Cyclopentadiene annulated polycyclic aromatic hydrocarbons: investigations of electron affinities

The adiabatic electron affinities of cyclopentadiene and 10 associated benzannelated derivatives have been predicted with both density functional and Hartree-Fock theory. These systems can also be regarded as benzenoid polycyclic aromatic hydrocarbons (PAHs) augmented with five-membered rings. Like the PAHs, the electron affinities of the present systems generally increase with the number of rings. To unequivocally bind an electron, cyclopentadiene must have at least two conventionally fused benzene rings. 1H-Benz[f]indene, a naphthalene-annulated cyclopentadiene, is predicted to have a zero-point energy corrected adiabatic electron affinity of 0.13 eV. Since the experimental E(A) of naphthalene is negative (-0.19 eV), the five-membered ring appendage contributes to the stability of the naphthalene-derived 1H-benz[f]indene radical anion significantly. The key to binding the electron is a contiguous sequence of fused benzenes, since fluorene, the isomer of 1H-benz[f]indene, with separated six-membered rings, has an electron affinity of -0.07 eV. Each additional benzene ring in the sequence fused to cyclopentadiene increases the electron affinity by 0.15-0.65 eV: the most reliable predictions are cyclopentadiene (-0.63 eV), indene (-0.49 eV), fluorene (-0.07 eV), 1H-benz[f]indene (0.13 eV), 1,2-benzofluorene (0.25 eV), 2,3-benzofluorene (0.26 eV), 12H-dibenzo[b,h]fluorene (0.65 eV), 13H-indeno[1,2-b]anthracene (0.82 eV), and 1H-cyclopenta[b]naphthacene (1.10 eV). In contrast, if the six-membered ring-fusion is across the C(2)-C(3) cyclopentadiene single bond, only a single benzene is needed to bind an electron. The theoretical electron affinity of the resulting molecule, isoindene, is 0.49 eV, and this increases to 1.22 eV for 2H-benz[f]indene. The degree of aromaticity is responsible for this behavior. While the radical anions are stabilized by conjugation, which increases with the size of the system, the regular indenes, like PAHs in general, suffer from the loss of aromatic stabilization in forming their radical anions. While indene is 21 kcal mol(-1) more stable than isoindene, the corresponding radical anion isomers have almost the same energy. Nucleus-independent chemical shift calculations show that the highly aromatic molecules lose almost all aromaticity when an extra electron is present. The radical anions of cyclopentadiene and all of its annulated derivatives have remarkably low C-H bond dissociation energies (only 18-34 kcal mol(-1) for the mono-, bi-, and tricyclics considered). Hydrogen atom loss leads to the restoration of aromaticity in the highly stabilized cyclopentadienyl anion congeners.     

Gamow-Teller beta decay of the very neutron-deficientN=50 nuclide98Cd

For the first time, detailed decay-spectroscopic investigations were performed for the very neutron-deficientN=50 nuclide⁹⁸Cd. The⁹⁸Cd activity was produced in spallation reactions between 600 MeV protons and a natural tin target, yielding a⁹⁸Cd beam intensity of 10 to 60 atoms/s at the collector of the ISOLDE massseparator. By means of-ray and conversion-electron spectroscopy, 19 transitions were found to follow the ⁺/EC decay⁹⁸Cd⁹⁸Ag. The transitions at 61 and 107 keV were shown to beM1(+E2) andE2, respectively, and the⁹⁸Cd half-life was measured as 9.2±0.3 s. TheQ _EC value of⁹⁸Cd is determined semiempirically and is compared to model predictions together with the measuredQ _EC values of the neighbouring cadmium isotopes^100,102Cd and theN=50 isotones⁹²Mo,⁹⁴Ru, and⁹⁶Pd, taken from the literature. The newly established decay scheme of⁹⁸Cd includes 9 excited states of⁹⁸Ag. Four states at 1691, 1861, 2164, and 2544 keV are directly fed by 0⁺ 1⁺ Gamow-Teller beta transitions with a summed strength of 3.5 _–0.7 ^+0.8 . This value corresponds to 25±5% of the strength predicted for the GT transformation of a g_9/2 proton (in⁹⁸Cd) into a g_7/2 neutron (in⁹⁸Ag) by the extreme single-particle shell model. The GT-strength splitting and quenching, observed for⁹⁸Cd, are compared with the corresponding data for lighter even-even N=50 isotones, and are discussed with reference to the predictions of more sophisticated nuclear models. We find that only in some cases it is possible to explain qualitatively the observed GT strength distribution and its total magnitude without renormalizing the free-neutron value of the axial-vector coupling constant.Dedicated to Prof. P. Armbruster on the occasion of his 60th birthday     

Oil-continuous microemulsions composed of hexane, water, and 2-propanol

On the basis of conductivity and centrifugation data and visual examination, ternary phase diagrams were prepared for systems composed of hexane, water, and 2-propanol. Certain ternary compositions were shown to be oil-continuous microemulsions, even though a soap or detergent was not present. Of a number of short-chain alcohols tested, only 2-propanol and 1-propanol could stabilize a microemulsified ternary solution. Addition of a small amount of hexadecyltrimethylammonium perchlorate to the ternary solutions produced only modest changes in the ternary phase diagram. However, in the presence of hexadecyltrimethylammonium salts, most short-chain alcohols containing less than eight carbons could stabilize an oil-continuous microemulsion.     

