IR Evidences for N-9 and N-7 Regioisomers of the Acyclic Purine Nucleoside Analogues

The IR spectra have been recorded in the solid state for the parent molecule, 6-(N-pyrrolyl)purine (1) and its N-9-and N-7-substituted derivatives: 9-and 7-(2-hydroxyprop-1-yl)-6-(N-pyrrol-1-yl)purine (2 and 3), 9-and 7-(2-acetoxyprop-1-yl)-6-(N-pyrrol-1-yl)purine (4 and 5), 9-and 7-(2,3-dihydroxyprop-1-yl)-6-(N-pyrrol-1-yl)purine (6 and 7) as well as 9-and 7-(2,3-diacetoxyprop-1-yl)-6-(N-pyrrol-1-yl)purine (8 and 9). Analysis of the characteristic bands has proved to be useful in differentiating between N-9 and N-7 regioisomers.     

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.     

Non-abelian electrodynamics and the vacuumB (3)

By using an 0(3) gauge group, a non-Abelian theory of vacuum electrodynamics is developed in which the newly discovered longitudinal vacuum fieldsB ⁽³⁾ andi E ⁽³⁾ appear self-consistently with the usual plane wavesB ⁽¹⁾,B ⁽²⁾,E ⁽¹⁾, andE ⁽²⁾ in the circular basis (1), (2), (3), a complex representation of space. Using the charge quantization condition the vacuum Maxwell equations are given in the non-Abelian representation.     

Structural Assignment of Stilbenethiols and Chalconethiols and Differentiation of Their Isomeric Derivatives by Means of 1H‐ and 13C‐NMR Spectroscopy

Abstract

The ¹H‐ and ¹³C‐NMR spectra of some substituted stilbenes and chalcones were assigned unambiguously on the basis of a combination of homo‐ (COSY) and heteronuclear (HETCOR) two‐dimensional methods, the chemical shifts, as well as spin‐coupling constants. The A_ik empirical parameters of the –O–C(S)–N(CH₃)₂, –S–C(O)–N(CH₃)₂, and –SH group were calculated to help predict the chemical shifts of substituted stilbenes, 4′‐nitrostilbenes, and chalcones. The ¹H‐ and ¹³C‐NMR spectra have been shown to be able to differentiate between the isomers of O‐stilbenyl (4, 5) and S‐stilbenyl N,N‐dimethylthiocarbamates (7, 8) as well as O‐chalconyl (6) and S‐chalconyl N,N‐dimethylthiocarbamates (9).     

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.     

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.     

Magnetization of an electron plasma by microwave pulses: Faraday induction

It has been argued theoretically that the recently proposed vacuum fieldB ⁽³⁾ is not accompanied by a real electric fieldE ⁽³⁾ . Experimental evidence for this interence is available in the data reported by Deschampset al. [10], using microwave magnetization of an electron plasma set up in helium gas. Faraday induction due toB ⁽³⁾ does not occur in the inert gas and is not observed experimentally in the absence of free electrons. WheneverB ⁽³⁾ interacts with free electrons, however, Faraday induction occurs through a pulse of induced magnetization (i.e., induced orbital electronic angular momentum).     

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.     

Magnetic properties of erbium iron garnet in high magnetic fields up to 150kOe

The magnetic properties of single crystals of erbium iron garnet (ErIG) were studied in applied fields up to 150kOe between 1.4 and 300K. At low temperature, the macroscopic easy direction of the bulk magnetization is [100]; below the compensation temperature (80±2K), the magnetization presents non-linear field evolution. On the assumption of an isolated ground doublet, the anisotropy constantsK _i (i=1,2) of ErIG are given byK _i (Er)+K _i (YIG); theK _i are calculated as a function of theG andg tensor components. It is worthwhile noting that theK _i (Er) are strongly temperature dependent; so at low temperature the anisotropy of the garnet is determined by the rare earth ions, while in the 50 K regionK ₁(Er) becomes comparable toK ₁(YIG) with the opposite sign which results in a very weak anisotropy of the garnet. Above 50 K,K ₁(YIG) is predominant and the Fe³⁺ ions determine the garnet anisotropy.     

