Polarized fluorescence of β-carotene and related polyenes

The spectral and polarization characteristics of trans-isomers ofβ-carotene, lycopene, retinal, and 1,6-diphenylhexatriene (DPH) in solutions have been investigated by the methods of polarized fluorescence and semiempirical calculations of AM1 and RM3. The high and constant values of the degree of polarization P ∼0.46, closely coinciding with the limiting value P₀=0.5, according to the S₂→S₀-fluorescence and S₂←S₀-fluorescence excitation spectra ofβ-carotene and lycopene in n-hexane at room temperature and also high and coinciding according to the S₁→S₀-fluorescence and S₂←S₀-fluorescence excitation spectra for retinal in EPA at 77 K and DPH in a polyvinylbutyral film, point to the coincidence of the directions of absorption and emission oscillators. These oscillators are aligned along the major axis of the polyene molecule, and the longwave S₂←S₀-absorption band is formed only by one electronic¹B _u ⁺ ←¹A _g ⁻ -transition. The oscillators of shortwave S_a←S₀-absorption bands are aligned at an angle to the oscillators of the S₂←S₀-transitions, which is related to the distortions in the structure of molecules (β-carotene, lycopene) or, as in the case of DPH, to the influence of transitions localized on the orbitals of phenyl rings and polarized perpendicularly to the major axis of the molecule. Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 67, No. 1, pp. 69–74, January–February, 2000.     

Effect of bridging aza-substitution on electronic structure and spectral-luminescent properties of isobacteriochlorin NH-isomers

We have investigated the spectral characteristics, quantum yield ϕ_F, lifetime τ_F, and polarization of fluorescence of NH-isomers of dibenzobarrelene disubstituted tetraazaisobacteriochlorin at 293 and 77 K. The following information has been obtained from low-temperature measurements: 1) the weak shoulder on the edge of the long-wavelength 0-0 absorption band disappears at 77 K and, therefore, can be assigned to the cis-NH-isomer [the principal component of the tautomeric mixture is the trans-isomer a (b)]; 2) the low value of ϕ_F at room temperature is due to temperature-viscosity quenching whereas ϕ_F at 77 K is close to 1 and τ_F = 5.3 nsec; 3) the energy of the weak electronic transition G → Q₂ and the interval have been determined. Quantum-chemical calculations found that replacing the methine bridges by nitrogen stabilizes the non-aromatic trans-isomer a (b) whereas the non-planarity of the macrocycle and the alternation of bond lengths increase for the cis-isomers. The calculated electronic absorption spectra of the a isomer reproduce rather well the experimental data. It is shown that the four-orbital model is applicable for the lower excited states Q₁ and Q₂ for all NH-isomers. __________ Translated from Zhurnal Prikladnoi Spektroskopii Vol. 74, No. 3, pp. 395–407, May–June, 2007.     

Fermi-type resonance in quasi-linear fluorescence excitation spectra of triazatetrabenzoporphine

The effect of deuteration of the central NH groups on the quasi-linear fluorescence and fluorescence excitation (with selective monitoring) spectra for triazatetrabenzoporphine, a close analog of phthalocyanine, has been investigated at 77K in n-nonane. Vibrational analysis of the spectra was carried out. The normal mode frequencies were determined for the electronic states S₀ (from fluorescence spectra) and S₁ (for fluorescence excitation spectra). It has been established that N-deuteration lowers the frequency of a vibration involving inplane NH bending down to ∼990 cm⁻¹ and leads to resonant vibrational-electronic (vibronic) interaction of Fermi-type resonance between the zero level of the S₂ state and the vibronic level of the S₁ state upon excitation of this mode. Thereby the possibility of the “vibronic analog of Fermi resonance” (a term coined by G. Herzberg) occurring in a simple (two-component) variant of phthalocyanine-type molecules has been shown. Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 75, No. 6, pp. 796–803, November–December, 2008.     

