The deexcitation of the S1 state of aminoanthraquinones: A steadystate and timeresolved study

The non-radiative processes of deactivation from the lowest singlet excited state of aminoanthraquinones have been studied using steady-state and time-resolved methods. The fluorescence decay rate constant, k_f correlates well with the solvent polarity parameter, E_T(30), in nonhydrogen bonding solvents. Large deuterium isotope effects in fluorescence lifetimes (τ_f) and quantum yields (ϕ_f) are observed in the case of 1-amino (AAQ) and 1-methylaminoanthraquinones (MAQ), where the S₁ state is mainly deactivated through internal conversion to the ground state. The temperature-dependence of the fluorescence quantum yields of various aminoanthraquinones was also investigated. The ϕ_f and τ_f exhibited strong temperature-dependence in the case of 1-acetylaminoanthraquinone (ACAQ). In the case of ACAQ, the intersystem crossing to the triplet state is a major deactivation channel from the S₁ and in this derivative a close-lying T₂ state seems to be responsible for the high k_isc rate. The fluorescence properties of 1,5-diaminoanthraquinone (DAQ) are affected by intermolecular hydrogen bonding with alcohols. Increasingn-alkyl chain length in the case of l-(n-alkyl)aminoanthraquinones from methyl to butyl does not produce any change in the fluorescence properties, whereas a hydroxypropyl substitution results in a small decrease of ϕ_f and τ_f in these compounds, indicating an interaction of the hydroxyl group with the carbonyl group of the aminoanthraquinones.     

PHOTOPHYSICAL AND PHOTOSENSITIZING PROPERTIES OF BENZOPORPHYRIN DERIVATIVE MONOACID RING A (BPD-MA)*

The photophysical properties of benzoporphyrin derivative monoacid ring A (BPD-MA), a second-generation photosensitizer currently in phase II clinical trials, were investigated in homogeneous solution. Absorption, fluorescence, triplet-state, singlet oxygen (O₂(¹Δ_g)) sensitization studies and photobleaching experiments are reported. The ground state of this chlorin-type molecule shows a strong absorbance in the red (λ≈ 688 nm, ?≈ 33 000 M^?1 cm^?1 in organic solvents). For the singlet excited state the following data were determined in methanol: energy level, E_s= 42.1 kcal mol^?1, lifetime, Φ_f= 5.2 ns and fluorescence quantum yield, Φ_f= 0.05 in air-saturated solution. The triplet state of BPD-MA has a lifetime, τ_f >. 25 ns, an energy level, E_T= 26.9 kcal mol^?1 and the molar absorption coefficient is ?_T= 26 650 M^?1 cm^?1 at 720 nm. A dramatic effect of oxygen on the fluorescence (φ_f) and intersystem crossing (φ_T) quantum yields has been observed. The BPD-MA presents rather high triplet (φ_T= 0.68 under N₂-saturated conditions) and singlet oxygen (φ_Δ= 0.78) quantum yields. On the other hand, the presence of oxygen does not significantly modify the photobleaching of this photostable compound, the photodegradation quantum yield (φ_Pb) of which was found to be on the order of 5 × 10^?5 in organic solvents.     

Photophysical properties of tetracene derivatives in solution

Photophysical properties of three tetracene (TET) derivatives were investigated in solution. The quantum yield of intersystem crossing (Q_ISC) and the fluorescence lifetime (τ_F) or 5-monophenyltetracene (MPT) and 5-naphthyltetracene (NAT) are similar to the parent molecule: Q_ISC = 0.6–0.7, τ_F = 4.8–5.2 ns. Distinctly different properties were found for 5,12-diphenyltetracene (DPT): Q_ISC = 0.17, τ_F = 15.2 ns. Of the molecules investigated only in DPT is (S₁-T₂) ISC a thermally activated process. The frequency factor A and the experimental activation energy E_a were determined according to an Arrhenius-type relationship. With E_a the energy of the T₂ state can be estimated. The T₁ state energy of DPT was measured with the method of reversible triplet energy transfer. These results permit to explain photophysical properties on the basis of a schematic energy level diagram and emphasize the role of higher triplet states in molecular deactivation processes. Previously we found thermally activated ISC in rubrene (RUB). The frequency factor of DPT exceeds that of RUB by more than one order of magnitude. This difference is discussed with respect to the effect of steric hindrances in RUB.     

