Tetra-2,3-pyrazinoporphyrazines with externally appended pyridine rings. 3. A new highly electron-deficient octacationic macrocycle: tetrakis-2,3-[5,6-di{2-(N-methyl)pyridiniumyl}pyrazino]porphyrazine, [(2-Mepy)8TPyzPzH(2)]8+

A new octacationic macrocycle, tetrakis-2,3-[5,6-di{2-(N-methyl)pyridiniumyl}pyrazino]porphyrazine, was obtained in its hydrated form as the water-soluble iodide salt. This compound, abbreviated as [(2-Mepy)(8)TPyzPzH(2)](I(8)).8H(2)O (2-Mepy = 2(N-methyl)pyridiniumyl moiety), was obtained by demetalation of the corresponding Mg(II) complex, [(2-Mepy)(8)TPyzPzMg(H(2)O)](I(8)).5H(2)O, which in turn was prepared from its corresponding neutral hydrated species tetrakis-2,3-[5,6-di(2-pyridyl)pyrazino]porphyrazinato(monoaquo)magnesium(II), [Py(8)TPyzPzMg(H(2)O)].4H(2)O, by reaction with CH(3)I in N,N-dimethylformamide. The quaternization reactions by using CH(3)I or methyl p-toluenesulfonate were also conducted on the monomeric precursor 2,3-dicyano-5,6-di(2-pyridyl)-1,4-pyrazine, [(CN)(2)Py(2)Pyz], with formation of the monoquaternized ion [(CN)(2)Py(2-Mepy)Pyz](+) neutralized by iodide and p-toluenesulfonate anions. Single-crystal X-ray work allowed elucidation of the structure of the two salt-like species. The diquaternized ion [(CN)(2)(2-Mepy)(2)Pyz](2+) could also be obtained as a p-toluenesulfonate salt, but attempts at direct macrocyclization of this dicationic species were unsuccessful. The iodide salt [(2-Mepy)(8)TPyzPzH(2)](I(8)).8H(2)O is water-soluble, with different solubilities depending on the range of pH explored. It was established that the macrocycle [(2-Mepy)(8)TPyzPzH(2)](8+) undergoes facile deprotonation and behaves as a strong acid. Aggregation phenomena are observed for both the octacation [(2-Mepy)(8)TPyzPzH(2)](8+) and its corresponding centrally deprotonated species [(2-Mepy)(8)TPyzPz](6+). Nevertheless, both cationic moieties exist in their monomeric form under specific experimental conditions. UV-visible monitored titrations with NaOH provide information about the type of protonation/deprotonation equilibria which are complicated by the occurrence of aggregation phenomena.     

Linear Sections of the Finite Veronese Varieties and Authentication Systems Defined Using Geometry

In this paper we deal with authentication systems in which one key is used to authenticate many source states. We answer a related question on the cardinalities of the intersections of quadrics in PG (d,q). We first generalize a class of geometric authentication systems, which has been introduced by Beutelspacher, Tallini and Zanella4. The source states are the lines through a special point N of PG (d,q) (the d-dimensional projective space over GF (q)). The keys are some hypersurfaces which have N as a nucleus ( N is a nucleus of if every line through N meets in exactly one point). The message belonging to a source state and a key is the unique point of intersection of the line with the hypersurface . We give the values of s for which the constructed authentication systems have a security which is comparable to the best allowed by a theoretical bound. In case the hypersurfaces are quadrics, we give further results on the security. To this end, we determine the greatest cardinality for the intersections of the finite Veronese varieties with the projective subspaces of any given dimension. Finally, we discuss a possible implementation.     

On flags in a topological projective plane

In this paper we study some properties of the flag space () of a topological projective plane . The line set, sayL, of (), splits into two subfamiliesL ₀ andL ₁ which an non-trivial partitions of the point set of (). For any two distinct lines , ' belonging to one of the two subfamilies, there is exactly one line in the other subfamily meeting botl and '; turns out to be a continuous mapping of (-,'–. Further, the intersection o: two lines, having exactly one point in common, is a continuous and open mapping. Conversely, every irreducible semilinear space, satisfying the above properties, is isomor phic to the flag space of a topological projective plane.This paper has been prepared from some results of a research project supported by N.A.T.O.     

Adsorption of d-alaninol on Cu(1 0 0)

Adsorption of d-alaninol on Cu(1 0 0) at room temperature has been investigated by photoelectron spectroscopy in the soft X-ray and VUV energy range and low energy electron diffraction (LEED). d-Alaninol was found by LEED to self-assemble at full coverage; core and valence photoemission spectra are presented at low and full coverage. Chemisorption occurs at room temperature. The bonding at low coverage takes place at the hydroxylic group; at full coverage there is evidence of bonding for both hydroxylic and amino groups.     