Manifestation of vibronic intensity borrowing in fluorescence spectra of metalloporphyrins

In selective laser excitation and at T=4.2 K, fine-structure spectra of the fluorescence of the complexes of Mg, Zn, In, and TiO with octaethylporphyrin are obtained. It is shown that the fine-structure fluorescence spectra of these compounds are formed to a large aegree by ribronic interaction between quasi-degenerate S₁ and S₂ electron states. An increase in the relative intensities of a number of negatively polarized fluorescence lines in displacement of the excitation line from a longwave edge of the band of an S₀→S₁ transition in the shortwave direction is revealed. Reported at the VIIIth International Conference on Spectroscopy of Porphyrins and Their Analogs, Minsk, September 22–26, 1998. Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 66, No. 4, pp. 518–522, July–August, 1999.     

Er<Superscript>3+</Superscript> as glass structure modifier of Ga–Ge–S chalcogenide system

Er³⁺ clustering phenomenon in Ga–Ge–S chalcogenide system is studied using Raman spectroscopy. The Raman spectra from 10 to 500 cm⁻¹ for glasses (100−y)[15Ga₂S₃–85GeS₂]–yEr₂S₃ (y=0.08−5.00 mol. %) have been analyzed. To reveal the influence of the chemical composition on the glass structure the intensity of the peak corresponding to Ge–Ge (Ga–Ga) homopolar bonds has been examined. The peak intensity increase with Er₂S₃ concentration change in the region 0<C(Er₂S₃)<2 mol. % has been interpreted in terms of the sulphur deficiency in the glass resulting in the formation of S₃Ge–GeS₃ (S₃Ga-GaS₃) structural units. The further increase in concentration beyond 2 mol. % reduces the sulphur deficiency, which can be attributed to the formation of the ternary compound Er₃GaS₆. The structural units Er₃GaS₆ contain a large mol. fraction of Er³⁺ or, in other words, Er³⁺ clusters. The data obtained from the low-frequency Raman spectra (boson band) indicate strong variations of the medium-range order (MRO) in the glasses induced by Er³⁺. The observed behavior of the MRO size (the correlation length) with increasing of Er₂S₃ concentration provides for additional evidence of the Er³⁺ clustering.     

Absorption and fluorescence spectra of C<Subscript>60</Subscript> fullerene concentrated solutions in hexane and polystyrene at 77–300 K

The locations of the 0₀⁰ 0_0^0 -bands for S₁← S₀ and S₁ → S₀ transitions have been found for C₆₀ solutions in hexane. It is shown that the profile of the S₁ ← S₀ band is mainly shaped by h_u(4), t_1u(4)- and h_g(1), a_g(2)- modes that are active in absorption. Bands involving the h_u(4)- and t_1u(4)-modes in the emission process have also been identified in the fluorescence spectrum. The appearance of the 0₀⁰ 0_0^0 -band in the forbidden 1¹T_1g ← 1¹A_g transition is explained by symmetry reduction in the C₆₀+environment system due to the interaction of electrons with local phonons. The temperature coefficients of the red shift for the 256.3- and 328.3-nm bands of allowed ¹T_1u ← 1¹A_g transitions for C₆₀ in hexane are equal to –1.45 and –0.46 cm^–1·K^–1, respectively. The peak and half-width values of the 337.2-nm band for C₆₀ in polystyrene remain unchanged on cooling to 77 K. Absorption in the 700–800-nm region for concentrated hexane solutions of fullerene at 292 K results from the production of (C₆₀)_n-clusters.     

Saturable absorption dynamics of mode-locking dye DODCI

0 –S₁–S_m–S_n multilevel system. An S_m→S₁ absorption recovery time of τ^S1 _A=(600±100) fs is determined. The picosecond and femtosecond pulse excitation leads to S₀→S₁ ground-state absorption bleaching and S₁→S_m first excited-state absorption bleaching. The excited-state absorption cross-sections σ^S1 _ex(S₁→S_m) and σ^Sm _ex(S_m→S_n) are determined. Received: 3 June 1996     

Spectral and kinetic characteristics of CdI<Subscript>2</Subscript> and CdI<Subscript>2</Subscript>:Pb scintillators