Pulsed NMR study of molecular motions and phase transitions in [N(CH3)4]PbX3 (XCl,Br, I)

Proton spin—lattice relaxation time (T₁) is measured in [N(CH₃)₄]PbX₃ (XCl, Br, I) from 300-77 K at 9.75 MHz. All the compounds show discontinuous changes in T₁ values (at 256, 270 and 277 K, respectively), indicating phase transitions. Single T₁ minimum is observed in all the cases and the T₁ variation is explained in terms of [N(CH₃)₄] and CH₃ group dynamics. The activation energy E_α decreases from chloride to iodide (from 4 to 2 kcal/mol). In bromide and iodide, T₁ is found to decrease with increase in temperature at higher temperatures, indicating the presence of spin—rotation interaction.     

Temperature dependence of radiationless processes. Isoquinoline in solution

The temperature dependence of the fluorescence quantum yield φ_f, the fluorescence lifetime τ_f, and the oscillator strength f(S₀→S₁) of isoquinoline in solution has been measured between room temperature and 77 K. Following an Arrhenius type expression, φ_f in ethanol increases from 0.012±0.002 at 295 K to 0.61±0.03 at 77 K paralleled by an increase of τ_f from 0.25±0.10 ns to 9.0±0.2 ns. Over the same temperature range f(S₀→S₁) and the radiative fluorescence lifetime remain constant. By analyzing the temperature dependent data, it is shown that a spin-allowed internal conversion process with an activation energy of ～1500 cm^?1 is responsible for the observed temperature effect. A mechanism is proposed based upon a thermally activated depopulation of the S₁(ππ^*) state of isoquinoline via a slightly higher state, presumably the S₂(ππ^*) singlet state. An extremenly fast process involving the dissociation of the hydrogen bond deactivates this latter state, by possing S₁.     

The vitrification of alkali borate and alkali silicate melts

Glasses and crystals of compositions corresponding to the congruently melting compounds M₂O·2SiO₂ (M = Na. Rb, and Cs) and M₂O·4SiO₂ (M = K, Rb, and Cs) were studied by differential scanning calorimetry. The structure temperatures (T _f) and excess entropies at T _f of glasses were measured depending on the rate of cooling of the corresponding melts. The activation energies of glass formation (ΔE) and scale of cooperative motion in the transition region (ξ_a) were estimated. The totality of the data obtained were used to compare the thermodynamic (the ratio between the excess (with respect to the corresponding crystals) entropy of glass at T _f and the entropy of crystal melting), kinetic (fragility m = f(ΔE, T _f)), and microscopic (ξ_a) parameters of the vitrification of alkali silicate melts. The behaviors of alkali silicate and alkali borate melts were shown to be similar.     

Ultrasensitive fluorescent probe for the hydrophobic range of solvent polarities

The new 3-hydroxychromone derivative 2-(6-diethylaminobenzo[b]furan-2-yl)-3-hydroxychromone (FA) displays a dramatic solvent-dependent transformation of fluorescence spectra in the range of low-polarity solvents. The two well-separated emission bands change their relative intensities so that the short-wavelength band being of a very low intensity in hexane becomes dominant in the more polar ethyl acetate and trichloromethane. We suggest the participation in this effect of excited-state intramolecular proton transfer, which is characteristic for other 3-hydroxychromone and 3-hydroxyflavone derivatives, in the range of solvents of much higher polarities. Because of these unique properties, a number of spectroscopic parameters (positions of absorption and two fluorescence maxima, the ratio of their intensities and the fluorescence quantum yield) can be measured in this solvent range with multiparametric analysis of the data. In terms of solvent polarity, the shifts in both emission bands and their intensity ratio demonstrate a good correlation with empirical polarity scales E_T^N, P_y and SPP, while the absorption spectra reveal some deviations for the tested oxygen-containing solvent molecules. A good cross-correlation is observed between fluorescence spectral shifts and the ratio of band intensities. The latter provides the means for a dramatic amplification of solvent response. Thus, a new approach for ultrasensitive scaling and probing the solvent polarity in the low-polararity range can be suggested. It involves very simple ratiometric measurements at two emission bands and can be posed for a variety of applications. We present examples of these applications for distinguishing of polarities between methylated benzene derivatives, for quantitative assay of polar impurities in low-polar solvents and for detection of the changes of solvent polarity as a function of temperature.     

