Fluorescence Studies on New Potential Antitumoral Benzothienopyran-1-ones in Solution and in Liposomes

Fluorescence properties of four new potential antitumoral compounds, 3-arylbenzothieno[2,3-c]pyran-1-ones, were studied in solution and in lipid membranes of dipalmitoyl phosphatidylcholine (DPPC), egg yolk phosphatidylcholine (Egg-PC) and dioctadecyldimethylammonium bromide (DODAB). The 3-(4-methoxyphenyl)benzothieno[2,3-c]pyran-1-one (1c) exhibits the higher fluorescence quantum yields in all solvents studied. All compounds present a solvent sensitive emission, with significant red shifts in polar solvents for the methoxylated compounds. The results point to an ICT character of the excited state, more pronounced for compound 1c. Fluorescence (steady-state) anisotropy measurements of the compounds incorporated in liposomes of DPPC, DODAB and Egg-PC indicate that all compounds have two different locations, one due to a deep penetration in the lipid membrane and another corresponding to a more hydrated environment. In general, the methoxylated compounds prefer hydrated environments inside the liposomes. The 3-(4-fluorophenyl)benzothieno[2,3-c]pyran-1-one (1a) clearly prefers a hydrated environment, with some molecules located at the outer part of the liposome interface. On the contrary, the preferential location of 3-(2-fluorophenyl)benzothieno[2,3-c]pyran-1-one (1b) is in the region of lipid hydrophobic tails. Compounds with a planar geometry (1a and 1c) have higher mobility in the lipid membranes when phase transition occurs.     

Conformational analysis of 2,3-dihydro-3-O-(1,4-naphthoquinon-2-yl)-2-oxo-1,4-naphthoquinone derivatives by the density functional method and IR spectroscopy

We have used the PBE/3z, B3LYP/6-31G, B3LYP/6-31G(d), and B3LYP/6-311G(d) methods to study the conformational mobility of 2,3-dihydro-3-O-(1,4-naphthoquinon-2-yl)-2-oxo-1,4-naphthoquinones (1–4). We have shown that more than 99% of these compounds exist as the major tautomeric form, while differences in the structure of the Q_2H (2,3-dihydro-2-oxo-1,4-naphthoquinones) and Q_1,4 (1,4-naphthoquinon-2-yl) moieties lead to qualitative differences in the internal rotation potentials of the ethyl substituents V(θ_Et−1) and V(θ_Et−2), and consequently each of compounds 1−4 exists as six different rotameric forms. For diquinone 3, we have calculated the dependences of the frequencies (ν) and intensities (A) of the normal vibrations on the torsional angles θ_Et−1 and θ_Et−2, and also on the changes in the geometry of the ether bond. We have found that the values of ν and A for the bands in the carbonyl region of the IR spectrum change little on going from one rotameric form to another, and also for the in-plane bends of the ether bond, and change considerably for the out-of-plane bends of the ether bond. However, for T ≤ 300 K, there is no qualitative change in the overall contour, and it can be interpreted based on a simple additive model. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 73, No. 5, pp. 573–581, September–October, 2006.     

Fluorescence of a Benzothienopyridopyrimidone in Solution and in Lipid Vesicles

Fluorescence properties of a biologically active benzothienopyridopyrimidone in solution and in lipid vesicles are reported. Assays at different pH values (0.5–10) allowed the determination of pK _a = 2.0, showing that this compound may be useful as a pH indicator for pH ≤ 4. In lipid vesicles, benzothienopyridopyrimidone locates in a water-rich environment, indicating that it can be carried in the hydrophilic region of liposomes for drug delivery applications.     

