Optical properties of pyridine funtionalized TbF<Subscript>3</Subscript> nanoparticles

The preparation of pyridine functionalized TbF₃ nanoparticles are described in this report. Synthesized nanoparticles were characterized using the TEM, UV/Vis, FTIR and photoluminescence spectroscopy. TEM micrograph reveals the nanorod shaped, uniform in size with a particles size in the range of 20–30 nm. FTIR spectrum shown characteristic absorption bands of pyridine and a small intensity band at 411 cm⁻¹ corresponding metal nitrogen ν(Tb–N) bonding. Uv-vis spectrum shown the characteristic absorption transitions of Tb³⁺ ion. A strong emission transition at 540 nm (⁵D₄ → ⁷F₅) was observed on excite by visible light at 414 nm.     

Broadband infrared luminescence from transparent glass–ceramics containing Ni<Superscript>2+</Superscript>-doped <Emphasis Type="BoldItalic">β</Emphasis> -Ga<Subscript>2</Subscript>O<Subscript>3</Subscript> nanocrystals

Transparent Ni²⁺-doped β-Ga₂O₃ glass–ceramics were synthesized. The nanocrystal phase in the glass–ceramics was identified to be β-Ga₂O₃ and its size was about 3.6 nm. It was confirmed from the absorption spectra that the ligand environment of Ni²⁺ ions changed from the trigonal bi-pyramid fivefold sites in the as-cast glass to the octahedral sites in the glass–ceramics. The broadband infrared emission centering at 1270 nm with full width at half maximum (FWHM) of more than 250 nm was observed. The fluorescence lifetime was about 1.1 μs at room temperature. The observed infrared emission could be attributed to the ³ T _2g (³ F )→³ A _2g (³ F ) transition of octahedral Ni²⁺ ions. It is suggested that the Ni²⁺-doped transparent β-Ga₂O₃ glass–ceramics with broad bandwidth and long lifetime have a potential as a broadband amplification medium. PACS 42.70.-a; 42.70.Ce; 81.40.Tv     

Reductive Fluorescence Quenching of the Photoexcited Free Base <Emphasis Type="Italic">meso</Emphasis>-Tetrakis (Pentafluorophenyl) Porphyrin by Amines

Steady state and time resolved fluorescence quenching behaviors of meso-Tetrakis (pentafluorophenyl) porphyrin (H₂F₂₀TPP) in presence of different aliphatic and aromatic amines have been executed in homogeneous dichloromethane (DCM) solution. At room temperature in DCM, free base (H₂F₂₀TPP) shows fluorescence with two distinct peaks at 640 and 711 nm and natural lifetime τ _f = 9.8 ns which are very similar to that of meso-tetraphenyl porphyrin (TPP). Unlike TPP, addition of both aliphatic and aromatic amines to a solution containing H₂F₂₀TPP results in an efficient decrease in fluorescence intensity without altering the shape and peak position of fluorescence emission. Upon addition of amines there was no change in optical absorption spectra of H₂F₂₀TPP. The fluorescence quenching rate constants ranged from 1 × 10⁹ to 4 × 10⁹ s⁻¹, which are one order below to the diffusion control limit, and temperature dependent quenching rate constants yield the activation energies which are found to be order of 0.1 eV. Femto second transient absorption studies reveal the existence of amine cation radical and porphyrin anion radicals with very short decay time (15 ps). The fluorescence quenching reaction follows Stern–Volmer kinetics. Steady state and time-resolved data are interpreted within general kinetic scheme of Marcus semi-classical model which attributes bimolecular electron transfer process between amines and the lowest excited singlet state of H₂F₂₀TPP. Calculated internal reorganization energies are found to be in between 0.04 and 0.22 ev. Variation of electron transfer rate as function of free energy change (∆G⁰) points the ET reactions in the present systems are in Marcus normal region. This is the first example of reductive fluorescence quenching of free base neutral porphyrins in homogeneous organic solvent ever known.     

