Bent-shaped mesogenic oxadiazoles and thiadiazoles with terminal methyl group

Rod-shaped 4-methylbenzoic acid-N′-(4′-n-alkoxybenzoyl) hydrazide (series I) have been synthesized by the Schotten–Baumann reaction of 4-methylbenzhydrazide with 4-n-alkoxy benzoyl chloride using dry pyridine, as a solvent. The series I compounds have been cyclized to bent-shaped mesogenic 2-(4′-methylphenyl)-5-(4″-n-alkoxyphenyl)-1,3,4-oxadiazoles (series II) and 2-(4′-methylphenyl)-5-(4″-n-alkoxyphenyl)-1,3,4-thiadiazole (series III) using POCl₃ and Lawesson's reagent, respectively. The synthesized compounds are characterized by the combination of elemental analysis and standard spectroscopic methods. In series II, lower and middle members are non-mesogenic. n-Dodecyloxy to n-hexadecyloxy derivatives exhibit enantiotropic nematic mesophase. In series III, all the compounds synthesized exhibit enantiotropic nematic mesophase. n-Tetradecyloxy and n-hexadecyloxy derivatives also exhibit enantiotropic SmA mesophase. The mesomorphic properties of the series II and III used in this study are compared with each other and with other structurally related compound to evaluate the effect of different heterocyclic moieties as well as terminal substituents on mesomorphism.     

Quantum condensates classified in superconductivity with topology in the Minkowski space-time

A substantial problem in the macroscopic theory of pure superconductivity has been left forgotten for a long time since London and London in 1935. An impression survived that the Meissner effect is more substantial than the zero-resistivity. But, the London equation [I], the Newtonian equation of motion, was abandoned, whereas the London equation [II], derived from the Maxwell equations, was postulated. The London equation [II] included the logical gap [ α ] in real time, whereas the London equation [I] has been ignored without even noting the logical gap [ β ] in space. Microscopically, after the publication of F. London's book and the discovery of the isotope effect in 1950, the success of the Bardeen--Cooper--Schrieffer (BCS) theory in 1957 was likely to have finally given the definitive explanation on superconductivity by proving only the London equation [II] that claimed the coherent condensation of Cooper pairs in the momentum space. Since then, these arguments have been regarded to be a standard among various preceding theories. Meanwhile, the London equation [I] has faded away and has been long-forgotten. But we must not abandon the London equation [I], and, rather, retrieve it. We later recognized also that the DC-component of a persistent current can never be determined by using the Fourier transform analysis, because of its singularity at ω?=?0 and q ?=?0 with huge differences of space-time domain. Quite recently, in 2003, we first recognized a proper and harmonious view to simultaneously account for (i) the zero-resistivity in an open system with (i-c) the resultant persistent current in a closed system, and (ii) the perfect diamagnetism at T???0?K in the space-time aspects in terms of the gauge field theory. Here, we further clarify where and how we have lost and found a properly perspective view of the superconductivity. Here, we eliminate two logical gaps [ α ] and [ β ] by using the gauge field theory for further clarifying a position of the previous and present works. We especially classify superconductors with topology which eventually leads us such as (ii-2D) magnetic flux quantization in a ring. By projecting the 3-dimensional BCS-theory with the concept of ‘coherence’ among an enormous number of Bosons like Cooper pairs onto the (1?+?3)-dimensional Minkowski space-time [β?=?(v/c)?=?0], we clarify responses of the ground state Ψ _macro at T???0?K in a set of the basic equations, for (i) the zero-resistivity, [E _K ???qφ( R )]?=?0 at ω?=?0 and (ii) the perfect diamagnetism [?K ???qA ( R )]?=?0 at q ?=?0 as an inevitable consequence at the gauge fields in the proper theory of superconductivity.     