We have studied the effect of lead dopant on the optical absorption, photoluminescence, and x-ray luminescence spectra, and the scintillation characteristics of CdI₂ at room temperature. The crystals for the study were grown by the Stockbarger-Bridgman method. Activation of CdI₂ from the melt by the compound PbI₂ leads to the appearance in the absorption spectra in the near-edge region of an activator band at 395–405 nm, which is interpreted as an A band connected with electronic transitions from the ¹S₀ state to the ³P₁ levels in the Pb²⁺ ion. For x-ray excitation, CdI₂:Pb²⁺ crystals with optimal dopant concentration (∼1.0 mol%) are characterized by a light yield with maximum in the 570–580 nm region that is an order of magnitude higher than for CdI₂ crystals in the 490–500 nm band. For α excitation, the radioluminescence kinetics for cadmium iodide is characterized by a very short (∼0.3 nsec) rise time and fast decay of luminescence, with τ₁ ≈ 4 nsec and τ₂ = 10–76 nsec. Depending on the conditions under which the crystals were obtained, the fast component fraction is 95%–99%. The crystal is characterized by a similar scintillation pulse in the case of excitation by x-ray pulses. The radioluminescence pulse shape for CdI₂:Pb in the decay stage is predominantly exponential, with luminescence decay time constants τ₁ ≈ 10 nsec and τ₂ = 200–250 nsec. This system is characterized by low afterglow, at the level for the Bi₄G₃O₁₂ scintillator. We have demonstrated the feasibility of using CdI₂:Pb as a scintillator for detecting α particles. Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 75, No. 6, pp. 825–830, November–December, 2008.     

Vibrational structure of quasiline fluorescence and absorption spectra of bisanthene molecules

The quasiline spectra of the fluorescence and absorption of bisanthene in n-hexane are obtained at 77 and 4.2 K, and their vibration analysis is carried out. Substantial violation of the mirror symmetry of the fluorescence and S₁ ← S₀-absorption bands with respect to both the frequencies and intensities is found. This allowed the conclusion that the S₂-level is localized in the region of vibronic sublevels of the S₁-state with . Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 67, No. 4, pp. 488–491, July–August, 2000.     

Spectral-luminescent properties of condensation products of 8-aminoquinoline,aromatic aldehydes,and dimedone

Hydrobenzophenanthrolinone derivatives were synthesized by three-component condensation of 8-aminoquinoline, aromatic aldehydes, and dimedone. The structures of the obtained substances were confirmed by NMR and IR spectroscopy and mass spectrometry. Spectral-luminescent investigations of the synthesized compounds showed that they were characterized by high oscillator strengths for allowed electronic transitions S _n ← S ₀ (n = 1–3). Low fluorescence quantum yields in EtOH (Φ_fl ~ 10^–4–10^–3) and an increase of the Φfl values in toluene (~10^–2) at room temperature and with lowering the temperature to 77 K (Φ_fl ~ 10^–1) for a number of the compounds under study were satisfactorily explained within the framework of Marcus theory.     

Double Fluorescence Conversion in Ultraviolet and Visible Region for Some Praseodymium Complexes of Aromatic Carboxyates

Four praseodymium complexes of aromatic carboxylates (benzoate, 4-tert-butylbenzoate, 2-benzoylbe-noate, and benzimidazole-5-carboxylate) have been synthesized and characterized, whose photophysical properties have been studied with ultraviolet spectra, phosphorescence spectra, and fluorescence spectra. The fluorescent emission spectra of all praseodymium complexes show two emission peaks under the excitation band of 245 nm at about 395 and 595 nm respectively, while one peak under 415 nm at about 595 nm, which attributed to be ¹S₀ → ¹I₆ (395 nm) transition and the characteristic emission ¹D₂ → ³H₄ (595 nm) transition of Pr³⁺ ion. The ¹S₀ → ¹I₆ transition can be ascribed as the transition of charge transfer state, and the ¹D₂ → ³H₄ can be further proved that there exists an antenna effect in the fluorescence of praseodymium with aromatic carboxylic acids. In conclusion, the praseodymium complexes systems can realize the double fluorescent conversion in both ultraviolet and visible region and can be further studied the application of this conversion.     