Theory of XMCD spectra at the L2,3 absorption edges of mixed valence Ce and Yb compounds in high magnetic fields

We examine the structure of aggregates formed due to DNA interaction with dipalmitoylphosphatidylcholine (DPPC) in presence of Ca²⁺ and Zn²⁺ using small-angle synchrotron X-ray diffraction (SAXD) and neutron scattering (SANS). SAXD shows structural heterogeneity as a function of the cation concentration and temperature: At low cation concentration (∼1 mM), aggregates show two DPPC phases, one with a lateral segregation of DNA and cation, while higher cation concentration improves the DNA packing and the condensed lamellar phase is observed in DNA+DPPC+20mMion²⁺ aggregates. The SANS detected the dissolution of the condensed lamellar phase into unilamellar DPPC+Zn²⁺ vesicles due to gel ↦ liquid-crystal phase transition in DNA+DPPC+20mM Zn²⁺ aggregates with the short fragmented salmon sperm DNA.     

Determination of the rate of rapid lipid transfer induced by poly(ethylene glycol) using the SLM Fourier transform phase and modulation spectrofluorometer

Rate constants were determined for the transfer of the fluorescent lipid probe 1-palmitoyl-2-[[2-[4-(6-phenyl-trans-1,3,5-hexatrienyl)phenyl]ethyl] oxy]carbonyl]-3-sn-phosphatidylcholine (DPHpPC) between large, unilamellar extrusion vesicles composed either of dipalmitoyl phosphatidylcholine (DPPC) or of DPPC mixed with a small amount (0.5 mol%) of lyso phosphatidylcholine (Lyso PC). Transfer of the lipid probe in the presence of varying concentrations of poly(ethylene glycol) (PEG) was monitored using the SLM 48000-MHF Multi-Harmonic Fourier Transform phase and modulation spectrofluorometer to collect multifrequency phase and modulation fluorescence data sets on a subsecond time scale. The unique ability of this instrument to yield accurate fluorescence lifetime data on this time scale allowed transfer to be detected in terms of a time-dependent change in the fluorescent lifetime distribution associated with the lipid-like DPHpPC probe. This probe demonstrates two short fluoresence decay times (ca. 1.1–1.4 and 4.3–4.8 ns) in a probe-rich environment but a single long lifetime (ca. 7 ns) in a probe-poor environment. A simple two-state model for initial lipid transfer was used to analyze the multifrequency data sets collected over a 4-s time frame to obtain the time rate of change of the concentrations of donor and acceptor probe populations following rapid mixing of vesicles with PEG. The ability to measure fluorescence lifetimes on this time scale has allowed us to show that the of rate of lipid transfer increased dramatically at 35% PEG in both fusing and nonfusing vesicle systems. These results are interpreted in terms of a distinct interbilayer structure associated with intimate bilayer contact induced by high and potentially fusogenic concentrations of PEG.     

Structural and electrical characterization of MxNb3Se4 (M = Cu, H)

The compounds Cu_xNb₃Se₄ (0≤x≤0,45) and H_xNb₃Se₄ (0≤x≤2·10⁻³) were prepared by electrochemical titration from Nb₃Se₄. The samples were characterized by X-ray analysis and q-probe conductivity measurements as a function of temperature. The Cu-compound is isostructural with Nb₃Se₄ for 0≤x≤0.2 and shows new phases for 0,2≤x≤0,45. The H-compound shows an impurity controlled conductivity in the temperature range from 20 to 200 °C and an intrinsic type conductivity in the temperature range from 330 to 450 °C. The activation engines are 0 and 0.15 eV, respectively. Rapid proton conduction in H_xNb₃Se₄ makes it difficult to control the composition as demonstrated by exposure of the samples to different atmospheres. An increasing H-concentration decreases drastically the conductivity by several orders of magnitude.     