Conformational analysis of <Emphasis Type="Italic">o</Emphasis>-allylphenol by density functional and IR spectroscopy methods

The two-dimensional cyclic potential energy surfaces for internal rotation of the allyl substituent and its vinyl fragment in o-allylphenol (o-APh) depending on the OH group orientation relative to the allyl substituent were constructed by a B3LYP/6-31G method. It is shown that o-APh exists in the gas phase as a mixture of eight non-planar rotamers (A, B, C, D, E, F, G, and H) and their eight optical isomers (A ₁, B ₁, C ₁, D ₁, E ₁, F ₁, G ₁, and H ₁). An intramolecular H-bond (IHB) O–H...π occurs only in four rotamers (A, B, A ₁, and B ₁). The content of such rotamers in the gas phase is 47.2% (as calculated by the B3LYP/cc-pVTZ method). Taking into account the solvation effect in the polarizable continuum model (PCM) for a solution of o-APh in cyclohexane decreases the total content of rotamers with an IHB (A and B) to 37.7%. The ratio of rotamers with OH groups bonded by an IHB and with free OH groups that is predicted theoretically agrees with the value measured experimentally from IR spectra of o-APH in CCl₄ solution.     

Conditional expectation and commutativity in von Neumann algebras

LetH be a Hilbert space,A the von Neumann algebra of all bounded operators onH,B a von Neumann subalgebra ofA, andw a bounded linear functional onA. The functionalw is said to commute withBA ifw(AB)=w(BA) for allAA. It is shown that the mapBw (BAB) is a complex measure on the orthocomplemented partially ordered set of all orthogonal projections inB for everyAA if and only ifw commutes with all members ofB. For anyAA, the conditional expectation ofA with respect toB andw is defined and it is shown that this expectation exists for an Abelian separableB ifw commutes with all members ofB. Using Gleason's theorem it is shown thatw commutes withB if and only if the density operator ofw commutes withB.     

Proton and Carbon‐13 NMR Studies of the Phencyclone Adducts of Medium Alkyl Chain‐Length N‐n‐Alkylmaleimides. Hindered Rotations and Magnetic Anisotropic Effects. Ab initio Calculations for Optimized Structures

Abstract

The Diels–Alder adducts, 3a–e, of phencyclone, 1, have been prepared from a series of N‐n‐alkylmaleimides, 2, with medium chain‐length n‐alkyl groups. The maleimides were obtained by cyclodehydration of the N‐n‐alkylmaleamic acids, 4, formed from reaction of maleic anhydride with the corresponding n‐alkylamines. The five adducts prepared included derivatives from n‐heptyl, 3a; n‐octyl, 3b; n‐nonyl, 3c; n‐decyl, 3d; and n‐dodecyl, 3e. The NMR spectra of the adducts were studied in CDCl₃ at ambient temperatures at 300 MHz for proton and 75 MHz for carbon‐13, with full proton assignments achieved by high‐resolution COSY45 spectra for the aryl and the alkyl regions. Slow exchange limit (SEL) spectra were observed for both ¹H and ¹³C spectra showing slow rotation on the NMR timescales of the unsubstituted bridgehead phenyl groups. Endo Diels–Alder adduct stereochemistry was supported by striking magnetic anisotropic shielding effects in the ¹H spectra of the alkyl groups, with the NCH₂ CH ₂ signal of each adduct appearing upfield of tetramethylsilane (TMS) at ca. ?0.32 ppm. Proton NMR spectra for precursor maleamic acids and maleimides are reported, with some solvent effects found (CDCl₃ vs. d ₆‐acetone) for the carbon‐bound HC?CH protons of 4. Ab initio molecular modeling calculations at the Hartree‐Fock level using the 6‐31G* basis set have been performed for two key conformers of the phencyclone adduct of N‐n‐octylmaleimide, as a representative structure for these hindered adducts, to estimate geometric parameters for the adduct. A syn conformer, with the alkyl chain directed into the adduct cavity, was found to be ca. 0.23 kcal/mol lower energy than an anti conformer (in which the alkyl chain was directed away from the phenanthrenoid moiety).     

Finite Quantum Tomography and Semidefinite Programming

Using the convex semidefinite programming method and superoperator formalism we obtain the finite quantum tomography of some mixed quantum states such as: truncated coherent states tomography, phase tomography and coherent spin state tomography, qudit tomography, N-qubit tomography, where that obtained results are in agreement with those of References (Buzek et al., Chaos, Solitons and Fractals 10 (1999) 981; Schack and Caves, Separable states of N quantum bits. In: Proceedings of the X. International Symposium on Theoretical Electrical Engineering, 73. W. Mathis and T. Schindler, eds. Otto-von-Guericke University of Magdeburg, Germany (1999); Pegg and Barnett Physical Review A 39 (1989) 1665; Barnett and Pegg Journal of Modern Optics 36 (1989) 7; St. Weigert Acta Physica Slov. 4 (1999) 613). PACs index: 03.65.Ud     

