STUDIES ON THYMINE AND URACIL TRIPLET EXCITED STATE IN ACETONITRILE AND WATER

Abstract— Thymine and uracil triplet-triplet absorption spectra and triplet excited state lifetimes have been observed in acetonitrile and water by nanosecond laser flash spectroscopy. A study of triplet energy transfer from these pyrimidines to retino! has also allowed an estimation of the triplet extinction coefficient ε_TT of thymine and uracil. These ε_TT were then used to determine the triplet quantum yields Ø_T of both pyrimidines in acetonitrile and water.     

Rearrangements in cobaltic fluoride fluorinations of cycloalkanes with seven or more ring carbons

Cyclo-heptane, -octane, -decane, -dodecane and -octadecane have been fluorinated in the vapour phase with cobaltic fluoride. The perfluorocarbons obtained revealed varying degrees of skeletal rearrangements. Thus, cycloheptane gave perfluoro-cycloheptane and -methylcyclohexane; cyclooctane gave at least eight fluorocarbons including-bicyclo(3,3,0)octane and -cyclooctane; cyclodecane gave a complex mixture from which were isolated perfluoro cis- and trans-bicyclo(4,4,0)decanes but no perfluorocyclodecane; cyclododecane and cyclooctadecane gave complex fluorocarbon mixtures in which none of the fluorocarbons with the original cycloalkene skeleton could be detected.Tetradecafluorobicyclo(3,3,0)octane gave dodecafluorobicyclo (3,3,0)oct-1(5)-ene and decafluorobicyclo(3,3,0)octa-di-1(5), 2-ene when pyrolysed over iron gauze.The fluorination of cyclooctane also afforded 1$\text{H}$-pentadecafluorocyclooctane which was dehydrofluorinated to tetradecafluorocyclooctene. This was converted to a range of derivatives including dodecafluorosuberic acid, 1,2-dichlorotetradecafluorocyclooctane, 1-methoxy tridecafluorocyclooctene and tetradecafluorocyclooctanone.     

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Contribution a l'électrochimie des thiols et disulfures : Partie I. Cystéine et cystine

A study of the electrochemical characteristics of cysteine and cystine was carried out by d.c., a.c. and differential pulse polarography. Up to three waves were observed depending on the concentration and pH. The waves of the two amino acids could be separated in a borate buffer of pH 9.2. Differential pulse polarography made it possible to determine as little 0.12 mg of cysteine and 0.24 mg of cystine per litre.     

The application of column redox-extraction chromatography to the separation of some actinide elements

The application of a new technique to the separation of some actinide elements by means of a single reducing and extracting column is described. Tri-n-octylphosphine oxide (TOPO) was used as the extractant. The following reducing agents were supported on microporous polyethylene together with TOPO: tetrachlorohydroquinone, 2,3-dichloro-1,4-naphthahydroquinone, 2,5-di-tert-butylhydroquinone and 2,5-di-tert-pentylhydroquinone. The last compound was chosen for the separation experiments; it allowed quantitative reduction of plutonium to Pu(III) and of neptunium to Np(IV). The separations Pu(III)-Np(IV), Pu(III)-U(VI) and Am(III)-Np(IV) in 6 M hydrochloric acid were obtained.     

A method for selection and use of numerical integration points for molecules with cylindrical symmetry

Boys and Handy [1] have discussed the solution of the bivariational equations with restricted numerical integration. One of the weaknesses of the method was that in the numerical summations over points, some points arose with r _ij= 0 and non-zero weights. This makes the method quite impractical for the Schrodinger Hamiltonian (because of the singularity at r _ij= 0), and it cannot be advantageous for the transcorrelated Hamiltonian C^–1HC because there will be some discontinuous higher derivatives at r _ij=0. Here it is shown how the symmetry of cylindrically symmetric molecules can be used to eliminate such points, without losing any of the advantages of the overall method, such as the convergence of the eigensolutions. It is also shown how the primary numerical integration points (z _i, r_i) may be chosen in any calculation such that each is associated with an equal amount of one-electron density. The choice of the angular coordinates are governed by the removal of the r _ij=0 points and maintaining the natural orthogonality between orbitals of different symmetry types. The method has been programmed and found to be practical, although no new molecular calculations have yet been performed. It is to be hoped that these points will give a basis for new transcorrelated calculations on diatomic molecules.This paper was presented during the session on numerical integration methods for molecules of the 1970 Quantum Theory Conference in Nottingham. It has been revised in the light of the interesting discussion which followed.     

Hydrogen bonded clusters of alcohol molecules in inert solvents: a chain statistics approach

A theory is proposed for modeling the autoassociation of alcohol molecules either in the neat liquid or in inert (non-complexing) solvents. This autoassociation by hydrogen bonds takes the form of clusters which can be predominantly open or cyclized chains, depending on the concentration. Chain conformation statistics are used for calculating the dipole moment of each type of chain. Cyclization equilibrium theory is employed for obtaining formulae for the fraction of all types of clusters. The total Kirkwood angular correlation factorg is calculated in function of the concentration. For this only two parameters are used; the first one is a common equilibrium constant for H bond dissociation; the second one is closely linked to the stiffness of the chains. A numerical illustration is presented for the case of normal hexanol in various aliphatic solvents, for which several dielectric data exist in the literature.