Possible production of O2(1Δg) and O2(1Σ+g) in the reaction of NO with O3

High-resolution spectra of the NO₂ continuum emission produced from the reaction NO + O₃ → NO₂ + O₂ have been investigated to detect any possible emission from O₂(¹Δ_g) at 1270 nm or O₂(¹Σ⁺_g) at 762 nm. The photolysis of O₃/O₂ mixtures at 253.7 nm, which produces both states of O₂ with known quantum efficiency, has been used as an internal standard. From the results it is concluded that less than 1/300 and 1/200 of the NO + O₃ reactive collissions result in production of O₂(¹Δ_g) or O₂(¹Σ⁺_g), respectively, at room temperature.     

SrSi2O2N2∶Eu2+荧光粉的制备及性能研究

以SrCO3,Si3N4,Eu2O3为原料,在N2气氛下,采用自还原高温固相法制备了SrSi2O2N2:Eu2+荧光粉。研究了该荧光粉的物相结构、发光性能和晶体形貌,同时对比在不同气氛下合成的荧光粉。结果表明,在N2气氛与N2/H2气氛下分别合成的SrSi2O2N2:Eu2+荧光粉物相结构和光谱特性基本一致。显示出合成了主晶相SrSi2O2N2,但还含有少量未知的中间项。Eu2+浓度的变化不影响激发状态,而发射光谱的波长在Eu2+浓度为1mol%-20mol%之间,从530 nm的绿光红移至550 nm的黄绿光区域。同时,激发光谱覆盖的范围宽,均能有效的被UV或蓝光激发,这意味着该类荧光粉在白光LED方面有可能得到广泛的应用。     

The effects of ZnGa2O4 formation on structural and optical properties of ZnO:Ga powders

Gallium-doped zinc oxide (ZnO:Ga 1, 2, 3, 4 and 5 at%) samples were prepared in powder form by modifying the Pechini method. The formation of zinc gallate (ZnGa₂O₄) with the spinel crystal structure was observed even in ZnO:Ga 1 at% by X-ray diffraction. The presence of ZnGa₂O₄ in ZnO:Ga samples was also evidenced by luminescence spectroscopy through its blue emission at 430 nm, assigned to charge transfer between Ga³⁺ at regular octahedral symmetry and its surrounding O²⁻ ions. The amount of ZnGa₂O₄ increases as the dopant concentration increases, as observed by the quantitative phase analysis by the Rietveld method.     

Oxciplex emission of naphthalenes in polymer matrices

In this communication we report the observation of oxciplex emission, (T₁ + O₂(¹Δ)) → (S₀ + O₂(³Σ)) + hν from naphthalene and octafluoronaphthalene in polystyrene fluffs. We detect this emission as an oxygen induced luminescence burst upon admission of oxygen to a phosphorescing sample. The assignment is based on a mirror image relationship of the emission to the absorption, and energetic, kinetic, and intensity considerations.     

Luminescence Properties of Mn2+-Doped Sol-Gel Glasses

Mn²⁺-doped 1Al₂O₃-99SiO₂ glasses have been prepared by a sol-gel method and their photoluminescence (PL) properties have been studied for the first time. The effect of ZrO₂ and TiO₂ on the luminescence properties has also been studied. In addition, the PL of Mn: 1Al₂O₃-99SiO₂ is compared with Mn:SiO₂. The emission spectra of all the samples containing Al₂O₃ show a band around 620 nm, and the sample without Al₂O₃ shows two bands around 620 and 650 nm. These emission bands are all assigned to the ⁴T₁ ⁶A₁ transition of octahedrally coordinated Mn²⁺ · ZrO₂ and TiO₂ have fluorescence quenching effect. The relative fluorescence intensity of Mn²⁺-doped sol-gel 1Al₂O₃-99SiO₂ is much stronger than that of Mn²⁺-doped sol-gel SiO₂. The difference of the emission wavelength between host materials is explained in terms of the ligand field effect.     

