Synthesis and Characterization of New Fluorene-Based Singlet Oxygen Sensitizers

The synthesis, photophysical characterization, and determination of singlet oxygen quantum yields (Φ_Δ) for a class of fluorene derivatives with potential application in two-photon photodynamic therapy (PDT) is reported. It has been demonstrated that these compounds possess the ability to generate singlet oxygen (¹O₂) upon excitation. A photochemical method, using 1,3-diphenylisobenzofuran (DPBF) as ¹O₂ chemical quencher, was employed to determine the singlet oxygen quantum yields (Φ_Δ) of the fluorene-based photosensitizers in ethanol. Φ_Δ values ranged from 0.35 to 0.75. These derivatives may have potential application as two-photon photosensitizers when pumped via two-photon excitation in the near-IR spectral region.     

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.     

Synthesis, Characterization, DNA-Binding and Antiproliferative Activity of Nd(III) Complexes With N-(Nitrogen Heterocyclic) Norcantharidin Acylamide Acid

Three novel complexes [Nd(L)(NO₃)(H₂O)₂]·NO₃·2H₂O (HL¹ = N-pyrimidine norcantharidin acylamide acid, C₁₂H₁₃N₃O₄; HL² = N-pyridine norcantharidin acylamide acid, C₁₃H₁₄N₂O₄; HL³ = N-phenyl norcantharidin acylamide acid, C₁₄H₁₅NO₄) were synthesized. HL¹, HL² and HL³ are the ligand of complex(1), complex(2) and complex(3), respectively. Their structures were characterized by elemental analysis, conductivity measurement, infrared spectra and thermogravimetric analysis. The DNA-binding properties of the complexes have been investigated by fluorescence spectroscopy and viscosity measurements. The results suggest that the complexes can bind to DNA by partial intercalation. The liner Stern-Volmer quenching constant K_sq values are 3.3(±0.21)(1), 1.7(±0.19)(2) and 0.9(±0.04)(3), respectively. Complex (1) and (2) have been found to cleave pBR322 plasmid DNA at physiological pH and temperature. The test of antiproliferation activity indicates that complex(1) has strong antiproliferative ability against the SMMC7721 (IC₅₀ = 131.7 ± 23.4 μmol·L⁻¹) and A549 (IC₅₀ = 128.4 ± 19.9 μmol·L⁻¹) cell lines. The inhibition rates of complex(2) (IC₅₀ = 86.3 ± 11.3 μmol·L⁻¹) are much higher than that of NCTD (IC₅₀ = 115.5 ± 9.5 μmol·L⁻¹) and HL² (111.0 ± 5.7 μmol·L⁻¹) against SMMC7721 cell lines.     

Centrifugal spray generator of singlet oxygen for a chemical oxygen-iodine laser

A centrifugal spray generator of singlet oxygen, O₂(¹Δ_g), for driving a chemical oxygen-iodine laser was developed and its operation was experimentally studied. Modeling of the liquid separation from the gas flow showed that the separator designed could remove droplets larger than 0.5 μm from gas, which is very important for the laser operation. This result was confirmed by experiments. Experimental studies proved that O₂(¹Δ_g) could be produced with a high efficiency (chlorine utilization 0.68–0.87 and O₂(¹Δ_g) yield 0.35–0.7) even at very high generator pressures (25–70 kPa), which cannot be attained by other O₂(¹Δ_g) generators.     

Study of the isobar configurations in the <Superscript>12</Superscript>C and <Superscript>16</Superscript>O ground states

Experimental research on positive-pion photoproduction on the oxygen nucleus in the ¹⁶O(γ, π⁺p) reaction at high recoil momenta of the residual nuclear system was performed. The yield for the ¹⁶O(γ, π⁺p) reaction was analyzed using a model that takes Δ-isobar configurations in nuclei ground states into account, together with the earlier-measured yield of the¹²C(γ, π⁺p) reaction. The estimated number of isobars per nucleon N _Δ = 0.012 ± 0.005 was obtained for the ¹²C nucleus, and ¹⁶O N _Δ = 0.018 ± 0.004 was obtained for the ¹⁶O nucleus.     