Determination of Tetracaine Hydrochloride by Fluorescence Quenching Method with Some Aromatic Amino Acids as Probes

A novel fluorescence quenching method for the determination of tetracaine hydrochloride (TA·HCl) concentration with some aromatic amino acids as fluorescence probe has been developed. In pH 6.3 acidic medium, tryptophane (Trp), tyrosine (Tyr) or phenylalanine (Phe) can react with tetracaine hydrochloride to form an ion-association complex by electrostatic attraction, aromatic stacking interaction and Van der Waals’ force, which lead to fluorescence quenching of above amino acids. The maximum fluorescence excitation and emission wavelengths of them are located at 278, 274, 258 nm and 354, 306, 285 nm, respectively. The relative fluorescence intensity (F ₀/F) is proportional to the TA·HCl concentration in certain range. The linear ranges and detection limits are 1.2–5.0 μg/mL and 0.37 μg/mL for Tyr-TA·HCl system, 1.3–6.0 μg/mL and 0.38 μg/mL for Trp-TA·HCl system, and 1.4–6.0 μg/mL and 0.41 μg/mL for Phe-TA·HCl system. The optimum reaction conditions, influencing factors and the effect of coexisting substances are investigated. And the results show the method has a good selectivity. Judging from the effect of temperature, the Stern-Volmer plots and fluorescence lifetime determination, the quenching of fluorescence of amino acids by TA·HCl is a static quenching process.     

Spectroscopy and laser properties of Tm<Superscript>3+</Superscript>:KY(WO<Subscript>4</Subscript>)<Subscript>2</Subscript> crystal

The polarized absorption spectra of Tm³⁺-doped potassium yttrium tungstate (Tm:KY(WO₄)₂) crystal at room temperature were measured. The emission spectrum and lifetime of the ³ F ₄ excited state were determined. Using standard and modified Judd–Ofelt theories, the intensity parameters and the radiative lifetimes were calculated and good agreement with the experimental results was obtained for both theories. Continuous-wave laser operation in Tm:KYW crystal under laser diode pumping at 802 nm and 1750 nm was demonstrated with slope efficiency of 53% and 28% and output power of about 555 mW and 86 mW, respectively. PACS 42.55.Xi; 42.60.Pk; 42.70.Hj     

Excimer Fluorescence as a Tool for Monitoring Protein Domain Dynamics Applied to Actin Conformation Changes Based on Circulary Polarized Fluorescence Spectroscopy

Fluorescence-detected circular dichroism (FDCD) was introduced into the study of protein conformation changes. Actin was used as a model protein which undergoes dynamic conformation changes as it polymerizes. Actin labeled with N-(1-pyrene)iodoacetamide (PIA) showed monomer fluorescence peak at 386 and 410 nm, and excimer fluorescence peak at around 480 nm. Excimer was formed by PIA-dimers labeled to different sites of amino acid residues. New information concerned with actin structural changes were monitored by fluorescence emission spectra excited with left- and right-circulary polarized light at 355 nm. FDCD intensities were shown as the difference in the fluorescence emission ΔF, where ΔF=(F _L−F _R)/(F _L+F _R) denoting F _L and F _R as emissions obtained by excitation with left- and right-circulary polarized light. When solvent conditions of PIA-actin were changed by addition of NaCl, TFE, or ATP, ΔF showed sensitive responses to these compounds. From the analysis of ΔF _M and ΔF _E which represent the peaks of ΔF at the monomer- and excimer-emission band, the information concerned with the actin intrastructural changes were obtained. This method based on monitoring the excimer fluorescence with FDCD could be used for other proteins to extract finer structural changes that cannot be detected by the normal fluorescence spectroscopy.     

Fluorescence of N,N-di(2-carboxyethyl)-<Emphasis Type="Italic">p</Emphasis>-anisidine in solution and crystalline states

The fluorescence properties of N,N-di(2-carboxyethyl)-p-anisidine (I) in solvents of various nature and in the crystalline state have been studied at room temperature (273 K) and at the boiling point of liquid nitrogen (77 K). Fluorescence in aqueous solutions of I with protonated (λ _ex /λ _fl ^max = 225/290 nm) and unprotonated (λ _ex /λ _fl ^max = 270/380 nm) amino nitrogen has been detected. On going from aqueous solutions to nonaqueous, the fluorescence band of unprotonated I experiences a blue shift and its intensity rises. The fluorescence intensity of the band in aprotic polar solvents is higher than that in protic solvents. A linear dependence of the fluorescence intensity of deprotonated I on Cu(II) concentration (ranging from 1.0 to 5.0 mg/dm³) in aqueous solution has been found. The fluorescence intensity of I in aqueous solutions at 77 K and pH 1–6 has been shown to increase in the presence of Zn(II) (1–170 mg/dm³) and Cd(II) (2–330 mg/dm³) although a similar dependence is not observed at 293 K.     

