新型全色发光材料NaCaPO_4:Dy~(3+)制备及发光性能

釆用高温固相法制备了NaCaPO4∶Dy3+系列样品,并在紫外(UV)及真空紫外(VUV)区域研究了系列样品的发光性能.紫外激发光谱显示在350nm处有最强的激发峰,可以有效地吸收紫外光并将其转化为可见光.真空紫外激发光谱表明,NaCaPO4∶Dy3+能有效地吸收无汞荧光灯的激发源并将其转化为可见光.系列样品发光均呈现为白色,这种材料有潜力作为全色显示材料应用于发光二极管(LED)和无汞荧光灯中.     

新型全色发光材料NaCaPO4∶Dy3+制备及发光性能

釆用高温固相法制备了NaCaPO4∶Dy3+系列样品, 并在紫外(UV)及真空紫外(VUV)区域研究了系列样品的发光性能. 紫外激发光谱显示在350 nm处有最强的激发峰, 可以有效地吸收紫外光并将其转化为可见光. 真空紫外激发光谱表明, NaCaPO4∶Dy3+能有效地吸收无汞荧光灯的激发源并将其转化为可见光. 系列样品发光均呈现为白色, 这种材料有潜力作为全色显示材料应用于发光二极管(LED)和无汞荧光灯中.     

Fluorescence properties of Ca2+-independent discharged obelin and its application prospects

Discharged obelin, a complex of coelenteramide and polypeptide, is a fluorescent protein produced from the photoprotein obelin, which is responsible for bioluminescence of the marine hydroid Obelia longissima. Discharged obelin is stable and nontoxic and its spectra are variable, and this is why it can be used as a fluorescent biomarker of variable color in vivo and in vitro. Here we examined light-induced fluorescence of Ca²⁺-independent discharged obelin (obtained without addition of Ca²⁺). Its emission and excitation spectra were analyzed under variation of the excitation wavelength (260–390 nm) and the emission wavelength (400–700 nm), as well as the 40 °C exposure time. The emission spectra obtained with excitation at 260–300 nm (tryptophan absorption region) included three peaks with maxima at 355, 498, and 660 nm, corresponding to fluorescence of tryptophan, polypeptide-bound coelenteramide, and a hypothetical indole–coelenteramide exciplex, respectively. The emission spectra obtained with excitation at 310–380 nm (coelenteramide absorption region) did not include the 660-nm maximum. The peak in the red spectral region (λ _max?=?660 nm) has not been previously reported. Exposure to 40 °C under excitation at 310–380 nm shifted the obelin fluorescence spectra to the blue, whereas excitation at 260–300 nm shifted them to the red. Hence, red emission and variation of the excitation wavelength form a basis for development of new medical techniques involving obelin as a colored biomarker. The addition of red color to the battery of known (violet to yellow) colors increases the potential of application of obelin.     

GdVO_4∶Eu~(3 )的真空紫外激发光谱研究

报道了GdVO4∶Eu3 的光致发光光谱和真空紫外 紫外激发光谱。GdVO4∶Eu3 是高效率的真空紫外 紫外激发荧光材料。GdVO4∶Eu3 在6 0～ 35 0nm真空紫外 紫外波段的激发可能主要来源于基质的吸收 ,有明显的Eu3 及Gd3 的 4fn - 1 5d吸收。在GdVO4∶Eu3 中 ,存在如下能量传递过程 :VO3 - 4 →Eu3 ,Gd3 →Eu3 ,Gd3 →VO3 - 4 →Eu3 ;通过后两个过程 ,Gd3 Eu3 可实现量子剪裁。     

pH对玫瑰红色素紫外和荧光光谱的影响

玫瑰是蔷薇科蔷薇属落叶丛生灌木,品种繁多,其花色、香、形具美,有极高的观赏和经济价值,我国玫瑰资源丰富,古代人们就将玫瑰用于染色、食品和药用等领域,现在玫瑰主要用于商品花卉和提取玫瑰精油.     

Photophysical properties of praseodymium complexes with aromatic carboxylic acids: double light conversion both in ultraviolet and visible region

A series of luminescent praseodymium complexes with different aromatic carboxylic acids have been synthesized and characterized. The photophysical properties of these complexes have been studied with ultraviolet spectra, phosphorescence spectra and fluorescence spectra. Ultraviolet absorption spectra show that the praseodymium complexes systems with aromatic carboxylate form the more extensive conjugated systems to be suitable for the distribution of electron in the whole coordination environment, resulting in the energy decrease and red-shifts of ultraviolet spectral bands. Phosphorescence spectra suggest that excited triplet state of aromatic carboxylic acids, which can indicate the energy match and intermolecular energy transfer process between the excited triplet state of ligands and the resonant emissive energy level of Pr ions. The 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 at about 595 nm under 415 nm excitation, 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 speculated to belong to the transition of charge transfer state, and the 1D2-->3H4 can be further proved that there exists an antenna effect in the luminescence of praseodymium with aromatic carboxylic acids. In conclusion, the praseodymium complexes systems can realize the double proton light conversion both in the ultraviolet and visible region, which can be further studied to have potential application.     