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     

The connection between photon mass andB (3) : The poincaré group

The longitudinal vacuum fieldB ⁽³⁾ is an experimental observable which produces by magnetization a well-defined square-root beam power density dependence. Its longitudinal polarization implies that the helicities of the photon are +1, 0, and –1, and that the little group of the Poincaré group is the rotation group 0(3) of a massive boson. The mass of the photon (m) is therefore related directly toB ⁽³⁾ through the Proca equation, and it is concluded that experimental evidence forB ⁽³⁾ is also evidence for finitem.     

Two-Particle Irreducible Effective Action in Gauge Theories

The goal of this paper is to develop the formalism of the two-particle irreducible (2PI) (G. Baym (1962). Physical Review 127, 1391; H. D. Dahmen and G. Jona Lasino (1962). Nuovo Cimento A 52, 807; C. de Dominicis and P. Martin (1964). Journal of Mathematical Physics 5, 14; J. Luttinger and J. Ward (1960). Physical Review 118, 1417; B. Vanderheyden and G. Baym (1998). Journal of Statistical Physics 98, 843; B. Vanderheyden and G. Baym (2000). In Progress in Nonequilibrium Green's Functions, World Scientific, Singapore). (or Cornwall–Jackiw–Tomboulis (CJT) (J. Cornwall, R. Jackiw, and E. Tomboulis (1974). Physical Review D 10, 2428; U. Kraemmer and A. Rebhan (2004). Reports on Progress in Physics 67, 351; R. Norton and J. Cornwall (1975). Annals of Physics 91, 106) effective action (EA) in a way appropiate to its application to nonequilibrium gauge theories. We hope this review article will stimulate new work into this field.     

Electron phonon interactions and superconductivity in α ′ -TTF[Pd(dmit)2]2

A simple model is developed to understand superconductivity in α ^′ -TTF[Pd(dmit)₂]₂. We include electron-intra molecular and intermolecular phonon interactions as the mechanism of superconductivity. Intramolecular vibrations included are the eight symmetric A_g modes of the Pd(dmit)₂ molecule. Intermolecular vibrations included are the longitudinal acoustic and transverse acoustic (LA and TA) modes of the Pd(dmit)₂ column. All the electron-phonon coupling constants are calculated from first principles. We find that largest el-intramolecular vibration coupling is to the A_g mode with the highest frequency (1449 cm^-1). The el-intermolecular coupling to the LA mode is found to be larger than the total el-intramolecular couplings. We also find el-(TA)phonon coupling to be at least an order of magnitude smaller than el-(LA)phonon coupling. Estimate of superconducting transition temperature is comparable to experimental result. We also provide a detailed discussion, employing the results of recent numerical calculations on two-chain Hubbard model and the specific material parameters, on the relative importance of el-ph and Coulomb-origin mechanisms of superconductivity in α ^′ -TTF[Pd(dmit)₂]₂ and TTF[Ni(dmit) ₂ ] ₂ . Received 29 March 2001 and Received in final form 7 August 2001     

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.     

Theoretical study on the influence of different NˆN ligands on the electronic structures and optoelectronic properties of heteroleptic Iridium(III) complexes

