Organophosphorus π-conjugated materials: the rise of a new field

The synthesis and electronic properties of new linear organic π-conjugated systems incorporating phosphole rings are described. Well defined α,α′-(phosphole-thiophene) oligomers possess low HOMO-LUMO gaps and their optical and electrochemical properties can be tuned via chemical modifications of the P-atoms. The physical properties of these compounds make them valuable materials for OLED’s. The coordination ability of phosphole-based dipoles has been exploited for the synthesis of efficient multipolar NLO-phores. Lastly, phospholes have been used for the synthesis of assemblies exhibiting through-bond interaction between two π-systems via P-P σ-skeletons.     

Variable Mott-Schottky plots acquisition by potentiodynamic electrochemical impedance spectroscopy

Potentiodynamic electrochemical impedance spectroscopy provides extraction of potential-dependent space charge layer capacitance from potentiodynamic impedance spectra of non-stationary semiconductor–electrolyte interface. The new technique has been applied for acquisition of Mott-Schottky plots of cathodically treated TiO₂ anodic films. Cathodic treatment in 1 M H₂SO₄ increases donor density and flat band potential of TiO₂. Freshly doped films show hysteresis in the space charge layer capacitance in cyclic potential scans. The subsequent cycling eliminates the hysteresis but preserves the greater part of the doping effect. Presented at the 4th Baltic Conference on Electrochemistry, Greifswald, 13–16 March 2005     

Ab initio calculations of vibronic activity in phosphorescence microwave double resonance spectra of p-dichlorobenzene

The phosphorescence spectrum of p-dichlorobenzene has been calculated using multiconfiguration self-consistent-field wave functions and the quadratic response technique. Attention has been paid to the intensity distribution of the singlet–triplet (³B_1u¹A_g) transition through a number of vibronic subbands. The second order spin–orbit coupling (SOC) contribution to the spin splitting of the ³B_1u (^3*) state is found to be almost negligible, and the calculations therefore provide a good estimate for the zero-field splitting (ZFS) parameters based only on the electron spin–spin coupling expectation values. Nuclear quadrupole resonance constants for the different Cl isotopes are also calculated to accomplish the ZFS assignment. The electric dipole activity of the spin sublevels in the triplet–singlet transitions to the ground-state vibrational levels is estimated by calculations of derivatives using distorted geometries which are shifted from the equilibrium position along different vibrational modes. A vibrational analysis of the phosphorescence spectrum, based on the SOC-induced mixing of the singlet and triplet states calculated along different vibrational modes, provides reasonable agreement with experimental data.Acknowledgment O. R.-P. would like to thank the European MOLPROP network for support. The authors thank Alexander Baev for fruitful discussions. This work was supported by the Swedish Royal Academy of Science (KVA).     

The binding of single-stranded DNA and PNA to single-walled carbon nanotubes probed by flow linear dichroism

The binding of single-stranded DNAs and a neutral DNA analogue (peptide nucleic acid, PNA) to single-walled carbon nanotubes in solution phase has been probed by absorbance spectroscopy and linear dichroism. The nanotubes are solubilised by aqueous sodium dodecyl sulfate, in which the nucleic acids also dissolve. The linear dichroism (LD) of the nanotubes, when subtracted from that due to the nanotubes/nucleic acid samples, gives the LD of the bound nucleic acid. The binding of the single-stranded DNA to the single-walled nanotubes is quite different from that previously observed for double-stranded DNA. It is likely that the nucleic acid bases lie flat on the nanotube surface with the backbone wrapping round the nanotube at an oblique angle in the region of 45 degrees . The net effect is like beads on a string. The base orientation with the single-stranded PNA is inverted with respect to that of the single-stranded DNA, as shown by their oppositely signed LD signals.     

Spectra of finite linear and unitary groups

The spectrum of a finite group is the set of its element orders. An arithmetic criterion determining whether a given natural number belongs to a spectrum of a given group is furnished for all finite special, projective general, and projective special linear and unitary groups. Supported by RFBR (grant Nos. 08-01-00322 and 06-01-39001) and by the Council for Grants (under RF President) and State Aid of Leading Scientific Schools (project NSh-344.2008.1). __________ Translated from Algebra i Logika, Vol. 47, No. 2, pp. 157–173, March–April, 2008.     

Estimation of a parameter of Morgenstern type bivariate exponential distribution by ranked set sampling

Ranked set sampling is applicable whenever ranking of a set of sampling units can be done easily by a judgement method or based on the measurement of an auxiliary variable on the units selected. In this work, we consider ranked set sampling, in which ranking of units are done based on measurements made on an easily and exactly measurable auxiliary variable X which is correlated with the study variable Y. We then estimate the mean of the study variate Y by the BLUE based on the measurements made on the units of the ranked set sampling regarding the study variable Y, when (X ,Y) follows a Morgenstern type bivariate exponential distribution. We then consider unbalanced multistage ranked set sampling and estimate the mean of the study variate Y by the BLUE based on the observations made on the units of multistage ranked set sample regarding the study variable Y. Efficiency comparison is also made on all estimators considered in this work.     

Manifold of nondegenerate affinor fields

We consider the quotient set of the set of nondegenerate affinor fields with respect to the action of the group of nowhere vanishing functions. This set is endowed with a structure of infinite-dimensional Lie group. On this Lie group, we construct an object of linear connection with respect to which all left-invariant vector fields are covariantly constant (the Cartan connection).     

Universal AC response of a 1D Luttinger liquid ring

The response of a spinless ballistic Luttinger liquid ring to an oscillating in time magnetic flux is considered in the discrete spectrum limit. The dependence of the magnitude of both AC response and the DC current on the frequency and magnitude of a magnetic flux at nonzero temperatures is calculated.     

A new general algorithmic method in reaction syntheses using linear algebra

We discuss here a new general linear algebraic method (both model and algorithm) for describing and generating (among others) minimal reactions and also minimal mechanisms in stoichiometry, or dimensionless groups in physics as well. (Further applications in process network syntheses will be discussed in .) With some minor modifications of the input this method can be extended for several related questions: for generating direct and overall reactions, direct (steady state) mechanisms, for finding the possible resulting (overall) reactions among all possible mechanisms, etc.Computational results in section 4 show the speed of our algorithm.We give also mathematical background and results in sections 3, 5 and 6. However, we do not restrict ourselves to mathematics only, we also talk on the language of chemistry, too.The theoretical results in sections 3.2, 3.3, 5 and the computational examples in section 4 are completely new, further theoretical results will appear in and in .