Formation and quenching mechanisms of excited particles in an oxygen-iodine laser medium

New values of a number of kinetic constants of processes proceeding in oxygen-iodine laser media are presented. The total probabilities of formation of I₂(X, 15 ≤ v ≤ 24) and I₂(X, 25 ≤ v ≤ 47) molecules in the course of quenching of I* atoms by I₂(X) are found to be 0.9 and 0.1, respectively. The quantum yield of singlet oxygen in the reaction O(¹ D) + N₂O → N₂ + O₂(a ¹Δ) is close to 100%. The quenching rate constants of I₂(A’) by O₂, H₂O, CO₂, I₂, and Ar and of I(² P _1/2) by O(³ P), O₃, NO₂, N₂O₄, and N₂O are presented.     

Spray generator of singlet oxygen for a chemical oxygen-iodine laser

A spray type of singlet oxygen generator for driving the Chemical Oxygen-Iodine Laser was developed. Singlet oxygen, O₂(¹Δ_g), is generated by a fast reaction of chlorine with basic hydrogen peroxide solution in the form of a dense spray. A mathematical model of this reaction system showed that O₂(¹Δ_g) can be generated in this system with a high yield (0.70–0.80), high utilization of chlorine (0.75–0.95), and effective utilization of liquid (0.36–0.54) at very high generator pressures (35–75 kPa). Experimental studies of this reaction system without an efficient separation of liquid proved an efficient O₂(¹Δ_g) production characterized by a rather high product of chlorine utilization and O₂(¹Δ_g) yield (0.4–0.9) at very high generator pressures (30–80 kPa). This pressure is much higher than the operation pressure used in other generators, which should be beneficial for a pressure recovery system of the COIL. These results provided the basis for designing a centrifugal spray generator with an efficient separation of liquid from the gas flow, which is the subject of the following paper.     

Azimuthal dependence of the two-photon absorption coefficient for CdP2 crystals with tetragonal syngony

We studied the two-photon absorption coefficient (β) for cadmium diphosphide (CdP₂) single crystals in the tetragonal modification vs. the polarization azimuth (φ) of the incident light for intensities close to the optical breakdown (or optical damage) threshold for the crystal (11 MW/cm²). We have established that the value of β_max = 0.16 cm/MW is reached for φ = 0, i.e., for the ordinary wave. At the lasing frequency of a ruby laser, β_⊥/β_|| = 2.13, which suggests anisotropy of the two-photon absorption in the studied crystals. These dependences are needed for design and fabrication of quantum electronics and nonlinear optics elements whose operation is based on the use of the two-photon absorption effect for high radiation fluxes. Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 76, No. 1, pp. 117–121, January–February, 2009.     

Mott-insulator-superfluid-liquid transition in a one-dimensional bosonic Hubbard model: Quantum Monte Carlo method

The values of the insulator gap Δ in one-dimensional systems of interacting bosons described by the Hubbard Hamiltonian are calculated at low temperatures by the quantum world-line Monte Carlo algorithm. The dependence of Δ on the size of the system, the temperature, and the parameters of the model is investigated. It is shown that a chain with N _a=50 sites is already sufficient to estimate the thermodynamic value of the critical quantity (t/U)_c for which a transition from the insulator into the superfluid state occurs in a commensurate system. To within the computational error, this value, (t/U)_c=0.300±0.005, agrees with the value (t/U)_c=0.304±0.002 obtained previously by the combined “exact diagonalization + renormalization-group analysis” method. The characteristic Kosterlitz-Thouless behavior of the insulator gap is demonstrated near the critical region: Δ∼exp[−b(1−t/t _c)^−1/2]. Pis’ma Zh. éksp. Teor. Fiz. 64, No. 2, 92–96 (25 July 1996)     

Synthesis,Electrochemical, and Optical Properties of New Fluorescent,Substituted Thieno[3,2-b][1]Benzothiophenes