A novel sensitized chemiluminescence flow injection system for the determination of adriamycin and mitomycin

A novel chemiluminescence (CL) method was established for two anticancer drugs, adriamycin (ADM) and mitomycin (MMC), based on potassium permanganate oxidation in the presence of formaldehyde. The sensitized CL emission mechanism was developed by comparing the fluorescence emission with CL spectra. Illuminant was the singlet state bi-molecule oxygen, ¹O₂ ¹O₂ (¹Δ_g ¹Δ_g), from ¹O₂ (¹Δ_g) which was produced in the reaction system, and emitted CL spectra at 639 nm or 649 nm. The presence of formaldehyde may accelerate the generation of ¹O₂ (¹Δ_g) and sensitized CL emission. The optimum conditions for CL emission were investigated and optimized. The relationships between the relative CL intensity and the concentration of the studied analytes found to be linear. The detection limit was 3 × 10^?8 g ml^?1 for ADM and 3 × 10^?9 g ml^?1 for MMC. The relative standard deviations are 2.2% and 1.8% for determinations of ADM at 2.0 × 10^?6 g ml^?1 and MMC at 2.0 × 10^?7 g ml^?1, respectively. The proposed sensitized CL system was successfully applied to the determination of ADM and MMC in their injections with satisfactory results.     

Flow-injection-enhanced chemiluminescence method for the determination of four anticancer drugs

Novel chemiluminescence (CL) reaction systems were established for the determination of anticancer drugs, including adriamycin (ADM), hydroxycamptothecin (HCPT), mitomycin (MMC), and fluorouracil (5-FU). The formaldehyde-sensitized CL emission mechanism was developed for four systems by comparing the fluorescence emission and CL spectra. For ADM-KMnO₄-HNO₃, HCPT-KMnO₄-H₂SO₄, MMC-KMnO₄-HNO₃, and 5-FU-KMnO₄-HCl systems, the illuminant was a singlet state bimolecule oxygen, ¹O₂ ¹O₂(¹Δ_g ¹Δ_g), which was formed from ¹O₂ (¹Δ_g) produced in the reaction system. The illuminant emits CL spectra at 539 or 549 nm. The presence of formaldehyde can sensitize CL emission because it may accelerate the generation of ¹O₂ (¹Δ_g). The optimum conditions for the CL emission were chosen. The relationships between the relative CL intensity and the concentration of the studied analytes are linear with the correlation coefficients in the range of 0.9959–0.9989. The proposed four enhanced CL systems provide a good linearity, a high sensitivity, precision, and the potential capability for the determination of anticancer drugs in biological samples. The text was submitted by the authors in English.     

Host-sensitized emission of LiInW2O8 wolframites: From red-Eu to white-Dy phosphors

The LiInW₂O₈:Eu³⁺, LiInW₂O₈:Dy³⁺ and LiInW₂O₈:Eu³⁺/Dy³⁺ phosphors were synthesized by solid-state reaction and their photoluminescence properties were studied. Under UV excitation, the LiInW₂O₈:Eu³⁺ phosphor exhibits an intense red emission whereas the LiInW₂O₈:Dy³⁺ and LiInW₂O₈:Dy³⁺/Eu³⁺ phosphors show a white emission. The WO₆ octahedra play a major role in the luminescence of the host lattice, characterized by a blue emission under UV excitation. The emission of activator ion results from an efficient energy transfer from the LiInW₂O₈ host lattice to the Eu³⁺ and Dy³⁺ ions. The LiIn_0.97Dy³⁺_0.03W₂O₈ and LiIn_0.965 Dy³⁺_0.03Eu³⁺_0.005W₂O₈ samples, optimized for white emission, are interesting candidates for solid-state lighting applications.     

