A UV resonance Raman investigation of poly(rI): Evidence for cation-dependent structural perturbations

Poly(rI) stabilized by either Na⁺ or K⁺ was investigated using uv resonance Raman (UVRR) spectroscopy. Raman excitation profiles of inosine 5′-monophosphate demonstrated the 250 nm excitation selectively enhances base stacking interactions, while ribose and carbonyl stretching vibrations are preferentially enhanced with 210 nm excitation. These wavelengths were used to examine the structure of poly(rI) in the presence of either K⁺ or Na⁺ as a function of temperature. UVRR studies revealed that the K⁺ stabilized form is more thermally stable, yielding a T_m of ∼ 47°C compared to a T_m of ∼ 30°C for the Na⁺ stabilized form. We observed that both the ribosyl conformation and the coordination of the carbonyl groups depend on the nature of the cation. The C₆O stretching frequency indicates that Na⁺ coordinates much more strongly to the carbonyl groups than K⁺ (1672 cm⁻¹ Na⁺ vs 1684 cm⁻¹ K⁺ at 4°C). Conformationally sensitive modes of the phosphate backbone and the ribosyl ring indicate that Na⁺ stabilized poly(rI) predominantly exists in a C_3′-endo ribose conformation, whereas K⁺ stabilized poly(rI) adopts a C_2′-endo conformation possibly as a consequence of the larger ionic radius of the K⁺ ion. © 1998 John Wiley & Sons, Inc. Biopoly 46: 475–487, 1998     

Influence of excitation light intensity and leaf age on the slow chlorophyll fluorescence transient in radish

The temporal characteristics of the slow phase of chlorophyll fluorescence induction-T _0.5 (half-decay time) and t _min (an integral-based index of the variable emission rate)-as well as the popular amplitude index F _P/F _S were determined at different excitation light intensities (I _ex [400?C500 nm] of 20?C80 W/m²) in dark-adapted leaves of different age (3?C24 days) taken from radish plants grown under continuous light of 100 W/m² PAR. All the profiles thus obtained were mutually consistent, and the age-related variations were minimized at I _ex > 40 W/m²; at that the age-averaged temporal indices proved to be more light-responsive than the standard amplitude ratio.     

Luminescence properties of Tb3+ doped Sr2SnO4 green phosphor in UV/VUV regions

Polycrystalline Sr₂SnO₄ phosphors doped with Tb³⁺ were prepared by conventional solid‐state reaction method. Materials were characterized by powder XRD and EDS techniques. The luminescence properties of these materials were investigated under UV and VUV excitation. Upon excitation at 272 nm, phosphors exhibited intense emissions at 492 and 543 nm due to ⁵D₄ → ⁷ F₆ and ⁵D₄ → ⁷ F₅ transitions of Tb³⁺ ions, respectively. Materials also exhibited strong emissions from these transitions under VUV excitation at 147, 173 and 230 nm. Quantitative analysis of the spectra indicated probable applications of these phosphors for PDP and other display devices as green emitting phosphors. Copyright © 2012 John Wiley & Sons, Ltd.     

Effect of preillumination on the P-680+ reduction kinetics in chloride-free photosystem II membranes

The re-reduction course of P-680⁺, the photooxidized PS II primary donor, was measured as a function of excitation number in Cl⁻-depleted PS II membranes. After the 1st and 2nd excitations the signal amplitude of P-680⁺ is small, indicating a submicrosecond reduction of P-680⁺ by Z, the secondary donor of PS II. After the 3rd excitation, however, a larger P-680⁺ signal with a 40–50 μs half-life is observed. The slow decay of this signal is attributed to a back-reaction with a reduced acceptor in the presence of the Z⁺S₂ state on the donor side. The state Z⁺S₂ has a lifetime longer than 300 ms and its formation was found to depend on the presence of the abnormal S₂ state created by the 1st excitation. The P-680 data and thermoluminescence measurements show that the S-state advancement beyond S₂ is blocked in the absence of Cl⁻ and that the Cl⁻-free abnormal S₂ state has a lifetime about 10-times longer than the normal S₂ state.     