Dual fluorescence of graphene oxide: a time-resolved study

The fluorescence properties of graphene oxide (GO) was studied by recording the fluorescence lifetime, fluorescence emission, and excitation spectra, as well as UV-visible and near-IR absorption spectra. For the first time, we showed that a blue band (ca. 440 nm) and a long wavelength (LW) band (ca. 700 nm) are coexistent, which can be recorded simultaneously by controlling concentration, excitation wavelength, and pH values. Two bands are closely related by the protonation or deprotonation of GO. The blue band is favored by low GO concentration, short excitation wavelength, and high pH value, while the LW band is favored by low pH and long excitation wavelength. To reveal the nature of the dual emission of GO, the fluorescence lifetimes under various conditions were also measured. The blue band contains three emitting components; one of them has a lifetime as long as 10 ns, and its emitting intensity is fairly sensitive to pH, showing the potential for applications in sensing H(+) and fluorescence lifetime imaging. Combining the results under various conditions, we conclude that the electronic transition for this component is very likely due to n-π* transition. The LW band contains two main emitting components (0.2 and 2.1 ns) that also appear in the blue band as minor contributors; the related emission is assigned to π-π* transition. In summary, GO emission is of broadband (300-1250 nm), long-lived, pH sensitive, and excitation wavelength dependent. This makes it easily tailored for versatile applications.     

A femtosecond study of excitation wavelength dependence of solvation dynamics in a PEO-PPO-PEO triblock copolymer micelle

Excitation wavelength (lambdaex) dependence of solvation dynamics of coumarin 480 (C480) in the micellar core of a water soluble triblock copolymer, PEO20-PPO70-PEO20 (Pluronic P123), is studied by femtosecond and picosecond time resolved emission spectroscopies. In the P123 micelle, the width of the emission spectrum of C480 is found to be much larger than that in bulk water. This suggests that the P123 micelle is more heterogeneous than bulk water. The steady state emission maximum of C480 in P123 micelle shows a significant red edge excitation shift by 25 nm from 453 nm at lambdaex=345 nm to 478 nm at lambdaex=435 nm. The solvation dynamics in the interior of the triblock copolymer micelle is found to depend strongly on the excitation wavelength. The excitation wavelength dependence is ascribed to a wide distribution of locations of C480 molecules in the P123 micelle with two extreme environments-a bulklike peripheral region with very fast solvent response and a very slow core region. With increase in lambdaex, contribution of the bulklike region having an ultrafast component (< or =2 ps) increases from 7% at lambdaex=375 nm to 78% at lambda(ex)=425 nm while the contribution of the ultraslow component (4500 ps) decreases from 79% to 17%.     

Compact fiber-optic fluorosensor employing light-emitting ultraviolet diodes as excitation sources

A compact fluorosensor using three different ultraviolet light-emission diodes as excitation sources for fiber-optic recording of fluorescence spectra from samples is described. A compact integrated spectrometer with linear array wavelength recording is used, yielding a spectral resolution of about 8 nm. In two system implementations ultraviolet light-emitting diodes at 300, 340 and 395 nm, or at 360, 385 and 410 nm were used as excitation sources with typical emission halfwidths of 12 nm, each combined with a matching long-path colored-glass filter automatically brought into the fluorescence light flow for suppression of reflected light. Spectra from measurements on vegetation, human skin tumors and a rare-earth ion-based thermographic phosphor were recorded to illustrate the system performance.     

Parametric investigation of laser-induced fluorescence of solid-state uranyl compounds

The combination of remote/standoff sensing and laser-induced fluorescence (LIF) spectroscopy shows potential for detection of uranyl (UO2(2+)) compounds. Uranyl compounds exhibit characteristic emission in the 450-600 nm (22,200 to 16,700 cm(-1)) spectral region when excited by wavelengths in the ultraviolet or in the short-wavelength portion of the visible spectrum. We report a parametric study of the effects of excitation wavelength [including 532 nm (18,797 cm(-1)), 355 nm (28,169 cm(-1)), and 266 nm (37,594 cm(-1))] and excitation laser power on solid-state uranium compounds. The uranium compounds investigated include uranyl nitrate, uranyl sulfate, uranyl oxalate, uranium dioxide, triuranium octaoxide, uranyl acetate, uranyl formate, zinc uranyl acetate, and uranyl phosphate. We observed the characteristic uranyl fluorescence spectrum from the uranium compounds except for uranium oxide compounds (which do not contain the uranyl moiety) and for uranyl formate, which has a low fluorescence quantum yield. Relative uranyl fluorescence intensity is greatest for 355 nm excitation, and the order of decreasing fluorescence intensity with excitation wavelength (relative intensity/laser output) is 355 nm > 266 nm > 532 nm. For 532 nm excitation, the emission spectrum is produced by two-photon excitation. Uranyl fluorescence intensity increases linearly with increasing laser power, but the rate of fluorescence intensity increase is different for different emission bands.     