The rate constant for the “dimol” transition of singlet oxygen,O2(a 1Δg), and the likely symmetry of the emitting species

A comparison has been made of the value of the rate constant for the simultaneous “dimol” emission of O₂(¹Δ_g), calculated from the absorption spectrum, with those from emission measurements. It is suggested that the emitting (O₂)₂ species has D_2h symmetry and that the transition is ¹B_2u-¹A_g. The best value is k = (3.3 ± 0.6) × 10^?2 dm³ mol^?1 s^?1 at 295 K. The temperature dependence is also discussed.     

Effect of Physiological Concentrations of Vitamin C on the Inhibitation of Hydroxyl Radical Induced Light Emission from Fe2+-EGTA-H2O2 and Fe3+-EGTA-H2O2 Systems In Vitro

Ascorbic acid (AA) has antioxidant properties. However, in the presence of Fe²⁺/Fe³⁺ ions and H₂O₂, it may behave as a pro-oxidant by accelerating and enhancing the formation of hydroxyl radicals (^•OH). Therefore, in this study we evaluated the effect of AA at concentrations of 1 to 200 µmol/L on ^•OH-induced light emission (at a pH of 7.4 and temperature of 37 °C) from 92.6 µmol/L Fe²⁺—185.2 µmol/L EGTA (ethylene glycol-bis (β-aminoethyl ether)-N,N,N′,N′-tetraacetic acid)—2.6 mmol/L H₂O₂, and 92.6 µmol/L Fe³⁺—185.2 µmol/L EGTA—2.6 mmol/L H₂O₂ systems. Dehydroascorbic acid (DHAA) at the same range of concentrations served as the reference compound. Light emission was measured with multitube luminometer (AutoLumat Plus LB 953) for 120 s after automatic injection of H₂O₂. AA at concentrations of 1 to 50 µmol/L and of 1 to 75 µmol/L completely inhibited light emission from Fe²⁺-EGTA-H₂O₂ and Fe³⁺-EGTA-H₂O₂, respectively. Concentrations of 100 and 200 µmol/L did not affect chemiluminescence of Fe³⁺-EGTA-H₂O₂ but tended to increase light emission from Fe²⁺-EGTA-H₂O₂. DHAA at concentrations of 1 to 100 µmol/L had no effect on chemiluminescence of both systems. These results indicate that AA at physiological concentrations exhibits strong antioxidant activity in the presence of chelated iron and H₂O₂.     

Crystal structure of Na2MMgP2O8 (M: Ba, Sr, Ca) orthophosphates and their luminescence properties activated by Eu; analogous structural behaviors of glaserite-type phosphates and silicates

Rietveld refinements of X-ray powder diffraction data and vibrational spectroscopy have confirmed the crystal structure of Na₂MMgP₂O₈ (M: Ba, Sr, Ca) prepared by a standard solid state reaction. They have glaserite-type layered structure. Na₂MMgP₂O₈ has a trigonal P3? form for M=Ba, and monoclinic P2₁/c forms for M=Sr and Ca. The observed structural transition is analogous to the corresponding layered orthosilicate M₃MgSi₂O₈.Eu²⁺-doped Na₂MMgP₂O₈ exhibits an intense blue to violet emission under ultraviolet excitation, based on 5d-4f electron transition of Eu²⁺ ions. The emission character is very sensitive to the structural transition induced by M²⁺ and the subsequent site symmetry changes.     

Oxidation of sulfites on vanadium-molybdenum oxides

The low temperature emission of ¹O₂ singlet oxygen from xV₂O₅ · yMoO₃ binary oxides is investigated by means of flash desorption. Conditions for the generation of ¹O₂ on their surfaces are determined, along with the correlation between the amount of ¹O₂ and the degree of NaHSO₃ conversion in the oxidation reaction. It is shown that on the surface of oxides there are oxygen species that upon decomposition produce ¹O₂ involved in the oxidation of HSO ₃ ^? .     