Luminescence properties of oxide coatings on aluminum alloys

This is a study of the luminescence properties of coatings formed on aluminum alloys by anodizing in electrolytic solutions based on oxalic, sulfuric, and tartaric-sulfonic acids. At least two emission centers, with band maxima in the ranges of 390–410 and 470–510 nm, can be reliably identified in the photoluminescence spectra. The first type of center is characterized by single-band photoluminescence excitation spectra and the second, by two-band spectra. An analysis of the two-band photoluminescence excitation (PLE) spectra in the range of 470–510 nm shows that the position of the narrow short-wavelength PLE spectrum near 272 nm is independent of the type of acid used in the anodization process. The position and shape of the other PLE spectral bands depend both on the type of acid used and on the processing of the alloy or alumina surfaces. It is assumed that defect-free alumina centers are responsible for the 272 nm PLE band, while the other photoluminescence bands are caused primarily by different divacancies of oxygen (F₂⁺ {F_2^+} , F ₂, and F₂⁺² {F_2^{+2}} centers) whose origin is governed by the type of electrolyte.     

Luminescence properties of pyron red—A new molecular probe for protein research

The dependence of the luminescence of the new anionic dye Pyron Red (PR) on the polarity of the medium is investigated. Upon passage from an aqueous phase to a nonpolar phase, PR shows a shortwave shift of the fluorescence emission maximum from 675 to 650 nm and an increase in the fluorescence quantum yield from 0.03 to 0.54–0.70. When complexed with human serum albumin, PR shows fluorescence excitation and emission maxima at 525 and 625 nm and a fluorescence quantum yield of 0.8. In a comparison of the luminescence properties of PR with those of the well-known probes ANS and K35 in water and a complex with albumin, PR is shown to have the maximum absolute sensitivity but a lower fluorescence enhancement upon binding with a protein compared to ANS. A convenient criterion of the probe sensitivity toward binding with a protein that is defined as the ratio of the fluorescence intensities of the protein-bound and the free probe A_F=F_b/F_f is proposed. The value of A_F(35) for the PR probe ranks between those for the K35 probe with a low A_F(18) and ANS with a high A_F(105). Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 66, No. 3, pp. 369–374, May–June, 1999.     

Hydrothermal synthesis and photoluminescent properties of YV1 − xPxO4:Eu3+ (x = 0–1.0) nanophosphors

A simple hydrothermal process has been proposed to systematically synthesize europium-doped yttrium phosphate-vanadates with general formula YV_1 − xP_xO₄:Eu³⁺ (x = 0–1.0). All the YV_1 − xP_xO₄:Eu³⁺ products were characterized by x-ray diffraction (XRD) and transmission electron microscopy (TEM), the results of which revealed they were single-phase tetragonal-structured nanocrystals with diameter of 20 nm and their cell parameter a exhibited a linear relationship with the x value. Photoluminescence (PL) excitation and emission intensities of the products were sensitive to the x value and the change of the PL intensity with x was a wave-like curve which reached the peak at x = 0.4 and 0.8. In addition, the x value had an obvious influence on the (⁵D⁰–⁷F₂)/(⁵D₀–⁷F₁) intensity ratio of Eu³⁺.     

Intense Upconversion Luminescence of Yb<Superscript>3+</Superscript>-Er<Superscript>3+</Superscript> in Li<Subscript>2</Subscript>O Content Tungsten-tellurite Glasses

The Er³⁺ -Yb³⁺ codoped in Li₂O content tungsten -tellurite (TWL) transparent glasses are synthesized and measured the absorption, Raman and upconversion luminescence (UPL) spectra. At room temperature intense green emission peak at 560 nm ( ⁴S_3/2→⁴I_15/2) and red emission peak at 670 nm ( ⁴F_9/2→⁴I_15/2) of Er³⁺ observed even at minimum 86 mW pumping power of infrared 980 nm excitation. For structure of the TWL glass, Raman spectrum result revealed that an important role of WO₃ in the formation of glass network linkage with Li₂O. Under this influence estimated lifetime of the ⁴I_11/2 of Er³⁺ was 1.89 μs and due to lower phonon energy of the glass produce strong upconversion signal. The effect of Er₂O₃ concentration on emission intensity result indicated that green emission intensity initially increase in compare to red emission. Under the 980 nm pump power variation measured the relatively increases the red emission to the green emission intensity and analyze the possible upconversion mechanism and process.     

