Selective and sensitive analysis of 1-nitropyrene in diesel exhaust particulate extract by multidimensional HPLC

Summary A multicolumn (MC) HPLC method for the determination of 1-nitropyrene (1-NP) at trace-levels via on-line reduction to 1-aminopyrene and fluorescence detection is presented. On the first column, packed with a pyrenebutyric acid amide stationary phase, the nitro-derivatives of PAHs are strongly retained and separated from other matrix components. The nitro-PAHs-containing fractions are transferred onto a RP₁₈-column via stepwise gradient elution and finally separated according to their various lipophilicities and sizes. To increase the overall selectivity and sensitivity of the multidimensional method (MD-HPLC system) post-column, on-line reduction of the nitro-PAHs to the respective amino-PAHs via a short catalysis column is performed thus enhancing the sensitivity significantly (to low pg levels). The applicability of this method for the determination of trace amounts of 1-NP in real samples (diesel particulate extracts) is demonstrated.     

Some peculiarities of π—π interactions between tetraphenylporphine metal complexes and aromatic solvents

The — complexes of metal tetraphenylporphinates with benzene, toluene, and xylenes were characterized by means of thermogravimetry. The ability of metalloporphyrins to form — complexes with certain -donor molecules depends largely on the -acceptor capacity of the macroheterocycle, and on the peculiarities of the metal—porphyrin coordinative linkage. Stoichiometry, energy parameters, and thermal stability of the - complexes of metalloporphyrins with various aromatic ligands are determined to a great extent by the molecular structure of solvents.Translated fromIzyestiya Akademii Nauk. Seriya Khimicheskaya, No. 5, pp.850–853, May, 1993.     

Solvent effects in electronically excited states using the continuum solvation model COSMO in combination with multireference configuration interaction with singles and doubles (MR-CISD)

An implementation of the COSMO continuum solvation model into the MCSCF and MR-CISD programs of the COLUMBUS program system is reported. Equilibrium solvation and non-equilibrium solvation models for the treatment of electronic excitations have been used. Solvatochromic effects have been computed for a representative set of n-* and -* states of formaldehyde, acrolein and pyrazine using several solvents ranging from some with apolar character to water. Agreement with experimental shifts is good within the limits of a continuum model.Contribution to the Jacopo Tomasi Honorary Issue     

Complexation of Paraquat Dication with Disodium 1,8-Disulfonato-3,4,5,6-Acridinetetracarboxylic Acid in Water

Disodium 1,8-disulfonato-3,4,5,6-acridinetetracarboxylic acidforms a complex of 1 : 1 stoichiometry with paraquatdication in water. The stability constant of thecomplex is 1.2 × 10⁴ M^-1 at 25 °C.     

Isomerization of (Het)arylbenzoins in Basic Media

The isomerization of the hetaryl analogs of unsymmetrical benzoins on heating in basic media is a convenient preparative method for the production of -hydroxyacyl derivatives of -excessive heterocycles. The motivating force here for the isomerization is the formation of a thermodynamically more stable product. It was established that isomerization is promoted by increase in the difference between the electron-donating characteristics of the (het)aryl residues     

Chemical interactions between 2-mercaptobenzazoles and π-acceptors

Summary 2-Mercaptobenzazoles (1a–c) interact with several -acceptors such as tetracyanoethylene (TCNE) 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ), 2,3,5,6-tetrachloro-1,4-benzoquinone (CHL) dicyanomethyleneindane-1,3-dione (CNIND), 2,3-dicyano-1,4-naphthoquinone (DCNQ), 9-dicyanomethylene-2,4,7-trinitrofluorene (DTF), and 2,3-dichloro-1,4-naphthoquinone (DCHNQ)via the formation of charge-transfer (CT) complexes to yield various heterocyclic compounds.

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Chemische Wechselwirkungen zwischen 2-Mercaptobenzazolen und -Akzeptoren

Zusammenfassung Die 2-Mercaptobenzazole1a–c reagieren mit verschiedenen -Akzeptoren wie Tetracyanoethylen (TCNE), 2,3-Dichlor-5,6-dicyano-1,4-benzochinon (DDQ), 2,3,5,6-Tetrachlor-1,4-benzochinon (CHL), Dicyanomethylenindan-1,3-dion (CNIND), 2,3-Dicyano-1,4-naphthochinon (DCNQ), 9-Dicyanomethylen-2,4,7-trinitrofluoren (DTF) und 2,3-Dichlor-1,4-naphthochinon (DCHNQ) unter Ausbildung von charge transfer — Komplexen (CT) zu heterocyclischen Verbindungen.