Room-Temperature Near-Infrared Metastable Species Measured by Phase-Sensitive Lock-in and Fourier Transform Techniques

An ultrasensitive detecting system coupled with either a lock-in or Fourier transform technique has been used to detect near-infrared (1000-2500 nm) metastable species in room temperature solutions. These species include O₂(¹Δ_g), O₂(¹σ⁺_g), the solvent induced satellite peak of molecular singlet oxygen (¹Δ_g) emission, and the triplet state of bis(triisobutylsiloxy)silicon-2,-3-naphthalocyanine (SilNC). Using the O₂(¹Δ_g) emission in benzene as a standard, the quantum yield and radiative decay rate of SiINC triplet state have been determined. Depending on types of spectral acquisition, special techniques such as phase-distinguishing and step scan capabilities were utilized. Their advantages and disadvantages are discussed.     

Anion‐directed assemblies of europium(III) coordination polymers based on 1H‐benzimidazole‐5,6‐dicarboxylate: structures and luminescence properties

Two europium(III) coordination polymers (CPs), namely, poly[[diaquabis(μ₄‐1H‐benzimidazole‐5,6‐dicarboxylato‐κ⁶N³:O⁵,O^5′:O⁵,O⁶:O^6′)(μ₂‐oxalato‐κ⁴O¹,O²:O^1′,O^2′)dieuropium(III)] dihydrate], {[Eu₂(C₉H₄N₂O₄)₂(C₂O₄)(H₂O)₂]·2H₂O}_n ( 1 ), and poly[(μ₃‐1H‐benzimidazol‐3‐ium‐5,6‐dicarboxylato‐κ⁵O⁵:O^5′,O⁶:O⁶,O^6′)(μ₃‐sulfato‐κ³O:O′:O′′)europium(III)], [Eu(C₉H₅N₂O₄)(SO₄)]_n ( 2 ), have been synthesized via the hydrothermal method and structurally characterized. CP 1 shows a three‐dimensional network, in which the oxalate ligand acts as a pillar, while CP 2 has a two‐dimensional network based on a europium(III)–sulfate skeleton, further extended into a three‐dimensional framework by hydrogen‐bonding interactions. The structural diversity in the two compounds can be attributed to the different acidification abilities and geometries of the anionic ligands. The luminescence properties of 1 display the characteristic europium red emission with CIE chromaticity coordinates (2/3, 0.34). Interestingly, CP 2 shows the characteristic red emission with CIE chromaticity coordinates (0.60, 0.34) when excited at 280 nm and a near‐white emission with CIE chromaticity coordinates (0.38, 0.29) when excited at 340 nm.     

Synthesis and optical properties of Gd2O3:Pr3+ phosphor particles

Spherical-shaped Gd₂O₃:Pr³⁺ phosphor particles were prepared with different concentrations of Pr³⁺ using the urea homogeneous precipitation method. The resulting Gd₂O₃:Pr³⁺ phosphor particles were characterized by X-ray diffraction, field emission scanning electron microscope, and photoluminescence spectroscopy. The effects of the Pr³⁺ doping concentration on the luminescent properties of Gd₂O₃:Pr³⁺ phosphors were investigated. Photoluminescence measurements revealed the Gd₂O₃:1?% Pr³⁺ phosphor particles to have the strongest emission. The luminescence properties of Gd₂O₃:Pr³⁺ particles are strongly affected by the phosphor crystallinity and X-ray diffraction measurements confirmed that the crystallinity of Gd₂O₃ cubic structure could be enhanced by increasing the firing temperature. The luminescent Gd₂O₃:Pr³⁺ phosphor particles have potential applications in areas, such as optical display systems, lamps and etc.     

Chemiluminescent spectra of HNO and DNO in the reaction of O(3P)/O2 with NO and hydrocarbons of aldehydes

The chemiluminescent emission from the electronically excited state of HNO (¹A″) was observed in the reactions of O(³P)/O₂ with NO and one of acetylene, ethylene, propylene, formaldehyde and acetaldehyde. The identification of the emitting species was confirmed by observing the emission from DNO in the reactin of O/O₂ with NO and ethylene-d₄. The emission spectra were different from those observed in the reaction of H(D) + NO + M.     