Realizations of causal manifolds by quantum fields

Quantum mechanical operators and quantum fields are interpreted as realizations of timespace manifolds. Such causal manifolds are parametrized by the classes of the positive unitary operations in all complex operations, i.e., by the homogenous spacesD(n)=GL(C _R ⁿ )/U(n) withn=1 for mechanics andn=2 for relativistic fields. The rankn gives the number of both the discrete and continuous invariants used in the harmonic analysis, i.e., two characteristic masses in the relativistic case. ‘Canonical’ field theories with the familiar divergencies are inappropriate realizations of the real 4-dimensional causal manifoldD(2). Faithful timespace realizations do not lead to divergencies. In general they are reducible, but nondecomposable—in addition to representations with eigenvectors (states, particle), they incorporate principal vectors without a particle (eigenvector) basis as exemplified by the Coulomb field. In theorthogonal andunitary groupsO(N ₊,N ₋), respectively, thepositive orthogonal and unitary ones areO(N) andU(N), respectively.     

The ideal polymer chain near planar hard wall beyond the Dirichlet boundary conditions

We present a new ab initio approach to describe the statistical behavior of long ideal polymer chains near a plane hard wall. Forbidding the solid half-space to the polymer explicitly (by the use of Mayer functions) without any other requirement, we derive and solve an exact integral equation for the partition function G _D(r,r′, N) of the ideal chain consisting of N bonds with the ends fixed at the points r and r′ . The expression for G(r,r′, s) is found to be the sum of the commonly accepted Dirichlet result G _D(r,r′, N) = G ₀(r,r′, N) - G ₀(r,r”, N) , where r” is the mirror image of r′ , and a correction. Even though the correction is small for long chains, it provides a non-zero value of the monomer density at the very wall for finite chains, which is consistent with the pressure balance through the depletion layer (so-called wall or contact theorem). A significant correction to the density profile (of magnitude 1/is obtained away from the wall within one coil radius. Implications of the presented approach for other polymer-colloid problems are discussed.     

Design and synthesis of novel (Z)-5-((1,3-diphenyl-1H-pyrazol-4-yl)methylene)-3-((1-substituted phenyl-1H-1,2,3-triazol-4-yl)methyl)thiazolidine-2,4-diones: a potential cytotoxic scaffolds and their molecular modeling studies

In an effort to discover potential cytotoxic agents, a series of novel (Z)-5-((1,3-diphenyl-1H-pyrazol-4-yl)methylene)-3-((1-substituted phenyl-1H-1,2,3-triazol-4-yl)methyl)thiazolidine-2,4-dione derivatives (8a–n) were designed and synthesized in various steps with acceptable reaction procedures with quantitative yields and characterized by ¹H NMR, ¹³C NMR, IR, HRMS and ESI–MS spectra. These newly synthesized novel derivatives were screened for their in vitro cell viability/cytotoxic studies against human breast cancer cell line (MCF-7) with various concentrations of 0.625 µM, 1.25 µM, 2.5 µM, 5 µM and 10 µM, respectively. The biological interpretation assay outcome was demonstrated in terms of cell viability percentage reduction and IC₅₀ values against standard reference drug cisplatin. Based on these results, most of the derivatives exhibited promising cytotoxic activity. Among them, particularly compounds 8j (R₁?=?OMe and R₃?=?NO₂) and 8e (R₃?=?CF₃) demonstrate remarkable cytotoxic activity with IC₅₀ values 0.426 µM?±?0.455 and 0.608 µM?±?0.408, which are even better than the standard drug cisplatin 0.636 µM?±?0.458 and compounds 8m (R₂?=?OMe and R₃?=?OMe) and 8c (R₃?=?OMe) exhibited closely equivalent IC₅₀ values to the standard drug with IC₅₀ values 0.95 µM?±?0.32 and 0.976 µM?±?0.313 and rest of the compounds exhibits moderate cytotoxic activity. Moreover, molecular modeling studies and ADME calculations of the novel synthesized derivatives are in adequate consent with the pharmacological screening results.