Eu2+ luminescence in SrCaP2O7 pyrophosphate phosphor

A series of Eu²⁺ activated SrCaP₂O₇ pyrophosphate phosphors were synthesized by the modified solid‐state reaction method. The X‐ray diffraction (XRD) and photoluminescence (PL) properties of these phosphors were investigated at room temperature. The excitation spectra indicate that these phosphors can be effectively excited by Hg‐free excitation. The emission spectra exhibit strong blue performance, which is due to the 4f⁶5d¹→4f⁷ transition of Eu²⁺. The Fourier transform infrared spectrum at room temperature was investigated and surface morphology has been studied by scanning electron microscope. The prepared phosphor exhibited intense blue emission at the 427 nm owing to Eu²⁺ ion by Hg‐free excitation at 330 nm, that is, solid‐state lighting excitation. Hence, the availability of such a phosphor will significantly help in the growth of blue‐emitting solid‐state lighting applications. Copyright © 2012 John Wiley & Sons, Ltd.     

Luminescence in Li3Al2(PO4)3:Eu2+

A series of efficient Li₃Al₂(PO₄)₃:Eu²⁺ novel phosphors were synthesized by the facile combustion method. The effects of dopant on the luminescence behavior of Li₃Al₂(PO₄)₃ phosphor were also investigated. The phosphors were characterized by X‐ray diffraction, field emission scanning electron microscope and photoluminescence techniques. The result shows that all samples can be excited efficiently by near‐ultraviolet excitation under 310 nm. The emission was observed for Li₃Al₂(PO₄)₃:Eu²⁺ phosphor at 425 nm, which corresponded to the d → f transition. The concentration quenching of Eu²⁺ was observed in Li₃Al₂(PO₄)₃:Eu²⁺ when the Eu concentration was at 0.5 mol%. The prepared powders exhibited intense blue emission at the 425 nm owing to the Eu²⁺ ion by Hg‐free excitation at 310 nm (i.e., solid‐state lighting excitation). Consequently, the availability of such a phosphor will significantly help in the development of blue‐emitting solid‐state lighting applications. Copyright © 2012 John Wiley & Sons, Ltd.     

Photoluminescence properties of LiTi2 − xEux(PO4)3 phosphor

A solid‐state reaction route‐based LiTi_{2 ? x}Eu_x(PO₄)₃ was phosphor synthesized for the first time to evaluate its luminescence performance by excitation, emission and lifetime (τ) measurements. The LiTi_{2 ? x}Eu_x(PO₄)₃ phosphor was excited at λ_exci. = 397 nm to give an intense orange–red (597 nm) emission attributed to the ⁵D₀ → ⁷F₁ magnetic dipole (ΔJ = ±1) transition and red (616 nm) emission (⁵D₀ → ⁷F₂), which is an electric dipole (ΔJ = ±2) transition of the Eu³⁺ ion. Beside this, excitation and emission spectra of host LiTi₂(PO₄)₃ powder were also reported. The effect of Eu³⁺ concentration on luminescence characteristics was explained from emission and lifetime profiles. Concentration quenching in the LiTi_{2 ? x}Eu_x(PO₄)₃ phosphor was studied from the Dexter's model. Dipole–quadrupole interaction is found to be responsible for energy transfer among Eu³⁺ ions in the host lattice. The LiTi_{2 ? x}Eu_x(PO₄)₃ phosphor displayed a reddish‐orange colour realized from a CIE chromaticity diagram. We therefore suggest that this new phosphor could be used as an optical material of technological importance in the field of display devices. Copyright © 2016 John Wiley & Sons, Ltd.     