What is Best Strategy for Water Soluble Fluorescence Dyes?—A Case Study Using Long Fluorescence Lifetime DAOTA Dyes**

The lipophilic nature of organic dyes complicates their effectiveness in aqueous solutions. In this work we investigate three different strategies for achieving water-solubility of the diazaoxatriangulenium (DAOTA⁺) chromophore: hydrophilic counter ions, aromatic sulfonation of the chromophore, and attachment of charged side chains. The long fluorescence lifetime (FLT, τ_f=20 ns) of DAOTA⁺ makes it a sensitive probe to analyze solvation and aggregation effects. Direct sulfonation of the chromophore was found to increase solubility drastically, but at the cost of greatly reduced quantum yields (QYs) due to enhanced non-radiative deactivation processes. The introduction of either cationic (4) or zwitterionic side chains (5), however, brings the FLT (τ_f=18 ns) and QY (ϕ_f=0.56) of the dye to the same level as the parent chromophore in acetonitrile. Time-resolved fluorescence spectroscopy also reveals a high resistance to aggregation and non-specific binding in a high loading of bovine serum albumin (BSA). The results clearly show that addition of charged flexible side chains is preferable to direct sulfonation of the chromophore core.     

Photochemical synthesis and electronic spectra of fulminene ([6]phenacene)

Facile synthesis of fulminene ([6]phenacene) was achieved through the Mallory reaction of 1-(1-naphthyl)-2-(1-phenanthryl)ethene or the 9-fluorenone-sensitized photo-ring-closure of 1-(1-naphthyl)-2-(1-phenanthryl)ethane. The electronic spectral properties of fulminene were investigated for the first time using photoluminescence as well as transient absorption spectroscopy. The spectral features were compared with those of a series of lower phenacene homologs such as phenanthrene ([3]phenacene), chrysene ([4]phenacene), and picene ([5]phenacene). For the [n]phenacene series, both the fluorescence and phosphorescence bands linearly red-shifted with an increase in the number of the benzene rings (n). Trends in the energy levels of the excited singlet (E _S) and the triplet (E _T) states were expressed as E _s = ?2.6n + 89.1 (kcal mol^?1) and E _T = ?1.8n + 66.2 (kcal mol^?1), respectively. In the case of fulminene, laser flash photolysis displayed a transient spectrum with an absorption maximum (λ _max ^T–T ) at 675 nm, which was assigned as the triplet fulminene excited state. The λ _max ^T–T values for the [n]phenacene series showed a linear correlation as a function of the ring number n, given by an equation, λ _max ^T–T  = 60n + 318 (nm).     

Spectrophotometric Study on Kinetics of Solvatochromism of Methyl Violet in Aqueous Methanol

The kinetics of the reaction of methyl violet with iodide in aqueous methanol system was studied by spectrophotometric method. The rate of reaction of methyl violet in different alcoholic composition in presence of potassium iodide was observed at pH 4 and 6 at various temperatures (298–318 K). Solvatochromic effect was studied in different percentages of methanol (0–50%). Bathochromic shift was observed with the decrease in polarity of solvent. The color change was attributed to molecule's structure, the delocalization of unit electrical charge causes deepening of color and decrease of delocalization causes fading of color due to reduction of dye. Increase in the rate of reaction was observed with increase in alcoholic content and also affected by potassium iodide salt and increased with increase in concentration of potassium iodide. Energy of activation (E_a) and transition energy (E_T) were calculated with the help of kinetic data. Thermodynamic parameters such as enthalpy change of activation (ΔH*), Gibbs free energy change of activation (ΔG*) and entropy change of activation (ΔS*) were evaluated as a function of concentration of solvent and salt.     