The synthesis, electrochemical and optical properties of three fluorescent substituted thieno[3,2-b][1]benzothiophenes (TBT) derivatives, including 3-methoxythieno[3,2-b][1]benzothiophene (3-MeO-TBT), 2,3-dimethylthieno[3,2-b][1]benzothiophene (2,3-diMe-TBT), and 6-methoxythieno[3,2-b][1]benzothiophene-2-carboxylate (6-MeO-TBT-2-COOMe), were investigated. The oxidation potential values varied between 1.40 and 1.20 V/SCE according to the electronic substituent effect, and electropolymerization attempts, performed in 0.1 M LiClO₄ acetonitrile solution, led to the formation of very thin films of poly(3-MeO-TBT) and poly(2,3-di-Me-TBT). Electronic absorption spectra, fluorescence excitation and emission spectra, fluorescence quantum yields (Φ_F) , lifetimes (τ_F), and other photophysical parameters of the three new TBT derivatives were measured in DMSO solutions at room temperature. For the methyl-and methoxy-substituted TBT derivatives, the fluorescence emission peak were slightly red shifted relative to that of unsubstituted TBT (Δλ_em = 1–12 nm) whereas, in the case of 6-MeO-TBT-2-COOMe, a rather strong red-shift (Δλ_em = 73 nm) was attributed to the existence of a “push-pull” electronic interaction of the MeO and COOMe groups. All Φ_F values were rather high, varying between 0.11 and 0.35, according to the substituent effect. Fluorescence decays were mono-exponential and τ_F values were very short, ranging between 0.11 and 0.30 ns for the substituted TBT derivatives until study.     

Fluorescence spectroscopy of potential electroluminescent materials: Substituent effects on DSB and segmented PPV derivatives

The absorption and fluorescence of substituted distyrylbenzene (DSB) derivatives and segmented poly(phenylene vinylene) (PPV) derivatives are characterized by long-wavelength absorption maxima and absorption coefficients of λ_a = 380–450 nm, ε = 20,000–60,000 M⁻¹ cm¹ and fluorescence maxima, quantum yields, and decay times of λ_r = 440–530 nm, Φ_f = 0.2–0.9, and Τ = 0.8–2.5 ns, respectively. Alkoxy substituents at the central phenylene ring of DSB groups increase the bathochromic shift in the spectra in comparison to DSB, without a significant decrease in the high DSB fluorescence quantum yield. Both phenyl and cyano substitutions at the vinylene bridge lead to a further bathochromic shift of the fluorescence and a decrease in the quantum yield to ca. 0.4. The DSB derivatives and the related segmented PPV derivatives show nearly the same absorption spectra, fluorescence spectra, and radiative rate constantsk _f= Φ_f/Τ, indicating the efficacy of the segmentation of the polymer chain. The radiative rate constants determined by the Φ_f and Τ values and by the Strickler/Berg formula are in reasonable agreement. This supports the possibility of interpreting the properties of the polymers in terms of their DSB units. The decrease in the emission anisotropy can be ascribed to multistep energy transfer processes between different oriented segments.     

Highly improved electroluminescence from double-layer devices based on a carbazole-functionalized europium<Superscript>3+</Superscript> complex

A novel europium complex Eu(TTA)₃(CPPO)₂ (1) (TTA=thenoyltrifluoroacetone, CPPO=9-[4-(diphenyl-phosphinoyl)-phenyl]-9H-carbazole) based on the phosphine oxide ligand with bipolar structure was used to fabricate double-layer devices. The strong hole injection and transport ability of 1 was proved. The luminance of 414 cd m⁻² was achieved with the device configuration ITO/Eu(TTA)₃(CPPO)₂(40 nm)/BCP (30 nm)/Mg:Ag (BCP = 2, 9-dimethyl-4, 7-diphenyl-1, 10-phenanthroline), which is favorable among double-layer organic light emitting devices based on small molecular Eu³⁺ complexes. The maximum current efficiency of 2.44 cd A⁻¹ and external quantum efficiency of 1.55% demonstrate the potential application of 1 as a promising candidate for high-efficiency, simple-structure and pure red-emitting devices.     