     

Ionic liquid-promoted multi-component reaction: novel and efficient preparation of pyrazolo[3,4-<Emphasis Type="Italic">b</Emphasis>]pyridinone,pyrazolo[3,4-<Emphasis Type="Italic">b</Emphasis>]-quinolinone and their hybrids with pyrimidine nucleoside

The utilization of an ionic liquid, [bmim][BF₄] as both reaction medium and promoter for a multi-component reaction of aldehyde (1) and 5-amino-3-methyl-1-phenylpyrazole (2) with Meldrum acid (3) or dimedone (5) is studied. From this reaction, pyrazolo[3,4-b]pyridinone (4) and pyrazolo[3,4-b]quinolinone (6) derivatives were prepared in high yields. This novel procedure showed such advantages as environmentally benign nature, enhanced efficiency, simple operation process, and mild reaction conditions. As an application, the procedure was successfully used in the preparation of a set of pyrimidine nucleoside–pyrazolo[3,4-b]pyridine and pyrazolo[3,4-b]quinolinone hybrids with potential biological activities.     

Mechanism of giant magnetoresistance in intermetallic compounds of rare-earth ions and actinides

Giant positive or negative magnetoresistance is calculated in a band model. The spectra of the band electrons in a two-sublattice antiferromagnetic intermetallic compound depend on the antiferromagnetism vector L(T,H). The metamagnetic transition to the ferromagnetic phase is accompanied by splitting with respect to the spin σ, displacement of the energy bands, and a decrease in the effective masses of the band electrons. This mechanism of giant negative magnetoresistance is also accompanied by an increase in the relaxation time τ_jσ. Scattering by chemical-bond fluctuations is considered as the main relaxation mechanism. Giant positive magnetoresistance results from a four-subband model of 4f and 5f intermetallic compounds. The electron effective masses m _jσ(J _jT ) of the (j,σ) bands increase with the mean angular momentum J _1T (T,H) of an ion in the jth sublattice of 4(5)f ions. The thermodynamics of such a four-sublattice model, the nonlinear magnetization and magnetoresistance curves, and the nonmonotonic dependence of the specific heat C _m(T,H) on the field H are calculated. Fiz. Tverd. Tela (St. Petersburg) 39, 1806–1814 (October 1997)     

Crystal structures of high-T c oxides

A comprehensive review of structure work on high-T _c oxides as reported during the years 1987 and 1988 is given. Thirteen structures are refined from X-ray single-crystal and/or neutron powder diffraction data:I. (Ba_1–x ,K _x )BiO₃ (T _c =30 K),II. (La_2–x , Sr _x )CuO₄ (T _c =40 K),III. (Nd, Ce, Sr)₂CuO₄ (T _c =28 K),IV. (Nd_2–x , Ce _x )CuO₄ (T _c =24 K),V. YBa₂Cu₃O₇ (T _c =90 K),VI. YBa₂Cu₄O₈ (T _c =80 K),VII. Y₂Ba₄Cu₇O₁₄ (T _c =40 K),VIII. Pb₂Sr₂NdCu₃O₈ (T _c =70 K),IX. TlBa₂CaCu₂O₇ (T _c =103 K),X. TlBa₂Ca₂Cu₃O₉ (T _c =120 K),XI. Tl₂Ba₂CuO₆ (T _c =90 K),XII. Tl₂Ba₂CaCu₂O₈ (T _c =112 K),XIII. Tl₂Ba₂Ca₂Cu₃O₁₀ (T _c =125 K). Except forI (perovskite type),II (K₂NiF₄ type) andIV (Nd₂CuO₄ type) they represent new structure types. Structure data, bond distances, structure drawings and calculated X-ray powder diffraction patterns are given for each compound. Structural features and correlations with superconductivity are discussed. The review contains 301 citations.     