Efficient synthesis and free-radical scavenging capacity of new 2,4-substituted tetrahydroquinolines prepared via BiCl<Subscript>3</Subscript>-catalyzed three-component Povarov reaction,using <Emphasis Type="Italic">N</Emphasis>-vinylamides

Efficient synthesis of new structurally different 2-(het)aryl-4-amidyl-substituted tetrahydroquinolines 8–29 is reported. The synthesis based on BiCl₃-catalyzed three-component Povarov reaction between anilines, (het)aryl aldehydes and enamides offers a fast, safe, and cheap way for efficient tetrahydroquinoline libraries construction. Using N-vinylamides (N-vinylpyrrolidin-2-one and N-vinylacetamide) in this reaction, it was possible to obtain two series of different cis tetrahydroquinolines with antioxidant properties. Among 14 tested compounds, 7 tetrahydroquinolines revealed a prominent anti-radical capacity, equal or higher than that of the commercial antioxidants. Being the most active molecule, the N-[2-(α-furanyl)-6-methoxy-1,2,3,4-tetrahydroquinolin-4-yl] acetamide 21 was ca. 2.2-fold more potent than the well-known antioxidant, vitamin E (α-tocopherol).     

Dipyrenylphosphatidylcholine as a probe of bilayer pressures

We have used dipyrenylphosphatidylcholines (dipyPCs) to study the pressure in the fluid lamellar phase formed by mixtures of fully hydrated dioleoylphosphatidylcholine (DOPC) and dioleoylphosphatidylethanolamine (DOPE). As we increase the DOPE mole fraction at 25°C we observe a linear increase in the ratio of the excimer-to-monomer signal (E/M1). We argue that this observation can be understood in terms of an increase in the lateral pressure in the chain region, i.e., in the bilayer plane. This change itself is driven by the decrease in lateral pressure between headgroups as we add DOPE. We expect the lateral pressure to vary in magnitude as we probe the bilayer at different depths [1]. We have confirmed this by recording E/M1 using di[10-(pyren-1-yl)decanoyl]phosphatidylcholine (10dipyPC) and di[4-(pyren-1-yl)butanoyl]phosphatidylcholine (4dipyPC). We find that in 100% DOPC the E/M1 for 4dipyPC is 2.5 times greater than that for 10dipyPC. The above observations can all be rationalized in terms of changes in the lateral pressure profile. An inverse hexagonal liquid crystalline phase is found in the range 100–83% DOPE [2]. In this region of the phase diagram we observe a quadratic variation in E/M1, with a minimum at 95% DOPE. We hypothesize that this variation reflects the chain stretching that is necessitated by the geometrical packing constraints of the hexagonal phase [3]. Again, we find that the E/M1 for 4dipyPC is greater than that for 10dipyPC, but in this phase only by a factor of two.     

Comment: “On the computation of molecular auxiliary functions<Emphasis Type="Italic">A</Emphasis><Subscript>n</Subscript>and<Emphasis Type="Italic">B</Emphasis><Subscript>n</Subscript>”

Guseinov, Mamedov, Kara and Orbay (Pramana - J. Phys. 56, 691 (2001)) propose methods for evaluating the molecular auxiliary functionsA _n(p) andB _n(pt) for the range 17 ≤n ≤ 60 and 25 ≤pt ≤ 60. However, their procedure forA _n(p) is not new, and that forB _n(pt) is less efficient for their target range than another well-known method. Their approach does have merit for smaller non-zero values ofpt. Two minor errors in table 1 of their paper are also identified.     

Spectrophotometric Characteristics of New Pyridylindolizine Derivatives Solutions

Three new pyridylindolizine derivatives, 1, 2, 3-tricarbometoxi-7-(4-pyridyl)-pyrrolo[1, 2-a]pyridine (I), 1,2-dicarboethoxy-3-(4-bromobenzoyl)-7-(4-pyridyl)-pyrrolo[1,2-a]pyridine (II) and its isomer 1,2-dicarboethoxy-3- (4-bromobenzoyl) -5- (2-pyridyl) -pyrrolo[1, 2-a]pyridine (III) have been investigated in different solutions by UV-VIS absorption, steady-state, and time-resolved fluorescence methods. The effects of the substituent and solvent on the spectroscopic properties have been demonstrated. The fluorescence decay data could be fitted to a single-exponential function. The lifetime values are higher in protic polar than in aprotic apolar solvents for compound I. In the case of compounds II and III the fluorescence intensities and lifetimes are very low, with the exception of III in aprotic solvents. The absorption and fluorescence properties of the compounds showed a solvent dependence.     