White‐ and blue‐light‐emitting dysprosium(III) and terbium(III)‐doped gadolinium titanate phosphors

Here we report the synthesis and structural, morphological, and photoluminescence analysis of white‐ and blue‐light‐emitting Dy³⁺‐ and Tm³⁺‐doped Gd₂Ti₂O₇ nanophosphors. Single‐phase cubic Gd₂Ti₂O₇ nanopowders consist of compact, dense aggregates of nanoparticles with an average size of ~25 nm for Dy³⁺‐doped and ~50 nm for Tm³⁺‐doped samples. The photoluminescence results indicated that ultraviolet (UV) light excitation of the Dy³⁺‐doped sample resulted in direct generation of white light, while a dominant yellow emission was obtained under blue‐light excitation. Intense blue light was obtained for Tm³⁺‐doped Gd₂Ti₂O₇ under UV excitation suggesting that this material could be used as a blue phosphor.     

Monitoring Receptor Mediated Regulation of Cytosolic Calcium in Single Pituitary Cells by Dual Excitation Microfluorimetry

Abstract

Receptor-mediated alterations in the cytosolic free calcium concentration, [Ca²⁺]_i are monitored with the intracellular fluorescent calcium probe fura 2 by dual excitation microfluori-metry. The calcium dependence on the excitation spectrum of fura 2 allows us to choose two wavelengths, λ₁ and λ₂, at which an increase in [Ca²⁺]_i causes either a rise or a fall in fluorescence; the ratio of fluorescence at λ₁ and λ₂ (R =Fλ₁/Fλ₂) is a measure of [Ca²⁺]_i. It appears essential for such measurements that the alteration between the two excitation wavelengths is done rapidly, to allow us to distinguish between effects on [Ca²⁺]_i and other effects on fluorescence. In addition, specific problems relating to the calibration of fura 2 measurements, such as its relative insensitivity at basal [Ca²⁺]_i, the role of intracellular viscosity on fura 2 fluorescence, and the difficulties encountered in establishing calibration constants have to be appreciated. In spite of these potential drawbacks, it appears that monitoring receptor-mediated [Ca²⁺]_i regulation in single cells will prove essential for the further comprehension of stimulus-secretion coupling in pituitary and probably many other cell types.     

Luminescent properties and energy transfer in the green phosphors LaBSiO5:Tb3+,Ce3+

LaBSiO₅ phosphors doped with Ce³⁺ and Tb³⁺ were synthesized using the conventional solid‐state method at 1100 °C. The phase purity and luminescent properties of these phosphors are investigated. LaBSiO₅:Tb³⁺ phosphors show intense green emission, and LaBSiO₅ phosphors doped with Ce³⁺ show blue–violet emission under UV light excitation. LaBSiO₅ phosphors co‐doped with Ce³⁺ and Tb³⁺ exhibit blue–violet and green emission under excitation by UV light. The blue–violet emission is due to the 5d–4f transition of Ce³⁺ and the green emission is ascribed to the ⁵D₄ → ⁷ F₅ transition of Tb³⁺. The spectral overlap between the excitation band of Tb³⁺ and the emission band of Ce³⁺ supports the occurrence of energy transfer from Ce³⁺ to Tb³⁺, and the energy transfer process was investigated. Copyright © 2014 John Wiley & Sons, Ltd.     

Pore water nutrient profiles and dynamics in soft bottoms of the northern Baltic Sea

Chemical profiles of nutrients at the sediment–water interface were measured in the northern Baltic Sea. A whole core squeezer technique capable of mm-scale resolution was used to obtain the vertical profiles of NO₃ ^–, NO₂ ^–, o-P, NH₄ ⁺ and Si in the soft bottom sediments. The profiles were compared with nutrient flux and denitrification measurements. In the Gulf of Finland, the profiles revealed a marked chemical zonation in NO₃ ^– and NO₂ ^– distribution indicating strong potential of nitrification just under the sediment surface followed by a layer of denitrification down to a depth of 30 mm. Below the depth of 20 mm NO₃ ^– was usually absent, whereas other nutrients were increasing steadily in concentration. A distinct minimum of NO₃ ^– was observed at the sediment–water interface, suggesting NO₃ ^– uptake by a microbial biofilm and/or active denitrification at the suboxic microniches usually present in organic-rich sediments. At the deep stations in the Baltic Proper, the NO₃ ^– concentration in pore water, as well as denitrification, were very low. The concentrations of NH₄ ⁺, o-P and Si were usually increasing steadily with depth.     