DFT/TDDFT calculations were carried out to investigate the electronic structures, absorption and phosphorescence properties of a series of heteroleptic Ir(III) complexes consisting of two N-heterocyclic carbene ligands and a conjugated bicyclic N,N′-heteroaromatic (N?N) ligand. On the basis of the results reported herein, we attempt to explain the experimental observations according to which complex (mpmi)₂Ir(pybi) (1) [Hmpmi = 1-(4-tolyl)-3-methyl-imidazole; Hpybi = 2-(pyridin-2-yl)-1H-benzo[d]imidazole] emits green light with an extremely high-quantum phosphorescence efficiency (Φ _PL ) of 79.3%, while a relatively lower Φ _PL (only 11%) was measured for (fpmi)₂Ir(tfpypz) (2) [fpmi = 1-(4-fluorophenyl)-3-methylimdazolin-2-ylidene-C, C^2′; tfpypz = 2-(3-(trifluoromethyl)-1H-pyrazol-5-yl)pyridinato] emitting blue light by tuning the N?N ligands. Besides, we also designed (fpmi)₂Ir(pyN3) (3) [pyN3H = 2-(5-(trifluoromethyl)-2H-1,2,4-triazol-3-yl)pyridine] and (fpmi)₂Ir(pyN4) (4) [pyN4H = 2-(1H-tetrazol-5-yl)pyridine] to explore the influence of electron-withdrawing substituents on N?N ligands on the electronic and optical properties of these Ir(III) complexes. The results revealed that electron-withdrawing substituents can stabilise both HOMOs and LUMOs and induce HOMO–LUMO energy gap change. Moreover, the emission properties can be significantly tuned by introducing different N?N ligands. While new insights were gained on structural and electronic properties, the extremely high Φ _PL of 1 was found to be not inherent to spin-orbital coupling effects, but determined by its large transition dipole moment (μ_{S 1}) upon S ₀–S ₁ transition compared with that of 2. On the basis of these results, the designed complexes 3 and 4 are considered to be the promising candidates for blue-emitting phosphorescence materials with higher Φ _PL than the complex 2.     

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     

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.

     

Passive scalar in a large-scale velocity field

We consider advection of a passive scalar θ(t,r) by an incompressible large-scale turbulent flow. In the framework of the Kraichnan model all PDF’s (probability distribution functions) for the single-point statistics of θ and for the passive scalar difference θ(r ₁)−θ(r ₂) (for separations r ₁−r ₂ lying in the convective interval) are found. Zh. éksp. Teor. Fiz. 115, 920–939 (March 1999) Published in English in the original Russian journal. Reproduced here with stylistic changes by the Translation Editor.     

Packing of molecules and hole formation in lyotropic systems

A vector field q (the order parameter of the molecular packing) describing the packing (specifically, the orientation) of membrane-forming amphiphilic molecules is introduced to describe the structures of lyotropic phases constructed from membranes. In the general case q·n≠0 (where n is the unit normal vector) and therefore the singularities of the vector field q are not determined uniquely by the topology of the surface. The condition q·n=0 signifies disruption of the packing of the molecules. This corresponds to holes, which can form in membranes when lyotropic systems are diluted. As an illustration, the simplest type of such singularities, in which the distribution of the field q around a hole is described by a part of an instanton with unit topological charge, is studied. It is shown that such a distribution guarantees the existence of a local minimum under the condition that the tension per unit length λ of the hole boundary is small compared with the deformation energy of the field q: λh/K≪l (K is the modulus of the orientational elasticity of the field q and h is the thickness of the membrane). The radius of the hole which is formed equals L≈2.52(K/λh)^1/3 and the energy E≈59.79K(λh/K)^1/3. Pis’ma Zh. éksp. Teor. Fiz. 64, No. 8, 575–580 (25 October 1996)     

The effect of ligands on the first hyperpolarizabilities of rich d electron molecular system: iridium clusters,a TDDFT study

A systematically varied series of tetrahedral iridium clusters have been studied using a TDDFT method focusing on their electronic and nonlinear optical properties. The clusters W₂Ir₂(CO)₁₀(η⁵-C₅H₄Me)₂ (1), WIr₃(μ-dppe)(CO)₉(η⁵-C₅H₄Me (2), W₂Ir₂(μ-L)(CO)₈(η⁵-C₅H₄Me)₂(L = dppe 3, dppf 4), Ir₄(μ-L)(CO)₁₀(L = dppm 5, dppe 6, Ph₂P(CH₂)₃PPh₂ 7, Ph₂P(CH₂)₄PPh₂ 8, (Ph₂P)₂CHMe 9), Ir₄(CO)₁₀(phen)(phen = 1,10-phenanthroline) (10) exhibit the first static hyperpolarizabilities of medium magnitude (β _tot ～ 10 × 10^?30esu). The origination of β is discussed in terms of the electronic structure calculation and the expanded orbital decomposition scheme. The result suggests the origination of β for all the clusters are mainly d–d electron transitions intra metal skeleton, and d–π* electron transitions from metals to carbonyls. For cluster 5, which contains the ferrocenyl group, the main origination of β involves charge transfer from d orbitals of ferrocene to d orbirals of Ir and W.