Lifetime of the He2(e), He2(d) and He2(f) states

Starting from the He₂(a) state absorption and induced fluorescence experiments were performed using a narrow band dye laser. The saturation intensity for the He₂(e)←He₂(a) transition yields a radiative lifetime of τ=(67±10) ns. Time resolved measurements of the laser induced fluorescence yield the radiative lifetimes for the states He₂(e): (57±10) ns, He₂(d): (25±5) ns and He₂(f): (19±5) ns. From the time integrated fluorescence data the collisional quenching rates between the above states were determined.     

Jahn-Teller activity in eight-coordinate Oh fx systems

The angular overlap model is used for the calculation of the Jahn-Teller coupling constants for O_h, MX₈, f^x systems in the (LSJM_J) basis. For the 5f¹ anion, [UF₈]^3?, the Γ₈ ground state is predicted to show substantial Jahn-Teller activity for coupling to the τ_2g bending mode, with E_JT comparable to ω, a result consistent with the available magnetic susceptibility data.     

On the nature of solubilized water clusters in aerosol OT/alkane solutions. A study of the formation of hydrated electrons and 1,8-anilinonaphthalene sulphonate fluorescence

The pulse radiolysis of dioctyl sulphosuccinate (aerosol-OT) H₂O/heptane solutions leads to formation of hydrated electrons in the aqueous core of the inverted aerosol-OT micelles. The hydrated electrons are produced via direct interaction of the radiation with the aqueous regions and scavenging of electrons formed initially in the hydrocarbon phase by the water bubbles. The scavenging efficiency decreases with decreasing radius of the water cluster. Hydrated electrons are not formed below a critical size of the solubilized water particles.The quantum yield and wavelength of the maximum of the aniline-naphthalene sulphonate (ANS) fluorescence are strongly dependent on the water content of aerosol-OT inverted micelles. The fluorescence behavior indicates an increase of polarity with increasing cluster radius. The polarity of very large water clusters (r ≈ 73 Å) is still lower than that of bulk water. Water which is bound to Na⁺ counterions cannot effectively participate in the solvation of the dipolar ANS excited states.     

Crystallization and melting behaviors of polystyrene-b-poly(ethylene-co-butene) block copolymers

Non-isothermal and isothermal crystallization behaviors of polystyrene-b-poly(ethylene-co-butene) (PSt-b-PEB) block copolymers with different compositions and chain lengths were investigated by differential scanning calorimetry (DSC). The results show that crystallization of PEB block is strongly dependent on the composition. Crystallization temperature (T_c), melting temperature (T_m) and fusion enthalpy (ΔH_f) increase rapidly with PEB volume fraction (V_E) for block copolymers with V_E below 50%, but there is little change when PEB block becomes the major component. Glass transition temperature (T_g) of the PSt block and order-disorder transition temperature (T_ODT) of block copolymers also have a weak effect. The isothermal crystallization kinetics results show that Avrami exponent (n) was strongly dependent on the composition and crystallization temperature. For the block copolymers with V_E below 38.7 vol%, the values of n vary between 0.9 and 1.3, indicating that crystallization is confined. For the PSt-b-PEB block copolymers with V_E higher than 50%, fractionated crystallization behavior is usually observed. A two-step isothermal crystallization procedure is applied to these block copolymers. It is found that breakout crystallization occurs at higher T_c, but confined at lower T_c. Two overlapped melting peaks are observed for the block copolymers with fractionated crystallization behavior after two-step crystallization, and only the higher melting peak corresponding to breakout crystallization can be used to derive equilibrium melting temperature.     

Intermolecular interactions in methyl formate-ethanol mixtures at 303–313 K according to ultrasonic data

Density (ρ), viscosity (η), and ultrasonic velocity (U) have been measured for a binary mixture composed of methyl formate and ethanol at 303, 308, and 313 K. The adiabatic compressibility (β), acoustic impedance (Z), free length (L _f ), free volume (V _f ), internal pressure (π _i ), viscous relaxation time (τ), and Gibbs free energy (ΔG) were calculated from the experimental data. The excess values of these parameters (β ^E , Z ^E , L _f ^E , V _f ^E , π _i ^E , τ ^E , and ΔG ^E ) have also been calculated using the determined parameters and interpreted in terms of molecular interactions. The deviations in the sign and values of these excess parameters from the ideal mixing reveal the nature of intermolecular interactions between components of the mixture.     