Novel red colour emitting Ca0.995Mg2(SO4)3:0.5Eu2+ phosphor under ultraviolet,blue, and green excitation for plant growth LEDs

In the recent few years, Eu²⁺- and Mn⁴⁺-activated phosphors are widely used as potential colour converters for indoor plant cultivation lighting application due to their marvellous luminescence characteristics as well as low cost. In this investigation, we synthesized novel red colour-emitting Ca_(2−x)Mg₂(SO₄)₃:xmol% Eu²⁺ (x = 0–1.0 mol%) phosphors via a solid-state reaction method in a reducing atmosphere. The photoluminescence (PL) excitation spectra of synthesized phosphors exhibited a broad excitation band with three excitation bands peaking at 349 nm, 494 nm, and 554 nm. Under these excitations, emission spectra exhibited a broad band in the red colour region at ~634 nm. The PL emission intensity was measured for different concentrations of Eu²⁺. The maximum Eu²⁺ doping concentration in the Ca₂Mg₂(SO₄)₃ host was observed for 0.5 mol%. According to Dexter theory, it was determined that dipole–dipole interaction was responsible for the concentration quenching. The luminous red colour emission of the sample was confirmed using Commission international de l'eclairage colour coordinates. The results of PL excitation and emission spectra of the prepared phosphors were well matched with excitation and emission wavelengths of phytochrome P_R. Therefore, from the entire investigation and obtained results it was concluded that the synthesized Ca_0.995Mg₂(SO₄)₃:0.5mol%Eu²⁺ phosphor has huge potential for plant cultivation application.     

Molten salt synthesis and luminescence of Dy3+‐doped Y3Al5O12 phosphors

Dy³⁺‐doped Y₃Al₅O₁₂ phosphors were prepared at a relatively low temperature using molten salt synthesis. The phase of the prepared Dy³⁺‐doped Y₃Al₅O₁₂ phosphors was confirmed using X‐ray powder diffraction. Results indicated that Dy³⁺ doping did not change the Y₃Al₅O₁₂ phase. Following excitation at 352 nm, emission spectra of the Dy³⁺‐doped Y₃Al₅O₁₂ phosphors consisted of blue, yellow, and red emission bands. The influence of Dy³⁺ concentration and excitation wavelength on emission was investigated. The ratio of yellow light to blue light varied with change in Dy³⁺ doping concentration, due to changes in the structure around Dy³⁺. Emission intensities also changed when the excitation wavelength was changed. This variation is luminescence generated a system for tunable white light for Dy³⁺‐doped Y₃Al₅O₁₂ phosphors.     

Optical analysis of Sr3Gd(PO4)3:Pr3+ phosphors for lighting applications

A series of praseodymium (Pr³⁺) ion activated Sr₃Gd_(1−x)(PO₄)₃:xPr³⁺ (0 ≤ x ≤ 2.0 mol%) phosphors were prepared and their structural, compositional and luminescence properties were investigated. The X-ray diffraction profiles indicate that the studied phosphors crystallized into body centred cubic structure and the Pr³⁺ ions have no influence on Sr₃Gd(PO₄)₃ phase. The high-resolution scanning electron microscopy images show the agglomeration of particles that are inter-connected and form irregular shape Sr₃Gd(PO₄)₃ structures. The excitation transitions corresponding to Pr³⁺:³H₄ → ³P_2,1,0 transitions at 445, 471 and 483 nm, respectively, matched well with the emission of blue-light-emitting diode (LED) chip. The emission spectra show strong reddish-orange luminescence through ¹D₂ → ³H₄ transition when excited at 445 nm blue wavelength. The synthesized phosphors have the potential to be used as reddish-orange lighting devices.     