Strychnine : A fast physical quencher of singlet oxygen (1Δg)

Pulsed laser excitation of 2-acetonaphthone in aerated benzene, toluene, acetone, acetonitrile or ethanol results in formation of O₂(¹Δ_g), the infrared luminescence of which has been monitored by time-resolved emission spectroscopy. The rate constants for the quenching of this emission by the indole alkaloid strychnine in all five solvents have been determined and compared with the corresponding values for the well-known O₂ (¹Δ_g) quencher DABCO. Strychnine (1) is the fastest known tertiary amine quencher of this species via a process which is at least 99% physical in character.     

Spectroscopic Investigation of the Europium(3+) Ion in a New ZnY4W3O16 Matrix

A new Zn and Eu tungstate was characterized by spectroscopic techniques. This tungstate, of the formula ZnEu₄W₃O₁₆, crystallized in the orthorhombic system and was synthesized by a solid‐state reaction. It melts incongruently at 1330°. The luminescent properties, including excitation and emission processes, luminescent dynamics, and local environments of the Eu³⁺ ions in ZnEu₄W₃O₁₆ and ZnY₄W₃O₁₆ : Eu³⁺ diluted phases (1, 5, and 10 mol‐% of Eu³⁺ ion) were studied basing on the f⁶‐intraconfigurational transitions in the 250–720 nm spectral range. The excitation spectra of this system (λ_em 615 and 470 nm) show broad bands with maxima at 265 and 315 nm related to the ligand‐to‐metal charge‐transfer (LMCT) states. The emission spectra under excitation at the O→W (265 nm) and O→Eu³⁺ (315 nm) LMCT states present the blue‐green emission bands. The emission of tungstate groups mainly originate from the charge‐transfer state of excited 2p orbitals of O^2? to the empty orbitals of the central W⁶⁺ ions. On the other hand, in the emission of the Eu³⁺ ions, both the charge transfer from O^2? to Eu³⁺ and the energy transfer from W⁶⁺ ions to Eu³⁺ are involved. The emission spectra under excitation at the ⁷F₀→⁵L₆ transition of the Eu³⁺ ion (394 nm) of ZnY₄W₃O₁₆ : Eu³⁺ diluted samples show narrow emission lines from the ⁵D₃, ⁵D₂, and ⁵D₁ emitting states. The effect of the active‐ion (Eu³⁺) concentration on the colorimetric characteristic of the emissions of the compound under investigation are presented.     

Luminescence of Mn2+ in SrGa12O19, LaMgGa11O19, and BaGa12O19

Lattice parameters are given of SrGa₁₂O₁₉, BaGa₁₂O₁₉, and LaMgGa₁₁O₁₉, three new gallates with the magnetoplumbite structure. The luminescence of the compounds without and with activation by Mn²⁺ is reported. The quantum efficiencies of the Mn²⁺ phosphors are between 15% (BaGa₁₂O₁₉:Mn) and 70% ({Sr_1?xLa_x}Ga_12?xMg_xO₁₉:Mn). The emission strongly resembles that of Mn²⁺ in MgGa₂O₄. The fine structure of the Mn²⁺ emission band at 77°K is due to phonon coupling.     

Reactions of O2(Δg) with ozone

The rate of the reaction O₂(¹Δ_g + O₃ → 2O₂(³Σ ⁻_g) + O(³P) was measured in a static reactor between 296 and 360°K. The decay of O₂(¹Δ_g) was determined from the emission of O₂(¹Σ⁺_g) at 7620 Å. The rate constant is 6.0 × 10⁻¹¹ exp (−5670/RT) cm³ molecule⁻¹ sec⁻¹. The reaction of O(³P) with ozone is found to produce O₂(¹Σ⁺_g) with approximately 0.01% efficiency.