Determination of the electric field and anomalous heating caused by exponential pulses with aluminum electrodes in electroporation experiments

Electroporation is well known to depend non-linearly on the magnitude and duration of the change ΔU(t) in transmembrane voltage. In the case of cell suspension experiments, an electric field E_e(t) within the electrolyte causes ΔU(t), which is governed by both the size and shape of a cell, and also by E_e(t). It is therefore important to determine the magnitude and time dependence of the electric field to which cells are actually exposed in electroporation experiments. This can be significantly different from the nominal field E_n, which is calculated by using electrode voltages and geometries alone. Throughout we used single, nominally exponential pulses with time constants τ_pulse ranging from about 0.6 to 5 ms and found that E_e was always less than E_n. In order to determine the actual electric field pulse, we measured the voltage across the electrodes, the current through the cuvette, the temperature rise of the pulsing medium, and the voltage across two special electrodes placed within the cuvette. From these measurements we calculated the field strength inside the cuvette using two different methods. In addition, we compared the measured temperature rise with that expected from the electrical power dissipation. In some cases there was much larger (“anomalous”) heating, due to interfacial electrochemical heat production; for one pulsing solution T_e(t) was about 30 K larger than expected. These effects are important for experiments aimed at elucidating the electroporation mechanism, comparing results obtained under different conditions, and guiding applications.     

Bichromophoric hemicyanine dyes as fluorescence probes applied for monitoring of the photochemically initiated polymerization

The spectroscopic properties of series homodimmeric hemicyanine dyes based on (p-N,N-dimethylaminostyryl)benzothiazolium, (p-N,N-dimethylaminostyryl)benzoxazolium, (p-N,N-dimethylaminostyryl)-2,3,3-trimethyl-3H-indolium residues were determined. The absorption and fluorescence spectra of the dyes under study were measured in different polarity solvents at room temperature. On the basis of the solvatochromic behavior the ground state (μ_g) and excited state (μ_e) dipole moments of bis-(N,N-dimethylaminostyryl) derivatives were evaluated. The dipole moments (μ_g and μ_e) were estimated from solvatochromic shifts of absorption and fluorescence spectra as function of dielectric constant (ε) and refractive index (n) of applied solvents. The absorption and fluorescence spectra are only slightly affected by the solvent polarity. The analysis of solvatochromic behavior of the fluorescence spectra as a function of Δf (ε, n) revealed that the emission occurs from a high polarity excited state. The large dipole moment changes along with the red-shifted fluorescence, as the solvent polarity is increased, demonstrates the formation of an intramolecular charge transfer state (ICT). Six bichromophoric hemicyanine dyes, possessing benzothiazole, benzoxazole or indolinium group linked by 5 or 10 methylene groups were evaluated as fluorescence probes applied for monitoring of the polymerization process. The study on the changes in fluorescence intensity and spectroscopic shift of studied compounds were carried out during photochemically initiated polymerization of 2-ethyl-2-(hydroxymethyl)-propane-1,3-diol triacrylate (TMPTA).     

5T2-1A1 Spin transition and residual paramagnetism in bis(2,4-bis(2-pyridyl)thiazole)iron(II) complexes: mössbauer effect and magnetism

The ⁵⁷Fe Mössbauer effect in [Fe(pythiaz)₂] (BF₄)₂ (I) and [Fe(pythiaz)₂] (C&O₄)₂ (II) has been studied between 298 and 4.2°K (pythiaz = 2,4-bis(2-pyridyl)thiazole). At 298°K compound I shows a doublet with ΔE_Q(⁵T₂) = 1.29 mm sec^?1 and δ^1S(⁵T₂) = +0.93 mm sec^?1 characteristic of a ⁵T₂ ground state. At 236°K, a second doublet, typical for a ¹A₁ ground state appears. The transition ⁵T₂ å ¹A₁ progresses as the temperature is lowered but levels off below ≈ 120°K. At 4.2°K, 59% of the intensity is due to the ¹A₁ state, and ΔE_Q(¹A₁) = 1.59 mm sec^?1 and δ^1S(¹A₁) = +0.26 mm sec^?1. In an applied magnetic field, V_zz(¹A₁) < 0 has been determined Similar results have been obtained with compound II.Debye-Waller factors f5_T2 and f1_A1. were determined from the Mössbauer spectra under the assumption of Curie-Weiss dependence of the magnetism for the ⁵T₂ and constant μ_eff for the ¹A₁ ground state. The resulting temperature dependence of f1_A1 is highly unusual thus suggesting complicated magnetic behaviour of both ground states in the transition region. Two mechanisms for the nature of the transition are discussed, a “spin-flip” mechanism being the physically more reasonable one. The assumption of a simple Boltzmann distribution (“spin equilibrium”) may be ruled out for the solid but could be encountered in solutions.     