Spectroscopic and photoluminescence characterization of Dy3+ in Sr0.5Ca0.5TiO3 phosphor

The spectroscopic and photoluminescence characteristics of trivalent dysprosium (Dy³⁺)‐doped Sr_0.5Ca_0.5TiO₃ phosphor materials synthesized via solid‐state reaction method were studied. The X‐ray diffraction profile confirmed the orthorhombic perovskite structure of the prepared samples. Judd–Ofelt analysis was carried out to obtain the intensity parameters and predicted radiative properties of Sr_0.5Ca_0.5TiO₃:2wt%Dy³⁺. The photoluminescence spectrum of Dy³⁺‐doped Sr_0.5Ca_0.5TiO₃ showed three emission peaks at 481, 574 and 638 nm corresponding to ⁴F_9/2→⁶H_15/2, ⁴F_9/2→⁶H_13/2 and ⁴F_9/2→⁶H_11/2 transitions respectively. The variation of luminescence intensity with different excitation wavelengths and Dy³⁺ concentrations is discussed. The decay profiles of ⁴F_9/2 excited levels of Dy³⁺ ions show bi‐exponential behaviour and also a decrease in average lifetime with increase in Dy³⁺ concentration. Yellow to blue luminescence intensity ratio, CIE chromaticity co‐ordinates and correlated color temperature were also calculated for different concentrations of Dy³⁺‐doped Sr_0.5Ca_0.5TiO₃ phosphor at different λ_ex. Copyright © 2015 John Wiley & Sons, Ltd.     

Preparation and luminescence properties of KLaSiO4:Tb3+ phosphors

KLaSiO₄:Tb³⁺ phosphors were synthesized using the sol–gel method. The structure and luminescence properties of the materials were characterized using X-ray diffraction, Fourier transform infrared (FTIR) spectroscopy, thermogravimetry–differential thermal analysis, fluorescence spectra and calculated Commission Internationale de l'éclairage coordinates. The results showed that the material had a hexagonal structure, and that doping of Tb³⁺ did not change the crystal structure of KLaSiO₄. FTIR spectroscopy confirmed the existence of stretching vibrations of Si–O, bending vibrations of Si–O–Si, and asymmetric tensile vibrations of Si–O in KLaSiO₄. The excitation spectrum of the sample consisted of 4f⁷→5d¹ broadband absorption and the characteristic excitation peak of Tb³⁺, the excitation peak at 232 nm belongs to the spin allowed ⁷F_J→⁷D_J transition of Tb³⁺, the excitation peak at 268 nm belongs to the spin forbidden ⁷F_J→⁹D_J transition of Tb³⁺, and the absorption band of ⁷F_J→⁷D_J transition is split. Under excitation at 232 nm, the emission peak of the sample was composed of the ⁵D₄→⁷F_J (J = 6, 5, 4, 3) energy level transition of Tb³⁺. The highest emission peak is located at 543 nm, which belongs to the ⁵D₄→⁷F₅ transition and emits green light. Concentration quenching occurred when the Tb³⁺ doping concentration was greater than 1% mol, the quenching mechanism was an electric dipole–electric dipole action. When the ratio of citric acid to total metal ions was 1:1 and the annealing temperature was 800°C, the surface defects of the phosphors were greatly reduced, the quenching effect was reduced, and the luminous intensity reached the maximum.     