Molecular structure of trimethyl[(3-indole)ethoxy]silane cooled in a supersonic jet

Conformations of He-jet-cooled trimethyl[(3-indole)ethoxy]silane (TIES) have been studied using a laser spectroscopy technique in combination with quantum-chemical computations. Six probable conformers of the molecule were computed, of which only two conformations were observed. Based on an analysis of fluorescence excitation spectra, fluorescence spectra, shapes of rotational band contours at the electronic S₀–S₁ transition of TIES, and theoretical computations, the above conformers were assigned to steric structures. Twisted structures have the lowest energy due to intramolecular hydrogen bonds C - H ?O < _C^Si C - H \cdots O <_C^{Si} between hydrogen atoms of methyl groups and an oxygen atom and C–H···π between H and the π-electron cloud of the indole ring.     

Luminescence of CaGa<Subscript>2</Subscript>Se<Subscript>4</Subscript>:Eu crystals

We have studied photoluminescence and thermoluminescence (PL and TL) in CaGa₂Se₄:Eu crystals in the temperature range 77–400 K. We have established that broadband photoluminescence with maximum at 571 nm is due to intracenter transitions 4f⁶ 5d–4f⁷ (⁸S_7/2) of the Eu²⁺ ions. From the temperature dependence of the intensity (log I–10³/T), we determined the activation energy (E _a = 0.04 eV) for thermal quenching of photoluminescence. From the thermoluminescence spectra, we determined the trap depths: 0.31, 0.44, 0.53, 0.59 eV. The lifetime of the excited state 4f6 5d of the Eu²⁺ ions in the CaGa₂Se₄ crystal found from the luminescence decay kinetics is 3.8 μsec. Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 76, No. 1, pp. 112–116, January–February, 2009.     

Spectral luminescence properties of hydroporphyrazine metallo complexes

We have studied the spectral luminescence properties of a zinc complex of dibenzobarreleno-substituted tetraazaisobacteriochlorin (a synthetic tetrapyrrole pigment which is the structural analog of the biologically important chromophore isobacteriochlorin) and a palladium complex of dibenzobarreleno-substituted tetraazachlorin. We have shown that despite the substantial effect of aza-substitution on the electronic structure and the electronic spectra of the tetrapyrrole molecules, the effect of hydrogenation of adjacent pyrrole rings on the spectral luminescence properties is similar in compounds with nitrogen and carbon bridges. As in the free base case, the fluorescence of the studied zinc complex is strongly quenched at 293 K but flares up at 77 K (temperature and viscosity-dependent quenching). To study the substituted Zn-tetraazaisobacteriochlorin, we determined the position of the 0-0 band of the low-intensity transition S₀ → S₂ and showed that the S₂ → S₁ energy difference increases with bridge aza substitution. For the Pd complex of dibenzobarreleno-substituted tetraazachlorin, we could not detect phosphorescence in the near IR region (to 1150 nm); we detected weak fluorescence. Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 75, No. 5, pp. 700–707, September–October, 2008.     

Evidence for formation of Se molecular clusters during precipitation of CdSe<Subscript>1−<Emphasis Type="Italic">x</Emphasis></Subscript>S<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript> nanoparticles in glass

While studying the effect of thermal treatment at 625–700°C on the formation of borosilicate glass-embedded CdSe or CdSe_1−x S _x nanocrystals, pronounced bands at 323 and 646 cm⁻¹ were observed in the Raman spectra. They are assigned to Se₂ clusters on the base of their frequency positions, widths, intensities, and resonance behavior. The precipitation of Se₂ molecular clusters in borosilicate glass is shown to occur when the heat treatment temperature and/or duration are beyond the range, most suitable for the formation of CdSe or CdSe-rich CdSe_1−x S _x nanocrystals.     

The Muonic Hydrogen Lamb Shift Experiment at PSI

A measurement of the 2S Lamb shift in muonic hydrogen (μ⁻p) is being prepared at the Paul Scherrer Institute (PSI). The goal of the experiment is to measure the energy difference ΔE(2⁵ P _3/2−2³ S _1/2) by laser spectroscopy (λ≈6μm) to a precision of 30 ppm and to deduce the root mean square (rms) proton charge radius with 10⁻³ relative accuracy, 20 times more precise than presently known. An important prerequisite to this experiment is the availability of long-lived μp_2S -atoms. A 2S-lifetime of ∼1 μs – sufficiently long to perform the laser experiment – at H₂ gas pressures of 1–2 hPa was deduced from recent measurements of the collisional 2S-quenching rate. A new low-energy negative muon beam yields an order of magnitude more muon stops in a small low-density gas volume than a conventional cloud muon beam. A stack of ultra-thin carbon foils is the key element of a fast detector for keV-muons. The development of a 2 keV X-ray detector and a 3-stage laser system providing 0.5 mJ laser pulses at 6 μm is on the way. This revised version was published online in August 2006 with corrections to the Cover Date.     

