Organosulphur compounds-XXXVIII Axial preference of a 2-dimethoxyphosphoryl substituent in 1,3,5-trithiane

¹H-NMR studies and X-ray analysis indicate that 2-dimethoxyphosphoryl-1,3,5-trithiane exists both in solution and in the crystal in a chair conformation with the dimethoxyphosphoryl group at C-2 being axial.     

Crystal structure of two oximes incis-pinane series

The structures of racemic 2-hydroxy-4-hydroxyiminopinan-3-one (1) and 3-hydroxyimino-cis-pinan-4-one monohydrate (2) have been determined by X-ray diffraction. The crystals of1 are monoclinic:P2₁/c, a=7.838(2),b=10.776(3),c=12.025(3) Å, =105.09(1)°,Z=4, room temp.; the crystals of2 are orthorhombic;P2₁2₁2₁,a=8.181(3),b=9.250(3),c=14.085(6)Å,Z=4, T=80K. Both structures were solved by direct methods, and refined toR=0.037 for 1920 reflections (1) and 0.032 for 1776 reflections (2). The absolute configuration of2 was not established. The hydroxyimine groups in both crystals and water molecules in2 participate in the network O–H...O of hydrogen bonds.     

The Boundary Harnack Principle for Non-Divergence form Elliptic Operators

If L is a uniformly elliptic operator in non-divergence form,the boundary Harnack principle for the ratio of positive L-harmonicfunctions holds in Hölder domains of order if > . A counterexample shows that is sharp. For Hölder domainsof order with (0,1], the boundary Harnack principle holds providedthe domain also satisfies a strong uniform regularity condition.     

An ‘odd’ formula for the volume of three-dimensional lattice polyhedra

Let be the tiling of R ³ with unit cubes whose vertices belong to the fundamental lattice L ₁ of points with integer coordinates. Denote by L _n the lattice consisting of all points x in R ³ such that nx belongs to L ₁. When the vertices of a polyhedron P in R ³ are restricted to lie in L ₁ then there is a formula which relates the volume of P to the numbers of all points of two lattices L ₁ and L _n lying in the interior and on the boundary of P. In the simplest case of the lattices L ₁ and L ₂ there are 27 points in each cube from whose relationships to the polyhedron P must be examined. In this note we present a new formula for the volume of lattice polyhedra in R ³ which involves only nine points in each cube of : one from L ₂ and eight belonging to L ₄. Another virtue of our formula is that it does not employ any additional parameters, such as the Euler characteristic.     

Transplanting maximal inequalities between Laguerre and Hankel multipliers

We supplement our previous paper [9] by adding a theorem that transplantsL ^p -norm maximal inequalities for Laguerre multipliers. As an immediate consequence we obtain negative results concerningL ^p -estimates of partial sum maximal operators for Laguerre expansions.Research supported in part by KBN grant No. 2 PO3A 030 09.     

PHOTOCHEMISTRY OF 2-MERCAPTOPYRIDINES. PART 3. EPR STUDY OF PHOTOPRODUCTION OF HYDROXYL RADICALS BY N-HYDROXYPYRIDINE-2-THIONE USING 5,5-DIMETHYL-1-PYRROLINE N-OXIDE IN AQUEOUS SOLUTIONS*

Abstract— N-Hydroxypyridine-2-thione, 2-S-PyrNOH, a potent antimicrobial, antifungal and anticancer agent, is photochemically active and upon UV irradiation generates free radicals. We have employed EPR and the spin-trap 5,5-dimethyl-l-pyrroline TV-oxide (DMPO) to investigate the photochemistry in aqueous solutions of 2-S-PyrNOH (used here in the form of a sodium salt, 2-S-PyrNONa). We found that upon photoactivation 2-S-PyrNONa can follow two different pathways: it can produce hydroxyl radicals and/or it can act as a photoreducing agent. The capacity of 2-S-PyrNONa to produce “OH” radicals has been demonstrated by: (1) EPR detection of the DMPO/OH adduct in UV-irradiated samples; (2) inhibition of the DMPO/OH formation by OH scavengers such as methyl alcohol, formate and DMSO and (3) by detection of EPR signals of DMPO adducts with radicals derived from reaction of OH with these inhibitors. The photoreductive capacity of 2-S-PyrNONa was deduced from the observation that the amplitude of the EPR signal of the spin adduct DMPO/OH decreased on UV irradiation in air-free pH 7.0 buffers and that the signal recovered in the dark and after aeration. The ability to generate free radicals upon UV irradiation suggests that 2-S-PyrNONa can be regarded as a potential photocytotoxic agent. This feature may be relevant to the biological action of this compound. Our findings also emphasize that caution should be used when 2-S-PyrNOH is employed as a source of OH radicals in biological or chemical systems.     