Red to blue tunable upconversion in Tm3+-doped ZrO2 nanocrystals

The effect of dopant concentration on the blue upconversion (UPC) emission of Tm(3+) -doped ZrO(2) nanocrystals under different excitation wavelengths in the red region is reported. The UPC emissions are due to the f-f electronic transitions from excited states (1)G(4) and (1)D(2) of Tm(3+). We observed a chromatic change in the UPC with tuning the excitation wavelength. The UPC emission bands at 475, 488, and 501 nm are observed under excitation at 649 nm, but bands centered at 454 and 460 nm are observed when the excitation wavelength is tuned to 655 nm. The UPC emission could be tuned from 501 to 454 nm ( approximately 47 nm) by changing the excitation wavelength from 649 to 655 nm ( approximately 6 nm). The pump power dependence of the emission bands at 475, 488, and 501 nm were investigated on excitation intensity at 649 nm, and the emission bands at 454 and 460 nm are investigated on excitation intensity at 655 nm, which confirms that all of these UPC emission lines are a two-photon absorption process.     

Different molecular constituents in pheomelanin are responsible for emission, transient absorption and oxygen photoconsumption

Steady-state absorption and emission spectroscopies, oxygen activation and transient spectroscopy on a single sample of synthetic pheomelanin are compared. The absorption, emission and excitation spectra of pheomelanin depend on the molecular weight (MW) of the dissolved pigment constituents. While weakly-depending on MW, the maximum of the emission excitation spectrum is approximately 400 nm. The electron paramagnetic resonance oximetry measurements show a clear increase in oxygen uptake between 338 and 323 nm, and also reveal a local enhancement around approximately 370 nm. Pump-probe absorption spectroscopy reveals that photoexcitation of pheomelanin by UVA light generates a transient absorption peak in the visible and UV regions within the instrument response. The action spectrum for the formation of the 780 nm transient species peaks at approximately 360 nm. While both transient absorption bands show the same ultrafast decay component, the 780 nm peak completely vanishes on the 10s of picosecond time scale, but the UV band shows a kinetic evolution to a subsequent intermediate. While in a similar wavelength range, the maximum of the action spectrum derived from the transient data, the emission excitation spectrum and the action spectrum for photoconsumption all differ from one another, suggesting that the chromophore responsible for each is not that same. This raises concern about comparing the results from different photochemical methodologies for melanin, which is a specific case of comparing data on systems where molecular constituents are not well defined.     

溶胶-凝胶法制备掺Sm3+的SiO2玻璃的结构及发光性能

利用溶胶-凝胶技术制备了掺不同量Sm3+和不同退火温度下的SiO2凝胶和玻璃,通过三维荧光光谱、激发光谱、发射光谱的测试,确定了Sm3+在SiO2凝胶玻璃中的最佳激发波长为360 nm,最强发射波长为610 nm,激发光谱的峰位置在360、393、464 nm处,发射光谱的峰位置在578、591、595、610、732nm处,分别归属于4G5/2-6H5/2、4G5/2-6H7/2、4G5/2-6H11/2跃迁,并证明当掺杂量达到1.15%时,Sm3+的发光最强,当Sm3+的掺杂量超过1.15%时,发生浓度猝灭效应.     

铝试剂的荧光光谱与荧光量子产率

首次研究了铝试剂的荧光光谱和荧光量子产率,发现pH3至pH12条件下,用紫外光照射铝试剂溶液可以产生荧光,最大激发波长和最大发射波长分别为297nm和409nm,荧光强度与铝试剂浓度之间存在良好的线性关系,线性范围为0.01～3μg/mL,检测下限为0.01μg/mL,以硫酸奎宁为参比,测得铝试剂的荧光量子产率为0.16。     

Constant-wavelength synchronous spectrofluorimetry for determination of riboflavin in anchovies

Constant-wavelength synchronous spectrofluorimetry was used for the analysis of riboflavin in anchovies. Synchronous fluorescence spectra were recorded between 300 and 600 nm at a scan rate of 240 nm min^–1 and with excitation and emission slit-widths both set to 5 nm. The excitation-emission wavelength difference was 65 nm. The fluorescence was measured by peak-area base between 430–509 nm. Recovery was higher than 90.8%.     