Predictability of ion transport properties from the structure of solid electrolytes

The concept of bond valence (BV) is widely used in crystal chemical considerations, e.g. to assess equilibrium positions of atoms in crystal structures from an empirical relationship between bond lengthR _M−X and bond valenceS _A−X =exp [(R ₀ −R _M−X ) /b] as sites where the BV sumV(A)=∑ s _M−X equals the formal valenceV _id of the cationM ⁺ . Our modified BV approach that systematically accounts for the softness of the bond may then be effectively used to study the interplay between structure and properties of solid electrolytes. This is exemplified for correlations to experimental data from IR, NMR, and impedance spectroscopy. Combining the bond valence approach with reverse Monte Carlo (RMC) modeling or molecular dynamics (MD) simulations provides a deeper understanding of ion transport mechanisms, especially in highly disordered or amorphous solids. Local structure models for crystalline electrolytes are derived by combining crystallographic structure information with simulations. A method for the prediction of the activation energy of the ionic conductivity from the bond valence analysis of the crystal structure is proposed. Taking into account the mass dependence of the conversion factor from bond valence mismatch into an activation energy scale, we could establish a correlation that holds for different types of mobile ions. The strong coupling of the H⁺ transfer to the anion motion in proton conductors requires a special treatment. For glassy solid electrolytes RMC structure models are BV-analyzed to assess the total number of equilibrium sites and to identify transport pathways for the mobile ions. Recently, we have reported a correlation between the pathway volume fraction and the transport properties that permits to predict both absolute value and activation energy of the dc ionic conductivities of disordered solids (including mixed alkali glasses) directly from their structural models. Here we discuss a corresponding BV analysis of molecular dynamics simulation trajectories that allows quantifying the evolution of pathways in time and the influence of temperature on the transport pathways. Paper presented at the Patras Conference on Solid State Ionics — Transport Properties, Patras, Greece, Sept. 14 — 18, 2004.     

Synthesis of Pyrazolopyridine Annulated Heterocycles and Study the Effect of Substituents on Photophysical Properties

Pyrazolo[3,4-b]pyridines having 4-chloro-5-chloroethyl side chain are synthesized by the reaction of 5-aminopyrazole and cyclic β-formylester gave aminopyrazolodihydrofuranone intermediate, which on cyclization in phosphorous oxychloride exclusively converted in to 4-chloro-5-chloroethyl pyrazolo[3,4-b]pyridines 4(a-b) in major amount. The side chain with acetic acid, thiourea and aromatic amines are used to form angular ring leads to formation of tricyclic Furo[2,3-d]pyrazolo[2,3-b]pyridines 5(a-b), pyrazolo[3,4-b]thieno[2,3-d]pyridines 6(a-b) and pyrazolo[3,4-b]pyrrolo[2,3-d]pyridines 7(a-n) respectively. The substituents effect at C₄ position on fluorescence properties of pyrazolopyridines has been studied. Moreover the effect of electron donor and halogen substituents on fluorescence properties of pyrazolopyrrolopyridines 7(a-n) has been investigated along with their fluorescent quantum yield.     

Large-scale amplification of a magnetic field by turbulent helicity fluctuations

In this paper the procedure of large-scale averaging of the magnetic-field diffusion equation with the α-term curlα(r,t)B(r,t) is used to show that a nonuniform distribution of the turbulent helicity fluctuations (more precisely, the fluctuations of the coefficient α) with a zero average value gives rise to large-scale amplification of the initial magnetic field. A detailed study is carried out of the dependence of the resulting large-scale α effect on the characteristics of the correlator 〈〈α(r, t)α(r″,t″)〉〉 in a rotating medium with a nonuniform distribution of the angular velocity ω=ω(ρ,z) (ρ is the distance for the rotation axis z). The effect of helicity fluctuations and the diffusion coefficient on the turbulent diffusion process is also investigated. Zh. éksp. Teor. Fiz. 116, 85–104 (July 1999)     

A Fluorescence Study of Novel Styrylindoles in Homogenous and Microhetrogeneous Media

In this paper are presented absorption and fluorescence emission properties of 3-styrylindoles viz. 3-(2-phenylethenyl-E)-NH-indole (1), 3-[2-(4-nitrophenyl)ethenyl-E)-NH-indole (2), 3-[2-(4-cyanophenyl)ethenyl-E]-N-ethylindole (3) and 3-[2-(4-cyanophenyl)ethenyl-E]-NH-indole (4) in organic solvents, 1,4-dioxane-water binary mixtures and micelles (SDS, CTAB and Triton-X-100). The fluorescence properties of 2-4 have been utilized to probe the microenvironment (binding constant, CMC, micropolarity and solubilization site) of the micelles.     