Thermally induced incomplete high-spin (5T2) ⇌ low-spin (1A1) transition in solid bis[2-(2-pyridylamino)-4-(2-pyridyl) thiazolato]iron (II)

The ⁵⁷Fe Mössbauer effect in two samples (A and B) of [Fe(papt)₂] and in its solvates with CHCl₃ and C₆H₆ has been studied between 4.2 and 343 K and clearly indicates a temperature induced high-spin (⁵T₂) ? low-spin (¹A₁) transition in these compounds [paptH = 2-(2-pyridylamino)-4-(2-pyridyl) thiazole]. At 343 K, sample B shows a doublet with ΔE_Q = 2.03 mm s^?1 and δIS = +0.87 mm s^?1, characteristic of a ⁵T₂ ground state. At 257 K, a second doublet, typical for a ¹A₁ ground state, is observed and its intensity increases as the transition progresses but levels off below ～ 100 K. At 4.2 K, 83% of the intensity is due to the ¹A₁ state, and ΔE_Q(¹A₁) = 1.56 mm s^?1 and δ^IS(¹A₁ = +0.32 mm s^?1. In an applied magnetic field, V_zz(¹A₁) < 0 and η ≈ 0.7 have been determined, whereas for the ^sT₂ ground state, V_zz(^sT₂) > 0, η ≈ 0.75, and an internal hyperfine field H_n ≈ ?13 kG have been observed. Similar results have been obtained with the other samples.Debye-Waller factors f5_T2 and f1_A1 were determined from the saturation corrected areas in the Mössbauer spectra, assuming Curie-Weiss dependence of the magnetic susceptibility for the ⁵T₂ and constant υ_cff for the ¹A₁ ground state. The temperature dependence of ?In f1_A1 closely follows the Debye model with Θ1_A1 = 165 K, whereas the same applies to ?ln f5_T2 only above ～ 210 K and Θ5_T2 = 134 K. The nature of the observed transition is discussed and the data presented are shown to be incompatible with a model based on a Boltzmann distribution between the two states.     

Photochemistry of dienones—X: Photochemistry of (e)-β-ionone oxime ethyl ether

(E)-β-ionone oximc ethyl ether [(E, E)-4] upon direct irradiation with λ either254or 313 nm yields the geometrical isomer (E, Z)-4 and (Z)-retro-γ-ionone oxime ethyl ether (Z,E)-5 as the sole primary products, illustrating (E)-(Z) isomerization (φ₃₁₃ =0.49) and a 1, 5-hydrogen shift (φ313 =0.15) respectively. From studies with triplet photosensitizers and with ethyl iodide (to enhance the singlet-triplet intersystem crossing) it is concluded that these two products in the direct irradiation result only from the singlet excited state, and that the inter-system crossing quantum yield is relatively low. Upon prolonged irradiation of (E,E)-4 with λ 313 nm the eventual products are (Z,E)-5 and (Z,Z)-5, whereas with λ 254 nm they are (E,E)-5 and [(Z,E)-5 and/or (E,Z)-5]. Upon triplet photosensitization (E,E)-4 undergoes only (E)-(Z) isomerization, leading to a mixture of all the four geometrical isomers of4. From the dependence of the geometrical isomer distribution in the photostationary state on the triplet energy of the sensitizer the triplet energies of (E,E)-4, (E, Z)-4, (Z, E)-4, and (Z, Z)-4 have been determined to be ca 55, < 55,57, and 57 $\text{kcal}\text{mol}$ respectively.