PHOTOACOUSTIC SPECTRA OF SOME BIOLOGICAL MOLECULES BETWEEN 300 AND 130 nm

Photoacoustic spectra of the biological molecules thymine, adenine, tyrosine, ergosterol and polyadenylic acid were obtained in the 300-130 nm region of photon wavelength using synchrotron radiation as a light source. Photoacoustic measurements were performed with thin solid films of these molecules made by vacuum evaporation, except for polyadenylic acid whose thin films were made from the aqueous solution. It was found that the spectra exhibit absorption structures which are in good agreements with those found from conventional transmission measurements. Some of the spectra, however, exhibit a marked deviation from the transmission data in the region below 145 nm, which may be indicative of photon absorption with subsequent photoelectron emission.     

SPECTROSCOPIC AND MICROSCOPIC CHARACTERISTICS OF HUMAN SKIN AUTOFLUORESCENCE EMISSION

To improve the understanding of human skin autofluorescence emission, the spectroscopic and microscopic characteristics of skin autofluorescence were studied using a combined fluorescence and reflectance spectroanalyzer and a fiber optic microspectrophotometer. The autofluorescence spectra of in vivo human skin were measured over a wide excitation wavelength range (350–470 nm). The excitation–emission matrices of in vivo skin were obtained. An excitation–emission maximum pair (380 nm, 470 nm) was identified. It was revealed that the most probable energy of skin autofluorescence emission photons increases monotonically and near linearly with increasing excitation photon energy. It was demonstrated that the diffuse reflectance, R, can be used as a first order approximation of the fluorescence distortion factor f to correct the measured in vivo autofluorescence spectra for the effect of tissue reabsorption and scattering. The microscopic in vitro autofluorescence properties of excised skin tissue sections were examined using 442 nm He–Cd laser light excitation as an example. It was demonstrated that the fluorophore distribution inside the skin tissue is not uniform and the shapes of the autofluorescence spectra of different anatomical skin layers vary. The result of this study confirms that the major skin fluorophores are located in the dermis and provides an excellent foundation for Monte Carlo modeling of in vivo autofluorescence measurements.     

Polarized fluorescence spectra of poly(ethylene terephthalate) films

The polarized excitation and fluorescence spectra of lowcrystalline, isotropic poly(ethylene terephthalate) (PET) film samples were measured in the glassy state at room temperature. Whereas the emission anisotropy r₀ of the excitation spectrum, recorded at the fluorescence maximum, changes sharply from 0.35 to 0 with decreasing wavelength in the region around 317 nm, the polarization of the fluorescence spectrum of PET is independent of wavelength. The fluorescence polarization of PET remains constant, if the temperature is increased up to 22 °C above T_g until the light scattering due to the crystallization causes complete depolarization. The photophysical behaviour supports the existence of a dilute solution of groundstate - stable sandwich dimers in the non-crystalline regions of PET.     

Eu2+掺杂KCaCl3晶体的生长及发光性能

通过坩埚下降法生长出不同物质的量分数Eu²⁺掺杂的KCa_1-xEu_xCl₃(x=0.005、0.01、0.02、0.03、0.05)单晶,并对晶体进行了X射线粉末衍射、热重、透过率、光致发光光谱、衰减时间、X射线激发发射光谱等测定。通过相图及结构分析,判断出该晶体为一致熔融化合物,并得出其为正交结构,晶胞参数为a=0.75604 nm,b=1.04823 nm,c=0.72657 nm,空间群为Pnma(62)。在紫外光的激发下,晶体在434 nm左右有一个宽的发射峰,对应于Eu²⁺的4f⁶5d¹→4f⁷跃迁;光致衰减时间1.473μs,晶体在X射线激发下的发光强度随Eu²⁺离子浓度增加而增强。     

Far‐UV‐Excited Luminescence of Nitrogen‐Vacancy Centers: Evidence for Diamonds in Space

The nitrogen‐vacancy (NV) centers in diamond are among the most thoroughly investigated defects in solid‐state matter; however, our understanding of their properties upon far‐UV excitation of the host matrix is limited. This knowledge is crucial for the identification of NV as the carrier of extended red emission (ERE) bands detected in a wide range of astrophysical environments. Herein, we report a study on the photoluminescence spectra of NV‐containing nanodiamonds excited with synchrotron radiation over the wavelength range of 125–350 nm. We observed, for the first time, an emission at 520–850 nm with a quantum yield greater than 20 %. Our results share multiple similarities with the ERE phenomena, suggesting that nanodiamonds are a common component of dust in space.