Metal-assisted in situ formation of a tridentate acetylacetone ligand for complexation of fac-Re(CO)3+ for radiopharmaceutical applications

Reaction of [NEt4]2[ReBr3(CO)3] with 2,4-pentanedione (acac) yields a complex of the type fac-Re(acac)(OH2)(CO)3 (1) under aqueous conditions. 1 was further reacted with a monodentate ligand (pyridine) to yield a fac-Re(acac)(pyridine)(CO)3 complex (2). Complex 1 was found to react with primary amines to generate a Schiff base (imine) in aqueous solutions. When a mixed-nitrogen donor bidentate ligand, 2-(2-aminoethyl)pyridine, that has different coordination affinities for fac-Re(acac)(OH2)(CO)3 was utilized, a unique tridentate ligand was formed in situ utilizing a metal-assisted Schiff base formation to yield a complex fac-Re(CO)3(3[(2-phenylethyl)imino]-2-pentanone) (3). Tridentate ligand formation was found to occur only with the Re-coordinated acac ligand. Reactions of acac with fac-Re(CO)3Br(2-(2-aminoethyl)pyridine) (4) or a mixture of [NEt4]2[ReBr3(CO)3], acac, and 2-(2-aminoethyl)pyridine did not yield the formation of complex 3 in water.     

Indium-based liquid clathrates. III. Inclusion compounds derived from [Bu4N][InCl3X] salts and their suitability as a catalysis medium

Tetrabutylammonium salts of the mixed haloindates, [Bu₄N][InCl₃X], X=Cl, Br, I, interact with aromatic solvents forming liquid inclusion compounds. The aromatic/cation ratio (A/C), a measure of the amount of guest aromatic, has been determined for a variety of simple aromatics. The values range from 2.6 to 0.4, substantially lower than the A/A of similar [Bu₄N][Al₂R₆X] liquid clathrates. The ability of these liquid clathrates to function as catalysis media has been explored. The solubility of (Ph₃P)₂Rh(CO)Cl and (Ph₃P)₃RhCl in the various clathrates was determined. It was found that significant leaching of the catalyst into the bulk aromatic solvent occurred, ranging from 13 to 94%. A related liquid clathrate, [Li·12-crown-4][InCl₄]·(C₆H₅CH₃)₂, had <1% of the dissolved catalyst leached.     

Itô correction terms for the radial parts of semimartingales on manifolds

Summary We consider functions,F, of a semimartingale,X, on a complete manifold which fail to beC ² only on, and are sufficiently well-behaved near, a codimension 1 subset . We obtain an extension of the Itô formula which is valid for all time by adding a continuous predictable process given explicitly in terms of two geometric local times ofX on and the Gâteaux derivative ofF. We then examine the cut locus of a point of the manifold in sufficient detail to show that this result applies to give a corresponding expression for the radial part of the semimartingale.     

Some Consequences of the Nature of the Distance Function on the Cut Locus in a Riemannian Manifold

We render the cut locus more accessible to analysis by showingthat each non-conjugate cut point has a neighbourhood on whichthe distance function is the minimum of finitely many smooth‘radial functions’. This enables us to generaliseto an arbitrary complete manifold a number of recent results,mainly from stochastic analysis, which were either limited ornot valid on the cut locus because of the lack of differentiabilitythere of the distance function.     

Semimartingales and geometric inequalities on manifolds

The purpose of this paper is twofold. First, we use resultson Jacobi fields to study the stochastic differential equations(SDEs) for exp_Xt( exp_Xt^-1(Y_t)) with specially constructed coupledsemimartingales X and Y on a complete, simply connected Riemannianmanifold M with constant sectional curvature. Secondly, we applythese SDEs to obtain an analogue for M of a result of Borellconcerning an inequality relating the solutions of the parabolicequation / t = 1/2 – h, with Dirichlet boundary condition,on three convex sets in Euclidean space. From the latter, therefollows an inequality involving the first eigenvalues of theLaplacian on those convex sets with the Dirichlet boundary condition,analogous to an inequality in Euclidean space which is equivalentto the Brunn–Minkowski inequality of these eigenvaluesobtained by Brascamp and Lieb.     

Stability-indicating RP-LC method for the determination of vildagliptin and mass spectrometry detection for a main degradation product

A simple, precise and stability-indicating reversed-phase liquid chromatography method was developed and validated for the determination of vildagliptin (VLG) in pharmaceutical dosage form. The chromatographic separation was obtained within 6 min and was linear in the range of 20-80 μg/mL (r(2) = 0.9999). Limit of detection and limit of quantitation were 0.63 and 2.82 μg/mL, respectively. The method was validated in accordance with International Conference on Harmonization acceptance criteria for specificity, linearity, precision, accuracy, robustness and system suitability. Stress studies were carried out and no interference of the degradation products was observed. The excipients did not interfere in the determination of VLG. Furthermore, the main degradation product obtained from the stress studies (thermal, oxidative and alkaline hydrolysis) was evaluated for mass spectrometry and its molecular structure was predicted. The proposed method was successfully applied for the quantitative analysis of VLG in tablet dosage form, which will help to improve quality control and contribute to stability studies of pharmaceutical tablets containing this drug.