Magnetic and structural transitions in La1−x Sr x MnO3: T-x phase diagram

The electrical conductivity, magnetic susceptibility, magnetization, and submillimeter (v=5∓20 cm⁻¹) permittivity and dynamic conductivity of La_1−x Sr _x MnO₃ (0≤x≤ 0.45) single crystals are investigated. The anomalies in the temperature dependences of these quantities are identified with diverse magnetic and structural phase transformations, including antiferromagnetic and ferromagnetic ordering, structural transitions between strongly distorted (Jahn-Teller) and weakly distorted (pseudocubic) orthorhombic phases, structural transitions to a rhombohedral phase and unusual transitions to a polaron-ordering state. As a result, the complete T-x phase diagram of the system La_1−2x Sr _x MnO₃ is constructed in a wide interval of temperatures T=4.2∓1050 K and concentrations x=0−0.45. Pis’ma Zh. éksp. Teor. Fiz. 68, No. 4, 331–336 (25 August 1998)     

Magnetic structure of Ce<Subscript>2</Subscript>Fe<Subscript>17 − <Emphasis Type="Italic">x</Emphasis></Subscript>Mn<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript> intermetallic compounds

The magnetic structure of intermetallic compounds Ce₂Fe_{17 − x} Mn _x (0 ≤ x ≤ 3) was studied using neutron diffraction. The neutron diffraction patterns measured at 4.2 K contain satellites indicating a modulated structure with the wave vector k = [0, 0, τ]. As the concentration x increases, the value of τ increases, while the average magnetic moment of Fe/Mn atoms decreases. A change in the magnitudes of the average magnetic moment and wave vector k is explained by competition between exchange interactions at distances of nearest neighbor transition element atoms.     

3D Visualization of the separated fluid flows

For the detailed investigation of the 3D unsteady incompressible viscous separated fluid flows around a sphere (for 200≤Re≤700) and a circular cylinder (for 200≤Re≤400) the direct numerical simulation and 3D visualization are used. For 3D visualization of the fluid flows around a sphere the definition of vortex core as a connected region containing two negative eigenvalues of theS ²+Ω ² tensor is used (whereS _i,j andΩ _ij are the rate of strain and the rate of rotation tensors). The formation mechanism of vortices in the sphere wake for Re=500 is described in detail. For 3D visualization of the fluid flows around a circular cylinder the 3D isosurfaces of the streamwise component of vorticity ω _x are used.     

Influence of magnetic field on the superconducting transition in a Nd1.82Ce0.18CuO4−δ film

The temperature and magnetic-field dependences of the resistivity ρ and Hall effect R(j‖ab, B‖c) in a Nd_1.82Ce_0.18CuO_4−δ single crystal film (T _c =6 K) is investigated at temperatures 1.4≤T≤20 K and magnetic fields 0≤B≤5.5 T. At the lowest temperature T=1.4 K the resistive state (exhibiting resistivity and the Hall effect) arises in a magnetic field B=0.5 T. A transition to the normal state is completed at B _c 2≃3 T, where the Hall coefficient becomes nearly constant. The negative magnetoresistance due to the weak-localization effect in the normal state is observed for B>3 T. The nonmonotonic behavior and the inversion of the sign of R(B) in the mixed state are explained in a reasonable way by the flux-flow model with the effect of pinning taken into account. Pis’ma Zh. éksp. Teor. Fiz. 64, No. 6, 407–411 (25 September 1996) Published in English in the original Russian journal. Edited by Steve Torstveit.     

