Solvent Effect on the Volume of the Diels-Alder Reaction between Tetracyanoethylene and trans,trans-1,4-Diphenyl-1,3-butadiene

From the partial molar volumes of tetracyanoethylene, trans,trans-1,4-diphenyl-1,3-butadiene, and their Diels-Alder adduct, the volumes of the reaction in a series of solvents at 25°C (cm³ mol^{- 1}) were calculated: in dioxane, -26.4; in chloroform, -34.9; in ethyl acetate, -34.5; in acetonitrile, -4.4; in cyclohexanone, -34.0; in 1,2-dichloroethane, -31.8; in benzene, -26.9; in toluene, -24.5; in o-xylene, -21.1; and in mesitylene, -16.9. The solvent effects on the activation and reaction volumes and on the partial molar volumes of the reactants, activated complex, and adduct were discussed.     

Electrodynamic properties of lead Zirconate-Titanate thin films in the terahertz frequency range

The transmission/reflection spectra of bilayer structures consisting of thin amorphous and polycrystalline Pb(Zr_0.52Ti_0.48)O₃ ferroelectric films deposited on dielectric substrates of magnesium oxide MgO and sapphire α-Al₂O₃ were measured in the frequency range of 5–4000 cm^?1. Based on these spectra and using the dispersion analysis method, the spectra of complex dielectric permittivity ?*(ν) and dynamic conductivity σ′(ν) of the films were simulated, the electrodynamic parameters of the films were determined, and the dielectric dispersion responsible for the formation of static permittivity was found.     

Diels-Alder reaction volumes in the solid state and solution

The densities of anthracene, tetracyanoethylene, maleic anhydride, N-phenylmaleineimide, trans, trans-1,4-diphenylbuta-1,3-diene, and their Diels-Alder adducts were measured in the solid state and in solution at 25 °C. The reaction volumes in the solid state were calculated from the difference in molar volumes. They turned out to be low, close to each other (–4 to –11 cm³ mol^–1), and slightly different from the reaction volumes (–8±1 cm³ mol^–1) calculated from the van der Waals radii. The reaction volumes in solutions (–15 to –32 cm³ mol^–1) were found from the difference in partial molar volumes of the reactants in dioxane, acetonitrile, and 1,2-dichloroethane, The experimental Diels-Alder reaction volumes in solution are determined not only by the formation of new bonds in an adduct: a considerably higher contribution (to 75%) is made by a change in the volume of intermolecular empty spaces in solution on going from reactants to adducts.__________Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 11, pp. 2386–2390, November, 2004.     

Solvent Effect on the Activation Volume of the Diels-Alder Reaction Between Tetracyanoethylene and trans,trans-1,4-Diphenyl-1,3-butadiene

The effect of increased hydrostatic pressure on the rate of the Diels-Alder reaction of tetracyanoethylene with trans,trans-1,4-diphenyl-1,3-butadiene at 25°C was studied to estimate the reaction volume and to show that it considerably varies with -donor properties of the medium.     

Effect of Elevated External Pressure on the Rate of the Diels-Alder Reaction of 9-Methylanthracene with Acrylonitrile,Catalyzed by Gallium Chloride

External pressure was found to similarly affect the rate of a gallium chloride-catalyzed Diels-Alder reaction between 9-methylanthracene with acrylonitrile and a noncatalyzed reaction of 9,10-dimethylanthracene with acrylonitrile. The observation of equal activation volumes is consistent with the assumption that elevated pressure very weakly affects the bond energy in the n, complex of acrylonitrile with gallium chloride.     

Amine-Reactive BODIPY Dye: Spectral Properties and Application for Protein Labeling

A boron-dipyrromethene (BODIPY) derivative reactive towards amino groups of proteins (NHS-Ph-BODIPY) was synthesized. Spectroscopic and photophysical properties of amine-reactive NHS-Ph-BODIPY and its non-reactive precursor (COOH-Ph-BODIPY) in a number of organic solvents were investigated. Both fluorescent dyes were characterized by green absorption (521–532 nm) and fluorescence (538–552 nm) and medium molar absorption coefficients (46,500–118,500 M⁻¹·cm⁻¹) and fluorescence quantum yields (0.32 – 0.73). Solvent polarizability and dipolarity were found to play a crucial role in solvent effects on COOH-Ph-BODIPY and NHS-Ph-BODIPY absorption and emission bands maxima. Quantum-chemical calculations were used to show why solvent polarizability and dipolarity are important as well as to understand how the nature of the substituent affects spectroscopic properties of the fluorescent dyes. NHS-Ph-BODIPY was used for fluorescent labeling of a number of proteins. Conjugation of NHS-Ph-BODIPY with bovine serum albumin (BSA) resulted in bathochromic shifts of absorption and emission bands and noticeable fluorescence quenching (about 1.5 times). It was demonstrated that the sensitivity of BSA detection with NHS-Ph-BODIPY was up to eight times higher than with Coomassie brilliant blue while the sensitivity of PII-like protein PotN (PotN) detection with NHS-Ph-BODIPY and Coomassie brilliant blue was almost the same. On the basis of the molecular docking results, the most probable binding sites of NHS-Ph-BODIPY in BSA and PotN and the corresponding binding free energies were estimated.     

Activation and Reaction Volumes for [4+2] and [3+2] Additions Involving Maleic Anhydride

The partial molar volumes of reactants and products of the [3+2] addition of C-(p-nitrophenyl)-N-phenylnitrone to maleic anhydride and of the [4+2] addition of 9,10-dimethylanthracene to the same dienophile were determined, and the reaction volumes were calculated. A new method was suggested for determining the reaction volume. The activation volumes of both reactions were calculated from the dependences of the reaction rates on the external pressure. The volume parameters of the reactions involving the reagents of close size are close. The ratios of the activation volumes to the reaction volumes are unity, which suggests a common concerted mechanism of the reactions. Factors that could be responsible for significant changes in the absolute values of the reaction volume parameters are discussed.     

Crystal structure and thermal stability of ammonium adipate (NH4)2C6H8O4

Scientific-Research Institute of Chemical Reagents and Ultrapure Chemical Substances. Translated from Zhurnal Strukturnoi Khimii, Vol. 31, No. 6, pp. 123–127, November–December, 1990     

Effect of External Pressure and Solvent on the Equilibrium Constant of the Diels-Alder Reaction of 9-Chloroanthracene with Tetracyanoethylene

The effect of external pressure and solvent on the equilibrium constant of the Diels-Alder reaction of tetracyanoethylene with 9-chloroanthracene at 25°C was studied. The molar reaction volume is strongly solvent-dependent, cm³/mol: -11.3±1.0 in o-xylene, -14.9±1.0 in toluene, -20.6±1.5 in 1,2-dichloroethane, -22.6±1.5 in ethyl acetate, and -24.2±1.5 in acetonitrile.