     

Charge control of phenol complexation with unsaturated compounds containing organosilicon substituents. Thiophene derivatives

The frequency shifts of the O-H stretching modes and the resonance components _R of these shifts in the IR spectra of H-complexes of phenol with thiophene derivatives having organic and organosilicon substituents have been analyzed. Relationship of and _R parameters to values calculated by nonempirical methods that characterize the electronic effect of organic substituents on the effective charges of the thiophene ring atoms has been established. It has been shown that in the complexation of phenol (hard acid) with thiophene derivatives charge control prevails over frontier orbital control. The changes in the effective charges of the thiophene ring atoms due to the effect of organosilicon substituents have been calculated.For the previous publication of this series see Ref. 1.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 12, pp. 2163–2168, December, 1994.This work was supported by the Russian Foundation for Basic Research, Project No. 93-03-18725.     

Matrix effect on the retention in reversed-phase liquid chromatography

Summary A polymer-based, reversed-phase column (VA-C18), prepared by grafting octadecyl chain onto vinyl alcohol copolymer gel, was investigated for its chromatographic characteristics. n-Alkanes and n-alkyl alcohols were found to be retained only by hydrophobic interaction between the solutes and the octadecyl chain. In the case of aromatic hydrocarbons, in addition to the hydrophobic interaction, - interaction between the solutes and the based material was elucidated to contribute to the retention. For aromatic tertiary amines which are known to strongly interact with the residual silanol group of the silica-based reversed-phase columns to produce broadened and skewed peakes, the VA-C18 column also retained these substrates strongly by the combination of hydrophobic, -, and ionic interactions. In this case, however, symmetrical peaks were observed. From these results, it was determined that in the case of VA-C18, the base material was found not to produce undesirable effect although the solutes interact with the base. Further conclusion obtained was that in reversed phase liquid chromatography, chromatographic properties of base matrix is highly responsible for the overall retention.     

Calculation of some electronic excited states of formaldehyde

The optimized MO's of several excited states of formaldehyde have been calculated by means of a large basis set of modified Gaussian functions; particular attention has been paid to the * transition. The total energy of the various states has been obtained as the sum of the SCF and correlation energies; the last one has been calculated as a functional of the electronic density. The calculated values for the transition energies are in good agreement with the experiment. A strong interaction of the * state with the continuum is evidentiated; this fact can justify the absence of the * band in the absorption spectrum.     

On the Distribution of π-Electrons into Rings of Conjugated Hydrocarbons Containing a Linear Polyacene Fragment

Summary. A method for assessing the -electron contents (EC) of rings of benzenoid hydrocarbons, based on the examination of their Kekulé structures, was recently put forward by Balaban and Randi. We now show that all hexagons belonging to a linear polyacene fragment of a conjugated hydrocarbon (not necessarily benzenoid) have mutually equal EC-values.     

Transition Metal Halide Salts of 1,3-bis(4-Pyridyl)propane: Synthesis and Structural Characterization

The resulting salts of (H₂bpp)MX₄ · n H₂O (M = Zn, X = Cl, n = 1, 1; M = Cd, X = Br, n = 0, 2; M = Hg, X = Cl, n = 1, 3; M = Cu, X = Cl, n = 0, 4; M = Cu, X = Br, n = 1, 5; M = Pt, X = Cl, n = 1, 6) were crystallized from the reaction mixture prepared by adding MX₂ to the HX solution of 1,3-bis(4-pyridyl)propane (bpp), while the salt of colorless (H₂bpp)SnCl₆, 7, was crystallized from the reaction mixture prepared by adding SnCl₂ to the HCl solution of bpp. Their structures have been determined by X-ray crystallography. All the compounds show supramolecular structures in the solid state by intermolecular hydrogen bondings and aromatic – interactions. The H₂bpp²⁺ cations in these metal salts adopt the gauche–gauche and anti–anti conformations with different dihedral angles for the two pyridyl rings.     

Konformationen diastereoisomererBis-(alkylaryl)-ether

Summary X-ray-analysis of the meso-ether2 showed the existence of two bridged species in the unit cell besides the expected molecule. The additional bonds between the 9- and 10-positions of the anthracene moieties were extraordinarily long. This fact leads to conclusions on the reactive behaviour of alkylaryl carbinoles upon acid-catalysed etherification.

