The synthesis and fluorescence properties of novel chromenone-crown ethers

o-Dihyroxy-3-phenylchromenone derivatives, namely, 6,7-dihydroxy-3-(3′,4′-dimethoxyphenyl)chromenone and 6,7-dimethoxy-3-(3′,4′-dihydroxyphenyl)chromenone, were obtained from 2,4,5-trihydroxybenzaldehyde/3,4-dimethoxyphenylacetic acid and 2-hydroxy-4,5-dimethoxybenzaldehyde/3,4-dihydroxyphenylacetic acid, respectively, in the presence of acetic anhydride and sodium acetate under an inert atmosphere, after treatment with MeOH/HCl(aq). The chromenone-crown ethers were prepared from cyclic condensation of o-dihydroxy-3-phenylchromenones with poly(ethylene glycol) ditosylates in the presence of CH₃CN/alkali metal carbonates. The chromatographically purified novel chromenone-crown ethers were identified by ¹H NMR, MALDI-TOF mass spectrometry and elemental analysis. The fluorescence and UV–vis spectroscopic properties of the obtained chromenone-crown ethers and their complexes with Li⁺, Na⁺ and K⁺ perchlorate salts were estimated in acetonitrile. The quantum yields of novel chromenone-crown ethers were determined by the comparative method.

     

Synthesis and complexation of a novel soluble vic-dioxime with hydroxyethyl pendant arms

A new soluble vic-dioxime ligand namely 1,4-bis(2′-hydroxyethyl)-2,3-bis(hydroxyimino)-5,6-diphenylpiperazine, (LH₂) containing optically active centers has been prepared as a mixture of isomers from (CNO)₂ and N,N-bis(2-hydroxyethyl)stilbendiamine (1) which has been made by the reduction of the condensation of the product of benzaldehyde and 2-aminoethanol in the presence of aluminum amalgam. N,N-coordinated planar metal complexes of this ligand have been synthesized with Ni^II, Cu^II, Co^II, Pd^II and U^VIO₂. Oxidation of (LH)₂Co in the presence of a base, such as pyridine, leads to an octahedral complex (LH)₂CopyCl containing pyridine and chloride as axial ligands in addition to vic-dioxime ligands. The structures of the ligand and its complexes are proposed on the basis of elemental analysis, ¹H-n.m.r., mass, i.r. and u.v.–vis. spectral data. This revised version was published online in June 2006 with corrections to the Cover Date.     

Theoretical calculations of high-pressure phases of NiF<Subscript>2</Subscript>: An ab initio constant-pressure study

We have studied the structural properties of the antiferromagnetic NiF₂ tetragonal structure with P4₂/mnm symmetry using density functional theory (DFT) under rapid hydrostatic pressure up to 400 GPa. For the exchange correlation energy we used the local density approximation (LDA) of Ceperley and Alder (CA). Two phase transformations are successfully observed through the simulations. The structures of XF₂-type compounds crystallize in rutile-type structure. NiF₂ undergoes phase transformations from the tetragonal rutile-type structure with space group P4₂/mnm to orthorhombic CaCl₂-type structure with space group Pnnm and from this orthorhombic phase to monoclinic structure with space group C2/m at 152 GPa and 360 GPa, respectively. These phase changes are also studied by total energy and enthalpy calculations. According to these calculations, we perdict these phase transformations at about 1.85 and 30 GPa.     

A string-like self-dual solution of Yang-Mills theory

We attempt to obtain Nielsen-Olesen strings in pure Yang-Mills theory without Higgs scalars. This is inspired by recent work interpreting the Prasad-Sommerfield monopole as a static self-dual Yang-Mills solution in which A₄^a plays the role of the Higgs field. In similar fashion, we make A₃^aA₄^a serve as the two required isovector fields in an ansatz independent of x₃ and x₄. The condition of self-duality results in a single Painlevé equation of the third kind (or equivalently, a radial sinh-Gordon equation in 2 + 0 dimensions), the solution of which determines A_μ^a. We make use of the extensive analysis of the former equation carried out by Wu, McCoy and collaborators in the context of the scaling limit of the two-dimensional Ising model. Their simplest solution yields a flux value of ?2π/e just as in the Nielsen-Olesen model and flux is quantized in multiples of this unit. The string tension (action per unit time per unit distance) diverges as r^?2 (In r)^?2 as r → 0 for the same Wu-McCoy solution.     

Solutions to euclidean gravity for infinitely many instantons

Self-dual solutions to euclidean Einstein equations are obtained by integrating over various configurations of an infinite number of Hawking-Gibbons multi-instantons. The resulting metrics are all stationary and of Bianchi type II (euclidean version). They may be previously unknown solutions. In the weak field approximation one finds related spatially increasing potentials reminiscent of confinement. Following Eguchi and Hanson, self-dual Maxwell fields for the coupled Maxwell-Einstein system are also constructed.     

Comparison of Two Reformulation-Linearization Technique Based Linear Programming Relaxations for Polynomial Programming Problems

In this paper, we compare two strategies for constructing linear programmingrelaxations for polynomial programming problems using aReformulation-Linearization Technique (RLT). RLT involves an automaticreformulation of the problem via the addition of certain nonlinear impliedconstraints that are generated by using the products of the simple boundingrestrictions (among other products), and a subsequent linearization based onvariable redefinitions. We prove that applying RLT directly to the originalpolynomial program produces a bound that dominates in the sense of being atleast as tight as the value obtained when RLT is applied to the jointcollection of all equivalent quadratic problems that could be constructed byrecursively defining additional variables as suggested by Shor.     

Amperometric Lactate Biosensor Based on Carbon Paste Electrode Modified with Benzo[c]cinnoline and Multiwalled Carbon Nanotubes

Amperometric lactate biosensor based on a carbon paste electrode modified with benzo[c]cinnoline and multiwalled carbon nanotubes is reported. Incorporation of benzo[c]cinnoline acting as a mediator and multiwalled carbon nanotubes providing a conduction pathway to accelerate electron transfer due to their excellent conductivity into carbon paste matrix resulted in a high performance lactate biosensor. The resulting biosensor exhibited a fast response, high selectivity, good repeatability and storage stability. Under the optimal conditions, the enzyme electrode showed the detection limit of 7.0×10^?8 M with a linear range of 2.0×10^?7 M–1.1×10^?4 M. The usefulness of the biosensor was demonstrated in serum samples.     

N—H⋯N and C—H⋯π inter­actions in 4‐amino‐3‐methyl‐5‐(p‐tol­yl)‐4H‐1,2,4‐triazole and 4‐amino‐3‐methyl‐5‐phenyl‐4H‐1,2,4‐triazole

The title compounds, C₁₀H₁₂N₄, (I), and C₉H₁₀N₄, (II), have been synthesized and characterized both spectroscopically and structurally. The dihedral angles between the triazole and benzene ring planes are 26.59 (9) and 42.34 (2)°, respectively. In (I), mol­ecules are linked principally by N—H⋯N hydrogen bonds involving the amino NH₂ group and a triazole N atom, forming R₄⁴(20) and R₂⁴(10) rings which link to give a three‐dimensional network of mol­ecules. The hydrogen bonding is supported by two different C—H⋯π inter­actions from the tolyl ring to either a triazole ring or a tolyl ring in neighboring mol­ecules. In (II), inter­molecular hydrogen bonds and C—H⋯π inter­actions produce R₃⁴(15) and R₄⁴(21) rings.