Silver Nanoparticle-Enhanced Chemiluminescence Method for Determining Naproxen Based on Europium(III)-Sensitized Ce(IV)-Na<Subscript>2</Subscript>S<Subscript>2</Subscript>O<Subscript>4</Subscript> Reaction

A simple and sensitive chemiluminescence (CL) method coupled with flow-injection technique is proposed to determine naproxen (NAP). The method is based upon the enhancement of the weak CL signal arising from the reaction of Ce(IV) and Na₂S₂O₄ with Eu³⁺ to form the Eu³⁺-Ce(IV)-Na₂S₂O₄ system. The CL intensity was significantly increased by the introduction of NAP into this system in the presence of silver nanoparticles (Ag NPs). Examination of the recorded UV–vis spectra and fluorescence spectra indicated that the energy of the intermediate SO₂*, which originated from the redox reaction of Ce(IV) and Na₂S₂O₄, was transferred to Eu³⁺ via NAP and that the process was accelerated by Ag NPs due to their catalytic activity. Under the optimum conditions, the CL intensity was increased with increasing NAP concentration and the correlation was linear (r = 0.9992) over the NAP concentration range of 1–420 ng mL⁻¹. The limit of detection (LOD) was 0.11 ng mL⁻¹ with a relative standard deviation (RSD) of 1.15% for 5 replicate determinations of 200 ng mL⁻¹ NAP. The method was successfully applied to determine NAP in pharmaceutical and biological samples.     

One-pot fabrication and enhanced thermoelectric properties of poly(3,4-ethylenedioxythiophene)-Bi<Subscript>2</Subscript>S<Subscript>3</Subscript> nanocomposites

Bi₂S₃ nanotubes and de-doped poly(3,4-ethylenedioxythiophene) (PEDOT) composite nanopowders were synchronously synthesized by a one-pot self-assembly method. The powders were characterized by X-ray powder diffraction, infrared spectroscopy, and transmission electron microscopy, respectively. Thermoelectric properties of the Bi₂S₃–PEDOT composite nanopowders with different Bi₂S₃ contents after being cold pressed into pellets were measured at room temperature. The sample with 36.1 wt% Bi₂S₃ has a highest power factor of 2.3 μWm⁻¹K⁻², which is higher than that of both pure PEDOT (0.445 μWm⁻¹K⁻²) and Bi₂S₃ (1.94 μWm⁻¹K⁻²).     

REMPI as a tool for studies of OH radicals in catalytic reactions

2 +? O₂→H₂O on polycrystalline Pt foils has been studied by detection of desorbing OH radicals using the Resonance Enhanced Multiphoton Ionization, REMPI, technique. The measurements were performed at catalyst temperatures of 1000–1400 K and a total pressure below 10^-4 mbar. The studies of OH desorption by REMPI were achieved using a two-photon excitation D²Σ^-–X²Π (1–0), followed by one-photon ionization. The ions were detected in a time-of-flight mass spectrometer, TOF-MS, in order to avoid interference from non-resonantly ionized molecules. By applying TOF-MS, a simultaneous non-resonant ionization and detection of H₂, O₂ and H₂O was achieved. Recorded REMPI spectra were compared with spectra simulated using known molecular constants. The kinetics of the reaction derived from the measurements were compared with what was obtained in earlier LIF detection of OH, performed at higher total reactant pressure using the A–X transition. REMPI TOF-MS is shown to be a complement to LIF for reaction studies below 5×10^-4 mbar total pressure, where LIF is too insensitive for quantification. The reaction kinetics was found to be in agreement with a theoretic model and previous LIF studies. Received: 8 March 1996/Revised version: 4 October 1996