Nitromethane dimer potential energy surface studies

The interaction energy of several conformations of the nitromethane dimer is investigated at the SCF level. The dispersion energy and counterpoise correction are computed for certain relative orientations of the monomers. Fourth-order many body perturbation theory SDQ-MBPT(4) energies are reported for selected points. Double zeta and double zeta plus polarization basis sets were used. All calculations were done with the monomer fixed at the isolated monomer geometry. Interaction energies as large as 6 kcal/mol are found at minima of hydrogen bonding orientations.     

Intermolecular potentials based on symmetry-adapted perturbation theory with dispersion energies from time-dependent density-functional calculations

Recently, three of us have proposed a method [Phys. Rev. Lett. 91, 33201 (2003)] for an accurate calculation of the dispersion energy utilizing frequency-dependent density susceptibilities of monomers obtained from time-dependent density-functional theory (DFT). In the present paper, we report numerical calculations for the helium, neon, water, and carbon dioxide dimers and show that for a wide range of intermonomer separations, including the van der Waals and short-range repulsion regions, the method provides dispersion energies with accuracies comparable to those that can be achieved using the current most sophisticated wave-function methods. If the dispersion energy is combined with (i) the electrostatic and first-order exchange interaction energies as defined in symmetry-adapted perturbation theory (SAPT) but computed using monomer Kohn-Sham (KS) determinants, and (ii) the induction energy computed using the coupled KS static response theory, (iii) the exchange-induction and exchange-dispersion energies computed using KS orbitals and orbital energies, the resulting method, denoted by SAPT(DFT), produces very accurate total interaction potentials. For the helium dimer, the only system with nearly exact benchmark values, SAPT(DFT) reproduces the interaction energy to within about 2% at the minimum and to a similar accuracy for all other distances ranging from the strongly repulsive to the asymptotic region. For the remaining systems investigated by us, the quality of the SAPT(DFT) interaction energies is so high that these energies may actually be more accurate than the best available results obtained with wave-function techniques. At the same time, SAPT(DFT) is much more computationally efficient than any method previously used for calculating the dispersion and other interaction energy components at this level of accuracy.     

All-plastic, disposable, low detection limit ion-selective electrodes

A novel concept for all-plastic and all-solid-state ion-selective electrodes (ISEs) is introduced. Planar, flexible ion-selective electrodes, comprising only polymeric materials, with no internal solution, were obtained. The cast conducting polymer layer (obtained from aqueous suspension) was covered with a solvent polymeric based membrane to obtain a planar all-plastic sensor. The conducting polymer layer served both as electrical contact and as ion-to-electron transducer. To illustrate this concept, the conducting polymer poly(3,4-ethylenedioxythiophene) doped with poly(4-styrenesulfonate) ions (PEDOT-PSS, Baytron P) was chosen. Due to interaction, analyte cations-poly(4-styrenesulfonate) anions, an extended linear range of potentiometric responses was obtained, with lowered detection limit.As example, Ca²⁺-selective and K⁺-selective all-plastic electrodes were fabricated and yielded with high selectivity, near Nernstian slopes and fast responses. The detection limits obtained for Ca²⁺- and K⁺-selective sensors were 5 × 10⁻⁹ M CaCl₂ and 4.4 × 10⁻⁷ M KCl, respectively.The possibilities of modifying the conducting polymer-phase composition is highlighted. This method is extremely useful to tune the desired type of responses, and cannot be directly applied for electrochemically deposited conducting polymers.