Spectroscopic properties of Nd<Superscript>3+</Superscript>:CaNb<Subscript>2</Subscript>O<Subscript>6</Subscript> crystal

The absorption spectra, fluorescence spectrum and fluorescence decay curve of Nd³⁺ ions in CaNb₂O₆ crystal were measured at room temperature. The peak absorption cross section was calculated to be 6.202×10⁻²⁰ cm² with a broad FWHM of 7 nm at 808 nm for E//a light polarization. The spectroscopic parameters of Nd³⁺ ions in CaNb₂O₆ crystal have been investigated based on Judd-Ofelt theory. The parameters of the line strengths Ω _t are Ω ₂=5.321×10⁻²⁰ cm²,Ω ₄=1.734×10⁻²⁰ cm²,Ω ₆=2.889×10⁻²⁰ cm². The radiative lifetime, the fluorescence lifetime and the quantum efficiency are 167 μs, 152 μs and 91%, respectively. The fluorescence branch ratios are calculated to be β ₁=36.03%,β ₂=52.29%,β ₃=11.15%,β ₄=0.533%. The emission cross section at 1062 nm is 9.87×10⁻²⁰ cm².     

Sensitizer-dependent up-conversion of Ho<Superscript>3+</Superscript> in nanocrystalline Y<Subscript>2</Subscript>O<Subscript>3</Subscript>

Ho³⁺–Yb³⁺ co-doped Y₂O₃ nanocrystals were synthesized by firing hydroxy carbonate precursors. Yb³⁺-concentration-dependent up-conversion properties of Ho³⁺ in Y₂O₃ nanocrystals have been investigated. The relative intensity of up-converted red emission increases more quickly than that of the green and the near-infrared ones with the enhancement of the concentration of Yb³⁺. It is believed that the energy process ⁵ S ₂ (⁵F₄) (Ho) + ⁵ I ₇ (Ho) →⁵ I ₆ (Ho)+⁵ F ₅ (Ho) plays an important role in the population of the ⁵ F ₅ level of Ho³⁺. The result indicates that the intensity ratio of the green emission to the red one can be tuned by changing the sensitizer concentration. PACS 78.55.-m     

The special features of the luminescence and light resistance of europium complexes and their mixtures with lanthanum complexes in polymethyl methacrylate

The kinetics of luminescence and transformation of short-lived products of the photolysis of europium and lanthanum complexes with thenoyltrifluoroacetone and 1,10-phenanthroline and their mixtures in polymethyl methacrylate films was studied by the nanosecond laser photolysis method with recording both light emission and absorption. Fast (535 and 585 nm, ⁵ D ₁ → ⁷ F ₀, ⁷ F ₃, decay time 0.7 μs) and slow (613 nm, ⁵ D ₀ → ⁷ F ₂, luminescence rise and decay times 0.7 μs and 0.5 ms, respectively) luminescence was studied. Induced absorption with a maximum at 600 nm and decay time ∼3 ms was observed; this absorption was assigned to triplet states of the deprotonated form of thenoyltrifluoroacetone. The dependences of luminescence intensity on the concentration of the components in a mixture of complexes were analyzed, and synergistic effects of luminescence strengthening were estimated. The kinetics of a decrease in luminescence intensity during photolysis was studied. Possible mechanisms of a decrease in the relative initial process rate and an increase in the quasi-stationary value of relative luminescence intensity as the concentration of complexes in the polymer increased were discussed.     

Amplification of radiation in atomic vapor induced by a linearly polarized laser radiation

We present the results of spectroscopic and polarization studies of dilute rubidium vapor exposed to a single-frequency linearly polarized diode laser radiation in a spectral range of atomic D₂ line. We report the origin of a circularly polarized radiation on V-type transitions of ⁸⁷Rb F _g = 2 → F _e = 3 and ⁸⁵Rb F _g = 3 → F _e = 4, and amplification of this radiation in backward direction caused by a partial population inversion among magnetic sublevels of the ground and excited levels. This is confirmed experimentally by high directivity of backward radiation, absence in its spectrum of ⁸⁵Rb F _g = 2 → F _e = 1 (Λ-type) radiation, as well as by different nature of intensity dependences of backward and fluorescence radiations.     

Synthesis of Functionalized ZnSe Nanoparticles and Their Applications in the Determination of Bovine Serum Albumin

Luminescent quantum dots (QDs)-semiconductor nanocrystals were promising alternative to organic dyes for fluorescence-based applications. In this paper, we developed procedures to use mercaptoacetic acid (MAA) to modify ZnSe nanoparticles and made the nanoparticles to be soluble for the quantitative and selective determination of bovine serum albumin (BSA). Maximum fluorescence intensity was produced at pH 7.0, with excitation and emission wavelengths at 242 and 348 nm, respectively. Under optimal conditions, the straight line equation: ^△ F = 0.38 + 0.34 C (μg/ml) was found between the relative fluorescence intensity and the concentration of BSA in the range of 9.6–124.8 μg/ml, and the limit of detection was 2 μg/ml.     