Photoluminescence in K3Ca2(SO4)3Cl‐doped Eu3+ phosphor

In this article we report Eu³⁺ luminescence in novel K₃Ca₂(SO₄)₃Cl phosphors prepared by wet chemical methods. The Eu³⁺ emission was observed at 594 nm and 615 nm, keeping the excitation wavelength constant at 396 nm nearer to light‐emitting diode excitation, Furthermore, phosphors were characterized by X‐ray diffraction for the confirmation of crystallinity. The variation of the photoluminescence intensity with impurity concentration has also been discussed. Thus, prominent emission in the red region makes prepared phosphors more applicable for white light‐emitting diodes. Copyright © 2013 John Wiley & Sons, Ltd.     

Sol‐gel synthesis and luminescent properties of red‐emitting Y(P,V)O4:Eu3+ phosphors

Eu³⁺‐activated Y(P,V)O₄ phosphors were prepared by the EDTA sol‐gel method, and the corresponding morphologies and luminescent properties were investigated. The sample particles were relatively spheroid with size of 2–3 µm and had a smooth surface. The excitation spectra for Y(P,V)O₄:Eu³⁺ consisted of three strong excitation bands in the 200–350 nm range, which were attributed to a Eu³⁺‐ O^2? charge‐transfer band and ¹A₁?¹ T₁/¹ T₂ transitions in VO₄^3?. The as‐synthesized phosphors exhibited a highly efficient red luminescence at 613 nm due to the Eu^{3+ 5}D₀?⁷ F₂ electric dipole transition. With the increase in the V⁵⁺/P⁵⁺ ratio, the luminescence intensity of the red phosphor under UV excitation was greatly improved due to enhanced VO₄^3? → Eu³⁺ energy transfer. Copyright © 2015 John Wiley & Sons, Ltd.     

Green synthesis,structure feature and energy transfer of yellow-emitting (Y,Gd)2O2SO4:Dy phosphors

A green chemical precipitation route was used to yield a hydrated basic sulfate precursor upon calcination at 1000°C into a series of (Y,Gd)₂O₂SO₄:Dy particles. The phosphors exhibited characteristic Dy³⁺ emissions from ⁴F_9/2→⁶H_J (J = 15/2, 13/2, 11/2) transitions under ultraviolet light excitation; the quenching concentration of Dy³⁺ was determined to be 2.5 at.%. Substitution of Gd³⁺ for Y³⁺ led to an additional strong sharp band at ~277 nm (⁸S_7/2→⁶I_J transition of Gd³⁺) in the photoluminescence excitation spectra, upon which the (Gd_0.975Dy_0.025)₂O₂SO₄ phosphor achieved a ~2.8-fold higher photoluminescence intensity via an effective energy transfer from Gd³⁺ to Dy³⁺ compared with the 354 nm excitation of Dy³⁺. Both the photoluminescence and photoluminescence excitation intensities of (Y,Gd)₂O₂SO₄:Dy phosphors increased with rising Gd³⁺ concentration and calcination temperature in the range 750–1000°C. A higher Gd³⁺ concentration slightly prolonged the effective fluorescence lifetime.     

Pulsed ENDOR of the photoexcited triplet states of bacteriochlorophyll a and of the primary donor P865 in reaction centers of Rhodobacter sphaeroides R-26

The photoexcited triplet states of bacteriochlorophyll a, ³BChl a, and of the primary donor in reaction centers of Rhodobacter sphaeroides R-26, ³P₈₆₅, are investigated by pulsed EPR and ENDOR spectroscopy. In ³P₈₆₅ a splitting of ENDOR lines and reduction of corresponding positive and negative hyperfine couplings as compared with the monomeric ³BChl a is observed. This indicates an asymmetric distribution of the triplet excitation over the two BChl a moieties, P_L and P_M, forming ³P₈₆₅. Based on the signs of the hyperfine couplings and on a comparison with the cation and anion radical of BChl a an assignment to nuclei in the different dimer halves is proposed. This yields an estimate for the extent of delocalization of the triplet excitation over P_L and P_M and for the charge transfer contribution of ³P₈₆₅.