The photophysics of 7H-adenine: A quantum chemical investigation including spin–orbit effects

Vertical and adiabatic electronic spectra have been investigated by means of combined density functional and multi-reference configuration interaction methods. Spin–orbit coupling has been determined employing a non-empirical spin–orbit mean-field operator. In the vertical absorption spectrum of isolated 7H-adenine, the transitions to the lowest ¹ state, the optically bright ¹ state, and a so far unknown ¹(π_H → (Ryd, σ^*)) state are predicted to lie very close to each other. The strong ¹ transition at 4.8 eV is the lowest excitation of ¹(π → π^*) type in 7H-adenine. It is red shifted by about 0.3 eV with respect to the corresponding excitation in the 9H-tautomer. We find the global minimum on the S₁ potential energy hypersurface at about 4.2 eV for a ¹ electronic structure. A potential well with a minimum at 4.3 eV exhibits mixed ¹ character. A planar ¹ structure with a potential energy of 4.6 eV constitutes a stationary point on the S₁ surface. At the present stage it is unclear whether it corresponds to a minimum or a saddle-point. The lowest-lying ¹(π → (Ryd, σ^*)) state is metastable with respect to N₇–H₁₄ bond dissociation. Its inner (Rydberg) potential well with an adiabatic excitation energy of 4.6 eV represents another minimum on the S₁ PEH. From the theoretical results presented in this work, we conclude that isolated 7H-adenine will be able to emit photons for excitation energies below 4.7 eV(264 nm). Above this threshold singlet excited 7H-adenine can undergo ultrafast non-radiative relaxation to the electronic ground state, either by hydrogen detachment via the ¹(π → (Ryd, σ^*)) channel or via a conical intersection of the ¹ state along a ring puckering mode. The ³ T₁ state can be efficiently populated via intersystem crossing from one of the S₁ potential energy wells. Large-amplitude motions in the T₁ state along an out-of-plane distortional coordinate lead to significant configuration interaction of the ¹ and ¹ structures which lend intensity to the phosphorescence.     

A fast liquid chromatographic tandem mass spectrometric method for the simultaneous determination of total homocysteine and methylmalonic acid

A liquid chromatography(LC)/electrospray ionization tandem mass spectrometry (MS) method for the quantitative determination of total homocysteine and methylmalonic acid and the monitoring of methionine, homocystine and succinic acid in plasma has been developed. The analytes are determined under the presence of the deuterated internal standards methylmalonic acid-d ₃ and homocystine-d ₈. Although methylmalonic acid can be determined directly, a reduction step has to be carried out to ensure the measurement of total homocysteine. Ultrafiltration was applied afterwards to deproteinize the samples prior to LC/MS injection. LC/MS analysis is carried out isocratically using a mobile phase consisting of 5% methanol and 95% of a 0.06 M formic acid solution on a reversed-phase C18 column at a flow rate of 0.5 mL/min. The MS measurement was separated into several periods: homocysteine, homocystine and methionine were determined in the positive-ion mode, whereas the determinations of methylmalonic acid and succinic acid were carried out in the negative-ion mode. The intraday coefficients of variation (CVs) were 2.9% or less and 3.2% or less for homocysteine and methylmalonic acid, respectively. Interday CVs ranged from 3.8 to 5.9% for homocysteine and from 3.5 to 6.3% for methylmalonic acid. Analyte concentrations could reliably be determined, also far below the reference values. Furthermore, the linearity was determined and a correlation study with respect to the existing homocysteine and methylmalonic acid methods at Medisch Spectrum Twente Hospital was carried out.     

Expanding the registry of aromatic amide foldamers: folding, photochemistry and assembly using diaza-anthracene units

The synthesis of various 1,8-diaza-4,5-dialkoxy-2,7-anthracene dicarboxylic acid derivatives and their incorporation into cyclic and helically folded aromatic oligoamides are reported. The ability of the diaza-anthracene monomers to undergo photoaddition or head-to-tail photodimerization was investigated in the solid state and in solution. Quantitative conversion of a monomer diester to the corresponding head-to-tail photodimer could be achieved in the solid state without protection from oxygen. The formation of an emissive excimer between two diaza-anthracene units appended at the end of a helically folded oligomer was demonstrated. Intramolecular photodimerization was not observed in this compound, possibly due to the low thermal stability of the head-to-head photoadduct. A cyclic oligoamide composed of two diaza-anthracene and two pyridine units was shown to adopt a flat conformation and to form columnar stacks in the solid state. Longer, noncyclic oligoamides composed of one or two diaza-anthracene units were shown to adopt helical conformations that exist preferentially as double helical dimers.     