Photoluminescence characteristics of ZnS nanocrystallites doped with Ti3+and Ti4+

Direct synthesis of ZnS nanocrystallites doped with Ti³⁺ or Ti⁴⁺ by precipitation has led to novel photoluminescence properties. Detailed X-ray diffraction (XRD), fluorescence spectrophotometry, UV–vis spectrophotometry and X-ray photoelectron spectroscopy (XPS) analysis reveal the crystal lattice structure, average size, emission spectra, absorption spectra and composition. The average crystallite size doped with different mole ratios, estimated from the Debye–Scherrer formula, is about 2.6±0.2 nm. The nanoparticles can be doped with Ti³⁺ and Ti⁴⁺ during the synthesis without the X-ray diffraction pattern being altered. The strong and stable visible-light emission has been observed from ZnS nanocrystallites doped with Ti³⁺ (its maximum fluorescence intensity is about twice that of undoped ZnS nanoparticles). However, the fluorescence intensity of the ZnS nanocrystallites doped with Ti⁴⁺ is almost the same as that of the undoped ZnS nanoparticles. The emission peak of the undoped sample is at 440–450 nm. The emission spectrum of the doped sample consists of two emission peaks, one at 420–430 nm and the other at 510 nm. Received: 27 April 2001 / Accepted: 16 August 2001 / Published online: 17 October 2001     

香蕉叶片Chla荧光动力学参量对激发光强的反应

在蓝色激发光(λ_m＝660nm)作用下,香蕉叶片的叶绿素a(Chla)发出波长为720～740nm的荧光信号,荧光强度随时间呈现有规律的变化.随着激发光强的增加,荧光动力学参量F₀和F_VI/F_V呈上升趋势,F_V/F₀与F_V/F_M逐渐达到饱和,而CA和T_1/2呈下降趋势.研究结果表明,保证香蕉叶片光合机构高速有序运转的适宜光强在20～60μmol·m^-2·s^-1之间,过量的光强将造成叶片光合机构的损伤.讨论了香蕉叶片诸荧光动力学参量的生物学意义及其随激发光强度增加而变化的原因.     

Thermal and optical properties of Tm<Superscript>3+</Superscript>:NaLa(WO<Subscript>4</Subscript>)<Subscript>2</Subscript> crystal

A Tm³⁺-doped NaLa(WO₄)₂ single crystal with a dimension of Φ20 mm×40 mm was grown by the Czochralski method. Anisotropic thermal expansion coefficients of this crystal were investigated. Polarized absorption spectra, emission spectra and decay curve were recorded at room temperature. The absorption and emission cross-section were presented. Based on the Judd–Ofelt analysis, we obtained the three intensity parameters: Ω₂=10.21×10^-20, Ω₄=2.66×10^-20, and Ω₆=1.46×10^-20 cm². The radiative probabilities, radiative lifetimes, and branch ratios of Tm³⁺:NaLa(WO₄)₂ were calculated, too. Luminescence lifetime of the ³ H ₄ level was measured to be 220 μs. The stimulated emission cross-section for the ³ F ₄→³ H ₆ transition were determined using the reciprocity method, potential laser gain for this transition were also investigated, the gain curves implied that the tunable range is up to 200 nm. PACS 42.70.Hj; 78.20.-e     

Radiative characteristics and kinetics of processes in low-pressure gas-discharge lamps based on a mixture of helium and iodine vapors

The UV radiation of glow- and capacitive-discharge lamps based on mixtures of inert gases with iodine vapors are optimized in the spectral range of 175–360 nm, in which working helium-iodine mixtures of different compositions are used. The most intense spectral lines in the bactericidal region of the spectrum were the atomic lines of iodine (183.0, 206.2 nm), and in the region of 320–360 nm, emission of the spectral band of an iodine molecule prevailed with a maximum at λ = 342 nm. For a capacitive lamp with a casing opaque in the spectral range λ < 250 nm, the main part of the plasma emission power is concentrated in the A′-D′ band of an iodine molecule with a maximum at 342 nm. The emission brightness of this lamp is optimized in iodine molecule transitions depending on the partial helium pressure. We present the results of simulating the kinetics of processes in a glow-discharge plasma in mixtures of He, Xe, and iodine vapors. We establish the dependence of the main part of the emission intensity of the 206.2 nm spectral line of an iodine atom and the 342 nm band of an iodine molecule on the helium pressure in a glow-discharge lamp operating on a He-I₂ mixture.