiley & Sons, Ltd.     

Interaction between β‐Cyclodextrin and Mixed Cationic‐Anionic Surfactants (2): Aggregation Behavior

The interactions between β‐cyclodextrin (β‐CD) and the mixtures of cationic‐anionic surfactants in the aqueous solution were investigated by surface tension, rheology, and dynamic light scattering measurements. It was shown that the key‐lock interactions between β‐CD and mixed cationic‐anionic surfactants were stronger than the electrostatic/hydrophobic interactions between cationic and anionic surfactants. The inclusion of β‐CD to surfactants could destroy the ion‐pair and aggregates of cationic‐anionic surfactants, and even inhibited the precipitation of the mixed cationic‐anionic surfactants. Furthermore, the inclusion of β‐CD to surfactants could also destroy the hydrogen bond between β‐CD molecules, inducing the disassociation of the aggregation formed by β‐CD themselves.     

Evaluation of SARs for the prediction of skin irritation/corrosion potential–structural inclusion rules in the BfR decision support system†

The German Federal Institute for Risk Assessment (BfR) has developed a Decision Support System (DSS) to assess certain hazardous properties of pure chemicals, including skin and eye irritation/corrosion. The BfR–DSS is a rule-based system that could be used for the regulatory classification of chemicals in the European Union. The system is based on the combined use of two predictive approaches: exclusion rules based on physicochemical cut-off values to identify chemicals that do not exhibit a certain hazard (e.g., skin irritation/corrosion), and inclusion rules based on structural alerts to identify chemicals that do show a particular toxic potential. The aim of the present study was to evaluate the structural inclusion rules implemented in the BfR–DSS for the prediction of skin irritation and corrosion. The following assessments were performed: (a) a confirmation of the structural rules by rederiving them from the original training set (1358 substances), and (b) an external validation by using a test set of 200 chemicals not used in the derivation of the rules. It was found as a result that the test data set did not match the training set relative to the inclusion of structural alerts associated with skin irritation/corrosion, albeit some skin irritants were in the test set.     

Macroscopic recognition of iodide by polymer appended calix[4]amidocrown resin

ABSTRACT

The current study reveals the synthesis of polymer appended Calix[4]amidocrown-5 with specific binding affinity for iodide at ppm-level. The low detection limits are observed via UV-vis and fluorescence spectroscopy. The time-dependent solution and solid-state ¹²⁷I NMR studies with 18.8 and 19 ppm shifts, indicate a strong sensing nature of resin towards iodide ion. A significant reduction in surface area and pore volume with higher thermostability of resin after iodide uptake indicated iodide inclusion in the amidocrown cavity. The mechanism of iodide sensing may be governed by noncovalent interactions of NH and OH protons present in amidocrown and phenyl ring as observed in terms of emission enhancement in fluorescence spectroscopy. The binding affinity and stoichiometric determinations are determined by Benesi-Hildebrand and Jobs plots, respectively.     

Interaction between tetramethylcucurbit[6]uril with α-furaldehyde-isonicotinyl-hydrazone hydrochloride

Interaction between tetramethylcucurbit[6]uril (TMeQ[6], host) and the hydrochloride salt of α-furaldehyde-isonicotinyl-hydrazone hydrochloride (FIHH⁺, guest) was investigated using X-ray crystallography and spectroscopic methods. X-ray crystallography showed that the π–π stacking effect and hydrogen bonding resulted in the formation of a dumbbell-shaped supramolecule which contained two FIHH⁺@TMeQ[6] host–guest inclusion complexes. The host–guest interaction provided identifiable changes in the vibrational frequencies in the IR spectra. ¹H NMR spectral analysis established a similar interaction model and revealed that TMeQ[6] preferred to include the furan moiety over the pyridine moiety of the FIHH⁺ guest molecule. Absorption spectrophotometric analysis suggested that the host and guest interact in a ratio of 1:1 with a stability constant K _s = (3.52 ± 0.74) × 10⁶ l mol^? 1.pH titration confirmed that the host–guest interaction led to a clear change in the protonation constant of the title guest. Quantum chemical calculations were used to determine the possible mechanism of formation of the dumbbell-shaped complex.     

Antibacterial,antioxidant and anthelmintic studies of inclusion complexes of some 4-arylidenamino-5-phenyl-4H-1,2,4-triazole-3-thiols

A series of 4-arylidenamino-5-phenyl-4H-1,2,4-triazole-3-thiols have been synthesised and their inclusion complexes have been prepared with β-cyclodextrin. The compounds and their inclusion complexes have been characterised by studying their physical and spectral properties. The thermodynamic stability constant and free energy of activation have been determined to know the stability of inclusion complexes. Finally, the compounds and their inclusion complexes are screened for antibacterial, antioxidant and anthelmintic activities. It is found that inclusion complexes of the newly synthesised compounds have appreciable stability and inclusion complex formation increases the antibacterial, antioxidant and anthelmintic activities significantly as compared to naked compound.     

Spectroscopic characterisation of the inclusion complexes between the antifungal drugs naftifine and terbinafine and cyclodextrins

The complexation of naftifine (NF) and terbinafine (TB) with cyclodextrins (CDs) has been investigated by UV/visible and ¹H NMR spectroscopy, ROESY techniques and also ESI-MS. Both drugs form 1:1 inclusion complexes with all the CDs tested except with α-CD, as deduced from the Benesi–Hildebrand plots and confirmed by ESI-MS and NMR spectroscopy (Job plot method). The K ₁₁ values for NF decrease in the order β-CD > methylated β-CD > 2-hydroxypropyl-β-CD >γ-CD. The determination of the enthalpy and entropy provides information about the main driving forces in the process. The stability constants of the complexes NF–β-CD, TB–β-CD and TB–γ-CD determined by ¹H NMR spectroscopy are in agreement with the values obtained by UV. For TB–β-CD, the value is higher, due to the fact that the length of the TB aliphatic chain allows a deeper inclusion of the naphthalene group inside the corresponding β-CD molecule, according to the 2D ROESY experiments.