Quantum chemical investigation of hydrogen-bond strengths and partition into donor and acceptor contributions

We present a simple increment model for use in the rapid scoring of hydrogen bond strengths employing 15 chemically diverse donor and 28 acceptor terms. The increments cover a large variety of hydrogen bond donor and acceptor groups and are more specific than SYBYL atom types. The increments have been fitted to quantum chemical ab initio interaction energies of 81 small hydrogen‐bonded complexes determined at the level of second‐order Møller‐Plesset perturbation theory (MP2). The complexes have been chosen such as to represent the most important types of donor‐acceptor pairs found in biological systems. Sulphur is found to be a strong hydrogen bond acceptor while its donor capacities are weak. By taking CH acidic H donors into account, a linear correlation between MP2 energies and the increment model with a coefficient of correlation of r² = 0.994 has been accomplished. The transferability of the fitted parameters has been assessed on a second set of complexes including larger molecules of biological relevance. Very good agreement has been achieved for noncyclic hydrogen bonds. Cooperative effects are not accounted for by the current increment model. For this reason, binding energies of strong cyclic hydrogen bonds, as e.g. present in DNA base pairs, are underestimated by about 30–40%. © 2007 Wiley Periodicals, Inc. J Comput Chem, 2007     

A Note on Malliavin Fractional Smoothness for Lévy Processes and Approximation

Assume a Lévy process (X _t ) _t?∈?[0,1] that is an L ₂-martingale and let Y be either its stochastic exponential or X itself. For certain integrands φ we investigate the behavior of $$ \bigg \|\int_{(0,1]} {{\varphi}}_t dX_t - \sum_{k=1}^N v_{k-1} (Y_{t_k}-Y_{t_{k-1}}) \bigg \|_{L_2}, $$ where v _k???1 is ${\mathcal{F}}_{t_{k-1}}$ -measurable, in dependence on the fractional smoothness in the Malliavin sense of $\int_{(0,1]} {{\varphi}}_t dX_t$ . A typical situation where these techniques apply occurs if the stochastic integral is obtained by the Galtchouk–Kunita–Watanabe decomposition of some f(X ₁). Moreover, using the example f(X ₁)?=?1_(K,?∞?)(X ₁) we show how fractional smoothness depends on the distribution of the Lévy process.     

Energy contracts management by stochastic programming techniques

We consider the problem of optimal management of energy contracts, with bounds on the local (time step) amounts and global (whole period) amounts to be traded, integer constraint on the decision variables and uncertainty on prices only. After building a finite state Markov chain by using vectorial quantization tree method, we rely on the stochastic dual dynamic programming (SDDP) method to solve the continuous relaxation of this stochastic optimization problem. An heuristic for computing sub optimal solutions to the integer optimization problem, based on the Bellman values of the continuous relaxation, is provided. Combining the previous techniques, we are able to deal with high-dimensional state variables problems. Numerical tests applied to realistic energy markets problems have been performed.     

Über den regulären Ort bei japanischen lokalen Ringen

In connection with the still unsolved problem: “Is the powerseries ring A?T? over an excellent ring A excellent again?” the following question arises: “Under which assumptions is the regular locus of an universal japanese ring open?” In this paper we give conditions for the openess of regular locus for a special class of universal japanese rings.     

Molecular structures of phosphorus compounds: Part VIII. Electron diffraction study of phenyltetrafluorophosphorane

The molecular structure of phenyltetrafluorophosphorane is determined in the gas phase using electron diffraction. The following geometric parameters (r_g values) are obtained: P-F_ax = 1.616(4) a, P-F_eq = 1.531(4) a, P-C = 1.796(9) a, C-C = 1.396(3) a, ∠F_eqPF_eq = 115.6(1.4)°, ∠F_axPC = 93.0(0.5)°, τ = 72.9(3.6)°. τ is the dihedral angle between the phenyl group and the equatorial plane of the PF₄ group. These results are compared to the molecular structures of methyl-and ethynyltetrafluorophosphorane.