A diversity oriented, microwave assisted synthesis of N-substituted 2-hydro-4-amino-pyrido[2,3-d]pyrimidin-7(8H)-ones

A protocol for the synthesis of N-substituted 2-hydro-4-amino-pyrido[2,3-d]pyrimidin-7(8H)-ones (11) is described. Thus, the formylation of a 2-aminopyridone 12 in 85% formic acid/Ac₂O, proceeding via in situ cyclization to the intermediate formamide 13, affords the corresponding 2-hydro-4-oxo-pyridopyrimidine 14, which is converted to a 4-chloro-pyridopyrimidine 15 upon treatment with POCl₃. The subsequent transformation to the title compounds is carried by treatment with the corresponding amine in MeOH under microwave irradiation conditions.     

Crystal Structures of Tetrakis‐(4‐chlorophenylthio)‐butatriene and Tetrakis‐(tert‐butylthio)‐butatriene

Tetrakis‐(4‐chlorophenylthio)‐butatriene (3a) and tetrakis‐(tert‐butylthio)‐butatriene (3b) were synthesized, and their crystal structures were determined. The compound 3a is monoclinic, space group P2₁/c, a=6.9785(8), b=8.6803(9), c=22.884(2) Å, β=93.887(6)^o, V=1383.0(3) ų, Z=2. The compound 3b is monoclinic, space group P2₁/n, a=11.0615(6), b=10.8507(4), c=11.2717(6) Å, β =116.427(2)^o, V=1211.5(1) ų, Z=4. The title compounds 3a and 3b reside on an inversion center so that only half of the molecule is crystallographically unique. Both compounds are not planar. The crystal structures of 3a and 3b have cumulated double bonds. The C7–C8–C8ⁱ and C5–C6–C6ⁱ angles that show the linearity in both structures, respectively, are 176.4(3)° in 3a and 175.6(2)° in 3b.     

EPR Study of Single Crystals of PROXYLs

Electron paramagnetic resonance study of the single crystals of two PROXYLs, trans-2,5-bis(4-methylphenyl)-2,5-dimethylpyrrolidine-1-oxy [(±)-1] and trans-2-(4-methylphenyl)-2,5-dimethyl-5-phenylpyrrolidine-1-oxy [(±)-2] was conducted. The obtained spectra were always fitted well by a single Lorentzian. The principal g-values (g _x , g _y , g _z ) of (±)-1 and (±)-2 were determined as (2.00990, 2.00639, 2.00266) and (2.01106, 2.00742, 2.00389), respectively. The profiles of half width at half maximum (HWHM) depending on two polar angles, θ and ϕ, were measured in all directions. The angular profiles of the exchange interaction (|J ₀|) were attempted to be estimated by dividing the experimental HWHM by the calculated total second moment (M ₂ ^tot) with the crystallographic data. For (±)-1, |J ₀| along the c-axis was estimated to be much larger than that along the a- or b-axis. This suggests that (±)-1 is a one-dimensional magnet along the c-axis. Authors' address: Yohei Noda, Electron Spin Chemistry Laboratory, Department of Chemistry, Graduate School of Science, Kyoto University, 606-8502 Kyoto, Japan     

The magnetic structure of neodymium crystal below the néel temperature

The phase transition in neodymium crystal from the paramagnetic to the magnetically ordered phase at the temperature T _N = 19.9 K is discussed in the terms of Landau's theory. It is shown that the calculated six-dimensional active representations at the point q = vb ₁, with—0.5 < v < 0.5, v ≠ 0, induce transitions to “single-q”, “double-q” and “triple-q” spin structures. A general formula for the spin vector S(r) for T < T _N is derived, from which a variety of spin structures can be obtained depending on the choice of the free parameters. The spin structure calculated by Bak and Lebech (1978) is obtained from that formula as a particular solution which is compatible with Landau's theory. An antiferromagnetic spin structure which represents a modification of that given by Bak and Lebech (1978) is calculated. The corresponding cross-section for neutron elastic magnetic scattering fulfils the experimental conditions listed by Lebech (1981). It is shown that the magnetic satellites of the type (h ± v, 0, 0) cannot appear for any type of structure following from our general formula for S(r). These satellites therefore can be connected only with representations at the point q = μ₁ b ₁ + μ₂ b ₂,—0.5 < μ₁, μ₂ < 0.5, μ₁, μ₂ ≠ 0, μ₁ ≠ μ₂.