Reliability of stopping power tables and codes for heavy ions (8 ≤ Z ≤ 92) in gases

A comparative study of various stopping power tables and codes for heavy ions in gases has been made through comparison of computed values and the corresponding experimental data. Ten gaseous media: five monatomic rare gases (He to Xe), two diatomic gases (H₂, N₂) and three polyatomic gaseous compounds (CH₄, CF₄ and CO₂) have been chosen to study the stopping power investigations of heavy ions (8 ≤ Z ≤ 92) having energy ranges of ∼0.10–10.00 MeV/n and ∼20.00–57.00 MeV/n. We compare the experimental data of stopping power to values calculated using various tables and computer codes by ICRU-73, Ziegler et al (SRIM2003.26), Grande and Schiwietz (CasP3.1), Paul and Schinner (MSTAR3.12), and Bazin and Tarasov (LISE ++:2-ATIMA1.2). On the basis of statistical analysis, we estimate the reliability of these tables and codes. It has been observed that the MSTAR3.12 code shows the best agreement with the experimental data for projectile ions (8 ≤ Z ≤ 18) in the entire energy range. The SRIM2003.26 code provides good results except for some heavy projectiles (Xe, Pb and U). The values tabulated by CasP3.1 code underestimate especially at low energy region. No significant trend is observed in case of LISE++:2-ATIMA1.2 code and ICRU-73 report.     

Magnetization and resistivity steps in the phase separated PrCaMn NiO manganites

The low temperature magnetic and transport properties of the Pr_0.5Ca_0.5Mn_1-xNi_xO₃ manganites ( 0≤ x ≤0.1) have been investigated. The presence of Ni hinders the charge and orbital ordering observed in Pr_0.5Ca_0.5MnO₃ and favors the creation of ferromagnetic regions, leading to phase separation. The ferromagnetic fractions induced by the Ni substitution have been estimated from magnetization measurements, they are large and reach 40% for 4% of Ni. Steps are observed in the M ( H ) and ρ( H ) curves of all the samples at T < 5 K. They are similar to the steps observed in Pr_0.5Ca_0.5Mn_1-xM_xO₃, where M is a non magnetic cation (Mg²⁺, Ga³⁺,...), and for which the ferromagnetic fractions are very small (less than 2%), however, their appearance is restricted to lower temperatures (T < 5 K) with Ni dopant than with non magnetic cations. This study shows that steps can be observed in a wide range of phase-separated systems, even when the ferromagnetic fraction is very large. Received 5 April 2002 / Received in final form 8 July 2002 Published online 14 October 2002 RID="a" ID="a"e-mail: antoine.maignan@ismra.fr     

A study of iso- and alio-valent cation doped Ag2SO4 solid electrolyte

2 SO₄. The solid solubility limits up to x≤3 mole% for monovalent, x≤5.27 mole% for divalent and x≤3.63 mole% for trivalent cation doped Ag₂SO₄ are set with XRD, SEM, IR and DSC techniques. A predominant dependence of conductivity on the ionic size of iso- and alio-valent cations is observed. In particular, the conductivity enhances in both α and β phases, despite having a lower ionic-size dopant cation (relative to that of Ag⁺) in the transition element cation doped Ag₂SO₄. Ca²⁺, Ba²⁺, Y³⁺ and Dy³⁺ doped samples show depature from the regular behaviour in the β-phase. The conductivity behaviour is discussed considering ionic size, valence and electronic structure of the guest cations. Received: 3 February 1997/Accepted: 27 May 1997     

Calculation of frequencies of normal vibrations and interpretation of IR spectra for 2,3-dihydro-3-O-(1,4-naphthoquinon-2-yl)-2-oxo-1,4-naphthoquinone derivatives

We have used B3LYP/6-31(d) density functional theory to calculate the frequencies and modes of the normal vibrations of 2-oxo-2,3-dihydro-and 2-methoxy-1,4-naphthoquinones. Based on these calculations within an additive model, we have assigned the carbonyl bands in the IR spectra of 2,3-dihydro-3-O-(1,4-naphthoquinon-2-yl)-2-oxo-1,4-naphthoquinones (diquinones 1–4). We have carried out a direct calculation of the vibrational spectra for diquinones 1–4 using PBE and B3LYP correlation functionals. We have shown that the calculation of the vibrational spectra of the diquinones based on an additive model on the whole is quite consistent with the results of direct calculations and the experimental spectra. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 73, No. 6, pp. 713–720, November–December, 2006.     

