Astemizole/Cyclodextrin Inclusion Complexes: Phase Solubility, Physicochemical Characterization and Molecular Modeling Studies

Guest–host interaction of astemizole (Astm) with cyclodextrins (CDs) has been investigated using phase solubility diagrams (PSD), differential scanning calorimetry (DSC), X-ray powder diffractometry (XRPD), proton nuclear magnetic resonance (¹H-NMR) and molecular mechanical modeling (MM⁺). Estimates of the complex formation constant, K ₁₁, show that the tendency of Astm to complex with CDs follows the order: β-CD>HP-β-CD>γ-CD, α-CD. 1:1 Astm/β-CD complex formation at pH=5.0 was largely driven by the hydrophobic effect (desolvation), which was quantitatively estimated at −16.5 kJ⋅mol⁻¹, whereas specific interactions contribute only −5.3 kJ⋅mol⁻¹ to 1:1 complex stability (ΔG ₁₁^o=−22.7 kJ⋅mol⁻¹). The percentage contributions of the hydrophobic effect and specific interactions were therefore 73 and 27%, respectively. Both enthalpic and entropic factors contribute equally well (−11 kJ⋅mol⁻¹ each) to 1:1 Astm/β-CD complex stability. ¹H-NMR and MM⁺ molecular modeling studies indicate the formation of different isomeric 1:1 and 1:2 complexes. The dominant driving force for complexation is evidently van der Waals with very little electrostatic contribution. PSD, ¹H-NMR, DSC, XRPD and MM⁺ studies proved the formation of inclusion complexes in solution and the solid state.     

Photodegradation kinetics of poly(para-substituted styrene) in solution

The UV irradiation effects on stability of polystyrene, poly(4-methoxystyrene), poly(4-methylstyrene), poly(α-methylstyrene), poly(4-tert-butylstyrene), poly(4-chlorostyrene), and poly(4-bromostyrene) in dichloromethane, dichloromethane, tetrahydrofuran, and N,N-dimethylformamide solutions were studied in the presence of oxygen at different intervals of irradiation time. The photodegradation was studied at 293 K using fluorescence spectroscopy. Solutions of these polymers were accompanied by quenching of monomer and excimer emissions during the exposure of their solutions to UV light, and by a change in the structure of the fluorescence spectrum. Irradiation of poly(4-methylstyrene) and poly(α-methylstyrene) at excitation wavelength of 265 nm showed an increase of fluorescence intensity of a broad band, at longer wavelength without clear maxima. This may indicate that photodestruction of these polymers by irradiation with light of frequency absorbed by the polymer, may start from a random chain scission, with the possibility of formation of polyene and carbonyl compounds.     

A facile rearrangement of pyrroloindoline derivative to pyrroloquinoline: A new analogues of duocarmycins

Free‐radical generated at C‐7 position of indole derivative bearing N‐(3′‐chloroallyl) group prompted a regioselective intramolecular cyclization to furnish pyrroloindoline derivative, through the more favorable 5‐exo‐trig cyclization mode. The pyrroloindoline compound smoothly rearranged to pyrroloquinoline under mild conditions.     

Gas‐phase pyrolysis in organic synthesis: New route for synthesis of functionally substituted imidazoles

1,2,3‐Triazolylpropanone was prepared and coupled with aryldiazonium salts yielding the corresponding arylhydrazones. Gas‐phase pyrolysis of the hydrazono derivative produced N‐arylamino‐2‐acetylimidazole as well as 2‐acetylimidazole. The latter is the product of further pyrolysis of the former.     

The viscosity of the methanol-<Emphasis Type="Italic">n</Emphasis>-heptane system at low methanol concentrations

The kinematic viscosity of the methanol-n-heptane system was measured at various temperatures at low methanol concentrations (over the range of miscibility). The dynamic viscosities of this system at 298.15 K were calculated according to free volume theory taking into account molecular association. No anomaly (negative Δlnη values) was observed for the system.     

Synthesis of Pd(II) 1-alkylperimidine complexes as efficient catalysts for Suzuki reactions involving arylchlorides

Three palladium(II) complexes of the type [PdCl₂(PPh₃)L] (L—1-alkylperimidine) have been prepared by reactions of [PdCl₂(PPh₃)]₂ with 1-alkylperimidine. The complexes were characterized by conventional spectroscopic methods and elemental analyses. The incorporation of N-coordinated perimidine complexes of palladium(II) gave high catalytic activity in the Suzuki coupling deactivated aryl chloride substrates.From Koordinatsionnaya Khimiya, Vol. 31, No. 2, 2005, pp. 153–156. Original English Text Copyright © 2005 by Özdemir, Alýcý, Gürbüz, B. Çetinkaya, E. Çetinkaya.This article was submitted by the authors in English.     

<Superscript>1</Superscript>H NMR study of complexation of α- and β-cyclodextrins with some biologically active acids

Reactions of - and -cyclodextrins with some biologically active acids were studied by ¹H NMR spectroscopy. Inclusion complexes are found to be formed only with aromatic amino acids (phenylalanine and tryptophan) and ascorbic acid. The complexes of cyclodextrin with citric acid are obtained through interactions between the polar groups of the guest molecule and the OH groups of the host molecule located on the outside.Translated from Koordinatsionnaya Khimiya, Vol. 31, No. 3, 2005, pp. 234–236.Original Russian Text Copyright © 2005 by Terekhova, Kulikov, Kumeev, Nikiforov, Alper.This revised version was published online in April 2005 with a corrected cover date.This revised version was published online in April 2005 with a corrected cover date.     

Circuit elements at optical frequencies: nanoinductors, nanocapacitors, and nanoresistors

We present the concept of circuit nanoelements in the optical domain using plasmonic and nonplasmonic nanoparticles. Three basic circuit elements, i.e., nanoinductors, nanocapacitors, and nanoresistors, are discussed in terms of small nanostructures with different material properties. Coupled nanoscale circuits and parallel and series combinations are also envisioned, which may provide road maps for the synthesis of more complex circuits in the IR and visible bands. Ideas for the optical implementation of right-handed and left-handed nanotransmission lines are also forecasted.     

Combinatorial lemma and structure of a class of binary codes

A class of complete binary code systems is presented in which one of the symbols of the alphabet is used in any code combination not more than once, in terms of prefix codes of this class and of the operations of inversion and substitution of codes.Translated from Matematicheskie Zametki, Vol. 7, No. 3, pp. 325–331, March, 1970.In conclusion the author expresses his gratitude to G. Pollak who proposed to characterize the factorizations N by a system of calculus with a variable base, and to L. Redei who discussed the problems related to the factorization of finite sets.