     

Molecular Orbital Calculations on the Electronic Structures of Some Arylhydrazones

The geometry and electronic structure of the parent formaldehyde hydrazone and some ethylcyanoacetate phenylhydrazones (ECPHs) are studied at the semiempirical level of MO theory using the AM1 method. The effect of substitution on the geometry of the hydrazone moiety is investigated. The optimized geometry of formaldehyde hydrazone is nonplanar while in the ECPHs the planarity of the hydrazone group and its coplanarity with the phenyl ring increase in the direction of the electron-attracting ability of the para substituent. This has been attributed to an increase in the p– conjugation between the lone pair of electrons on the amine nitrogen and the phenyl ring. Variations of ionization potentials and bond orders with the Hammett constant, _p , are examined and straight-line relationships are obtained. The results are correlated with the observed variations in the experimentally measured electrical conductivities of the studied compounds.     

Complexation of monosubstituted benzenes and methanes by cyclotetrachromotropylene in aqueous solution: Substituent effects on π-π and Ch-π interactions

The stability constantsK of 11 complexes formed in aqueous solution between several monosubstituted benzenes (C₆H₅X) and methanes (CH₃X) as guests and cyclotetrachromotropylene as host were determined by proton NMR spectroscopy. Variations ofK with the substituent X are attributed to the electronic effect of X and the presence of C–H or aromatic bonds, if any, interacting with the host bonds.     

Conformational rigidity and flexibility of the paracyclophane skeleton in substituted [2.2]paracyclophanes

The character of distortions of the paracyclophane skeleton in various substituted [2.2]paracyclophanes was analyzed based on X ray diffraction data. The rigidity of the skeleton is provided by ethylene bridges and flexibility of the benzene rings, which adopt a boat conformation. The flexibility of the skeleton is manifested in the displacement of the benzene rings with respect to each other and conformational changes of ethylene bridges. The changes in these characteristics are very sensitive to intra- and intermolecular steric factors and are indicative of the absence of strong specific stacking interactions between the be nzene rings. Precision X-ray diffraction study and quantum-chemical calculations for unsubstituted [2.2]paracyclophane and 4,7-benzoquinono[2.2]paracyclophane demonstrated that there are no attractive interactions between the benzene rings, and the electron density is localized predominantly on the outer surface of the rings. This fact can be considered as the cage molecular effect of the [2.2]paracyclophane skeleton.Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 1707–1732, September, 2004.     

Volumetric studies on the binary mixtures of furan with some aromatic hydrocarbons

Molar excess volumes of mixing for the binary mixtures of furan with benzene, toluene, ethylbenzene, o-, m-, and p-xylenes have been calculated from the precise experimental density data at 25°C over the entire composition range. The results have been discussed in terms of molecular interactions and geometric effects in the binary mixtures.     

Calculations on the π→1π* transitions in large conjugated carbonyl compounds using the molecules-in-molecules method

Assignments of the ^1* electronic transitions in large carbonyl compounds have been carried out using the molecules-in-molecules method.     

Quantum-chemical study of allylic compounds with two bonded heavy atoms

It has been shown by the CNDO method that the bathochromic shift of the long-wave absorption band in the transition from allylstannane to compounds of the type C=C-C-Sn-X and C=C-Sn-X (where X is a heavy atom) is connected with the formation of a low-energy vacant *_S-X orbital, localized mainly in the region of the Sn-X chemical bond, and of an occupied _Sn-X orbital, the energy of which is somewhat higher than of the _C-Sn orbital. The dependence of the position of the long-wave absorbance region on conformation is related to the fact that, in planar and nonplanar conformers, the long-wave transitions are of a different type ( * and *, respectively); the bathochromic shift is determined to a large degree by the difference in the energies of the highest occupied MO ( - ) in the s-trans form. In the nonplanar conformers the heavy atom orbitals interact with the -orbital of the ethylene moiety through the bridge group; this leads to a significant delocalization of the HOMO and to a considerable change in its energy. On the other hand, their interaction with the *-orbital in compounds of the C=C-C-Sn-X type is very low and does not favor the delocalization of lower vacant MO. In vinyldistannane the *-orbital is noticeably delocalized, due to the interaction with the *_Sn-Sn orbital in planar and with the *_Sn-Sn orbital in nonplanar conformers.N. D. Zelinskii Institute of Organic Chemistry, Russian Academy of Sciences, 117913 Moscow. Translated from Izvestiya Akademii Nauk, Seriya Khimicheskaya, No. 3, pp. 636–641, March, 1992.     

Synthese von α-Methyl-homocysteinthiolacton

Summary A facile high yield large scale methylation procedure affording2c is reported utilizing the N-[bis(methylthio)-methylen-protected derivative4a as an intermediate. The optical resolution of racemic2c is described leading to (S)-2b. In addition the thiolactone2c undergoes oxidative ring opening by bromine to the corresponding sulphonic acid5.