Polarization dependence of luminescence induced by two-photon excitation in LiF crystals with F 3 + laser color centers and the symmetry of the excited state

The energy level structure of F ₃ ⁺ laser color centers in crystals of LiF is discussed. A high-power laser (λ _ex=920 nm) is used to excite luminescence from LiF crystals with F ₃ ⁺ centers via two-photon absorption, and the dependence of the polarization and intensity of this luminescence on the polarization of the laser light is measured and calculated. It is shown that the two-photon transition involves the excitation of a previously unknown state of the F ₃ ⁺ center—a spin singlet whose wave function has ¹ A ₁ symmetry. Fiz. Tverd. Tela (St. Petersburg) 39, 1373–1379 (August 1996)     

Synthesis, characterization, DNA binding and cleavage studies of mixed-ligand Cu(II) complexes of 2,6-bis(benzimidazol-2-yl)pyridine

Four novel copper(II) complexes of the composition [CuLX] where L = 2,6-bis(benzimidazole-2yl)pyridine, X = dipyridophenazine (L₁), 1,10-phenanthroline (L₂), hydroxyproline (L₃) and 2,6-pyridine dicarboxylic acid (L₄) were synthesized and characterized by using elemental analysis, FT-IR, UV–vis, ESI-MS, molar conductance and magnetic susceptibility measurements. The complexes [CuLL₁](NO₃)₂ [1], [CuLL₂](NO₃)₂ [2], [CuLL₃](NO₃) [3] and [CuLL₄] (NO₃) [4] are stable at room temperature. In DMSO the complexes [1] and [2] are 1:2 electrolytes, [3] and [4] are 1:1 electrolytes. Based on elemental and spectral studies five coordinated geometry is assigned to all the four complexes. The interaction of four copper ion complexes with calf thymus DNA were carried out by UV–vis titrations, fluorescence spectroscopy, thermal melting and viscosity measurements .The binding constant (K_b) of the above four metal complexes were determined as 5.43 × 10⁴ M_,⁻¹ 2.56 × 10⁴ M⁻¹, 1.21 × 10⁴ M⁻¹ and 1.57 × 10⁴ M⁻¹ respectively. Quenching studies of the four complexes indicates that these complexes strongly bind to DNA, out of all complex 1 is binding more strongly. Viscosity measurements indicate the binding mode of complexes with CT DNA by intercalation through groove. Thermal melting studies also support intercalative binding. The nuclease activity of the above metal complexes shows that 1, 2 and 3 complexes cleave DNA through redox chemistry.     

Fluorophotometric Determination of Hydrogen Peroxide with Fluorescin in the Presence of Cobalt (II) and Reaction Against Other Reactive Oxygen Species

A fluorophotometric method for the determination of hydrogen peroxide (H₂O₂) using fluorescin was developed. This method was based on the oxidative reaction of fluorescin, a colorless, non-fluorescent lactoid fluorescein, by H₂O₂ to give highly fluorescein fluorescence emission. In the determination of H₂O₂, the calibration curve exhibited linearity over the H₂O₂ concentration range of 1.5–310 ng mL⁻¹ at an emission wavelength of 525 nm with an excitation of 500 nm and with relative standard deviations (n = 6) of 2.51%, 2.48%, and 1.31% for 3.1 ng mL⁻¹, 30.8 ng mL⁻¹, and for 308 ng mL⁻¹ of H₂O₂, respectively. The detection limit for H₂O₂ was 1.9 ng mL⁻¹ six blank determinations was performed (ρ = 6). This proposed method was applied to detection of other reactive oxygen species and nitrogen species (ROS/RNS) such as singlet oxygen (¹O₂), hydroxyl radical (^•OH), peroxynitrite (ONOO⁻) etc., and it was possible to detect them with a high sensitivity. In addition, this proposed method was applied to the recovery tests of H₂O₂ in calf serum, human saliva, rain water, and wheat noodles; the results were satisfactory.     

Kinetics of formation of O2(1Σ) molecules in reactions involving excited O2(1Δ) oxygen molecules and I(2P1/2) iodine atoms

The results of our experimental study of the kinetics of formation of O₂(¹Σ) molecules in energy-exchange reactions O₂(¹Δ) + I(⁵ p,² P _1/2) and O₂(a,¹Δ) + O₂(a,¹Δ) are presented. The ratio of rate constants was obtained for these reactions (4800 ± 300). Setting the rate constant of the deactivation of O₂(¹Σ) molecules on CO₂ molecules at 4.1 · 10^–13 cm³/s, we evaluated the rate constants for these reactions at a temperature of approximately 330 K: (1.7 ± 0.2) · 10⁻¹³ and (3.6 ± 0.5) · 10⁻¹⁷ cm³/s, respectively.     