Towards integrated devices for computer screen photo-assisted multi-parameter sensing

The computer screen photo-assisted technique (CSPT) utilizes consumer electronic devices such as computer screens and web cameras for distributed chemical sensing. Key to this method is the development of small and disposable sensing assays able to aid the CSPT optical detection, and the evaluation of multiple indicators. Here we demonstrate CSPT identification of fluorescent indicators from individual 100 μm SU-8 (10) pillars covering an area of 4 mm × 4 mm with a density of 47 elements mm⁻². The extraction of distinctive spectral fingerprints is aided by the exploitation of a three-band Moiré interference that enables the partial Bayer decoding of the CSPT images.     

Poly(1,4‐cyclohexylenedimethylene 1,4‐cyclohexanedicarboxylate): Influence of stereochemistry of 1,4‐cyclohexylene units on the thermal properties

A series of poly(1,4‐cyclohexylenedimethylene 1,4‐cyclohexanedicarboxylate) (PCCD) samples, characterized by different cis/trans ratio of the 1,4‐cyclohexanedicarbonyl unit, have been synthesized and analyzed by thermogravimetry (TGA), calorimetry (DSC), and X‐ray diffraction (WAXD). The thermal stability results are good and are not affected by the stereochemistry of the 1,4‐cyclohexylene units. On the other hand, the thermal transitions are notably influenced by the cis/trans content. With the increment of the trans content the polymer changes from completely amorphous to semicrystalline material. T_g, T_m, and crystallinity increase. These results suggest that the trans configuration induces a better chain packing and higher symmetry, improving the crystallizability of the samples. The effect of the molecular structure on the thermal properties is analyzed by using a statistical approach. From the effective correlations found between stereochemistry of the C₆ rings and transition temperatures it is possible to extrapolate that the configuration of 1,4‐cyclohexylene ring deriving from 1,4‐cyclohexanedicarboxylic acid or dimethyl 1,4‐cyclohexanedicarboxylate results to be the main element responsible for the thermal properties. This is due to the high rigidity of the 1,4‐cyclohexanedicarbonyl unit with respect to 1,4‐cyclohexanedimethyleneoxy unit, deriving from the diol. © 2008 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 46: 619–630, 2008     

Incidence and Combinatorial Properties of Linear Complexes

In this paper a generalisation of the notion of polarity is exhibited which allows to completely describe, in an incidence-geometric way, the linear complexes of h-subspaces. A generalised polarity is defined to be a partial map which maps (h−1)-subspaces to hyperplanes, satisfying suitable linearity and reciprocity properties. Generalised polarities with the null property give rise to linear complexes and vice versa. Given that there exists for h > 1 a linear complex of h-subspaces which contains no star – this seems to be an open problem over an arbitrary ground field – the combinatorial structure of a partition of the line set of the projective space into non-geometric spreads of its hyperplanes can be obtained. This line partition has an additional linearity property which turns out to be characteristic. Received: December 3, 2007. Revised: December 13, 2007.     

Synthesis,crystal structure and antibacterial activity of manganese(III) and cobalt(III) complexes containing pentadentate Schiff bases of a common amine and thiocyanate

Abstract

Four new mononuclear Schiff base manganese(III) and cobalt(III) complexes viz. [Mn(L¹)(NCS)] (1), [Mn(L²)(NCS)] (2), [Co(L³)(NCS)] (3), and [Co(L⁴)(NCS)]·0.5CH₃OH·0.5H₂O (4), containing thiocyanate as a common pseudohalide ion are reported. The pentadentate Schiff base ligands H₂L¹, H₂L², H₂L³, and H₂L⁴ were obtained by the condensation of substituted salicylaldehydes with N-(3-aminopropyl)-N-methylpropane-1,3-diamine. The syntheses of the complexes have been achieved by the reaction of manganese(II) perchlorate or cobalt(II) perchlorate with the respective Schiff bases in the presence of thiocyanate in methanol medium. Complexes 1–4 have been characterized by microanalytical, spectroscopic, single-crystal X-ray diffraction and other physicochemical studies. Structural studies reveal that 1–4 adopt nearly similar structures containing the MN₄O₂ (M?=?Mn, Co) chromophore in which each central M(III) ion adopts a distorted octahedral geometry. Weak intermolecular H-bonding interactions are operative in these complexes to bind the molecular units. The antibacterial activity of 1–4 and their constituent Schiff bases has been tested against some common bacteria.     

On Relaxation Hyperbolic Systems Violating the Shizuta–Kawashima Condition

In this paper, we start a general study on relaxation hyperbolic systems which violate the Shizuta–Kawashima ([SK]) coupling condition. This investigation is motivated by the fact that this condition is not satisfied by various physical systems, and almost all the time in several space dimensions. First, we explore the role of entropy functionals around equilibrium solutions, which may not be constant, proposing a stability condition for such solutions. Then we find strictly dissipative entropy functions for one dimensional 2 × 2 systems which violate the [SK] condition. Finally, we prove the existence of global smooth solutions for a class of systems such that condition [SK] does not hold, but which are linearly degenerated in the non-dissipative directions.