Synthesis and Characterization of Triphenylethylene Derivatives with Aggregation-Induced Emission Characteristics

New aggregation-induced emission (AIE) compounds derived from triphenylethylene were synthesized. The thermal, photophysical, electrochemical and aggregation-induced emissive properties were investigated. All the compounds had strong blue light emission capability and good thermal stability. Their maximum fluorescence emission wavelengths were between 443 to 461 nm in solid states, while their glass transition temperatures ranged from 86 to 129 °C. The decomposition temperatures of the synthesized compounds were in the range of 432–534 °C. The synthesized compounds possessed aggregation-induced emission properties, namely exhibited enhanced fluorescence emission in aggregated states. The highest occupied molecular orbital (HOMO) energy levels estimated from the oxidation potentials were between 5.61 and 5.66 eV and the lowest unoccupied molecular orbital/highest occupied molecular orbital (LUMO/HOMO) energy gap values were found to be in the range of 3.18–3.22 eV. The compounds 4-(4-(2,2-bis(4-(naphthalen-1-yl)phenyl)vinyl)phenyl) dibenzothiophene [(BN)₂Bt] and 4-(4-(2,2-di(biphenyl-4-yl)vinyl)phenyl) dibenzothiophene [(BB)₂Bt] exhibited vibronic fine-structure photoluminescence spectra when the water fraction was less than 70%.     

Photophysics and Electrochemistry of some Thione Far-Red/Near-IR Triplet Emitters

The photophysics and cyclic voltammetry of two novel phosphorescent thiones, 2,2-dimethyl-indan-1-one-3-thione (DMIKT) and 2,2-dimethyl-indan-1,3-dithione (DMIDT), and three known phosphorescent thiones, 4H-pyran-4-thione (PT), 4H-1-benzopyran-4-thione (BPT) and 2,2-dimethylindan-1-thione (DMIT), have been characterised and compared. The phosphorescence emission of DMIT, DMIKT and DMIDT extends from the red into the near-IR spectral region. The additional carbonyl or thione group of DMIKT and DMIDT causes a significant shift in the emission maxima to 680 nm compared to that of DMIT, at 637 nm, in perfluorinated hydrocarbons. In acetonitrile the emission maxima of DMIKT and DMIDT are at 696 and 706 nm, respectively, and the spectra show vibronic bands which extend out beyond 850 nm. There is a significant reduction in triplet lifetime along this series (from 44 (±2) μs (DMIT) to 10 ((±0.8) μs (DMIKT) in perfluorinated solvents, and 8.6 (±0.5) (DMIT), 1.3 (±0.5) (DMIKT) and 0.35 (±0.07) μs (DMIDT) in acetonitrile), as well as a reduction in the rate constant for ground-state quenching of the triplet, (from 9.8 ((±0.9) to 3.5 ((±0.6) and 1.3 ((±0.2) × 10⁹ mol⁻¹ dm³ s⁻¹ for the same compounds). The addition of the C=O or C=S groups also causes a decrease in phosphorescence quantum yield with the highest emission quantum yield obtained for DMIT (Φ _P = 0.149 (±0.015)). Electrochemical studies show that while PT and BPT exhibit irreversible redox behaviour, DMIT, DMIKT and DMIDT all show at least one reversible reduction wave attributed to a one-electron process centred on the C=S moiety. The suitability of these lumophores for use in OLEDs is discussed.