Dynamics and efficiency of the photosensitized singlet oxygen formation by chlorin <Emphasis Type="Italic">e</Emphasis><Subscript>6</Subscript>: The effects of the solution pH and polyvinylpyrrolidone

The effects of the solution pH and polyvinylpyrrolidone on the dynamics and efficiency of the formation of singlet oxygen ¹O₂ in buffer media (pH 6.3–8.5) photosensitized by chlorin e ₆ are studied. It is demonstrated that the quantum yield of the ¹O₂ formation photosensitized by chlorin e ₆ decreases with decreasing solution pH due to the aggregation of photosensitizer molecules. Polyvinylpyrrolidone facilitates the disaggregation of chlorin e ₆, thus increasing its photosensitizing ability. For a complex of chlorin e ₆ with this polymer, the luminescence kinetics of singlet oxygen is inverted, which should be taken into account in the determination of the lifetime of ¹O₂ in real biological systems.     

Role of charge-transfer complexes in oxygen quenching of excited states of anthracene derivatives in the gas phase

Oxygen quenching of excited triplet and singlet states of gas-phase anthracene and its derivatives that have similar energies of the lower triplet levels but widely different oxidation potentials (0.44 < E_ox < 1.89 V) was studied. Quenching rate constants for singlet (k_S^O2) and triplet (k_T^O2) states in addition to the fraction of oxygen-quenched singlet and triplet states q_{S 1}(T₁^O2 were determined from the decay rates, fluorescence intensities, and delayed fluorescence as functions of oxygen pressure. It was found that k_S^O2 values vary from 2·10⁴ (9,10-dicyanoanthracene) to 1.2·10⁷ sec⁻¹·torr⁻¹ (anthracene, 9-methylanthracene, 2-aminoanthracene) and k_S^O2 values from 5·10² to 1·10⁵ sec⁻¹·torr⁻¹. The k_S^O2 values for anthracene, 9-methylanthracene, and 2-aminoanthracene, which have fast rates of interconversion from S₁ to T₁, are close to the rate constants for gas-kinetic collisions and are independent of the oxidation potentials (E_ox). The quenching rate constants k_S^O2 for the other anthracene derivatives and k_T^O2 for all studied compounds decrease with increasing free energy of electron transfer ΔG_ET, which indicates the important role of charge-transfer interactions in the oxygen quenching of singlet S_1- and triplet T₁ states. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 75, No. 1, pp. 36–42, January–February, 2008.     

Kerr effect of molecular oxygen at λ=1064 nm

We report a new measurement of the Kerr effect of molecular oxygen at λ= 1064 nm. The experimental value reported for the anisotropy of the index of refraction Δ n_u^l, (3.15±0.85)×10^-25 m² V^-2 atm^-1, is in good agreement with the value of 3.4×10^-25 m² V^-2 atm^-1 obtained via an ab initio calculation. We show that the dependence of the effect on the pressure is not linear because of the presence of a collision-induced absorption band around 1060 nm due to the transition from the X³ Σ^-_g ground state to the ¹Δ_g state. We also give the value of the quadratic anisotropy Δn_u^q (-1.03±0.68)×10^-25 m² V^-2 atm^-2. We finally compare our ab initio theoretical and experimental results with previous existing data.     

Cooper pairing and superfluidity in the Emery model

The energy E of the system as a function of the gauge phase Φ is calculated by exact diagonalization in a two-dimensional Cu₄O₈ cluster and by the slave-boson method for large systems. It is shown that motion of carriers with charge 2e, i.e., Cooper pairs, is observed for certain values of the parameters in the Hamiltonian. This motion is identified from the onset of a characteristic maximum of E(Φ) at Φ≈Φ₀/2, where Φ₀ is the flux quantum. The phase diagram is constructed and the range of values of the model parameters where the effect is observed is determined. Pis’ma Zh. éksp. Teor. Fiz. 63, No. 2, 78–82 (25 January 1996)