Li4SrCa (SiO4)2:Eu3+红色荧光粉的合成及其发光性能

采用硅酸盐作为基质材料,通过高温固相法合成了Li₄SrCa（SiO₄）₂：Eu³⁺红色荧光粉。通过X射线粉末衍射、X射线光电子能谱、透射电镜和荧光光谱,对所得样品的物相、形貌及其发光性能进行了表征分析。结果表明,掺入Eu³⁺后,Li₄SrCa（SiO₄）₂的晶体结构并没有发生改变。在393 nm光激发下,荧光粉的荧光光谱中693 nm处发射峰强度最强。以693 nm作为监测波长,荧光激发峰分别为361 nm（⁷F₀→⁵D₄）、375 nm（⁷F₀→⁵G₃）、413 nm（⁷F₀→⁵D₃）、393 nm（⁷F₀→⁵L₆）和464 nm（⁷F₀→⁵D₂）,即样品对近紫外和蓝光有较好的吸收。利用发射光谱研究了Eu³⁺掺杂浓度（物质的量分数）对荧光粉发光强度的影响。当Eu³⁺的掺杂浓度x=0.10时,样品发射强度最强,发射红光,其色坐标为（0.637 5,0.353 7）。通过Dexter强度与浓度关系分析了浓度猝灭机制。     

水热合成LuF3:Yb3+,Er3+微晶及其上转换发射与温度传感特性

通过在不同pH值下的简易水热法合成不同Yb³⁺离子（n_YB³⁺/n_Lu³⁺=5%~15%）和Er³⁺离子（n_Er³⁺/n_Lu³⁺=1%~5%）掺杂浓度的LuF₃∶Yb³⁺,Er³⁺微晶荧光粉。发现pH值对正交相LuF₃∶Yb³⁺,Er³⁺的合成起着关键作用。在980 nm激发下,LuF₃∶Yb³⁺,Er³⁺荧光体呈现出以523 nm（²H_11/2→⁴I_15/2）和539 nm（⁴S_3/2→⁴I_15/2）为中心的强绿光上转换（UC）发射以及以660 nm（⁴F_9/2→⁴I_15/2）为中心弱红光上转换发射。通过使用X射线衍射（XRD）和光致发光（PL）分析测定了最强发射强度的Er³⁺和Yb³⁺的最佳掺杂浓度。浓度依赖性研究表明,达到最强的绿光上转换发光时最佳掺杂浓度为10% Yb³⁺,2% Er³⁺。通过改变泵浦功率来研究LuF₃∶Yb³⁺,Er³⁺荧光粉UC发光机制。通过980 nm二极管激光器在293~573 K的范围内研究了在523和539 nm处的2个绿光UC发射带的荧光强度比（FIR）的温度依赖性,发现在490 K得到最大灵敏度约为15.3×10^-4 K^-1。这表明LuF₃∶Yb³⁺,Er³⁺荧光体可应用于具有高灵敏度的光学温度传感器。     

绿色荧光粉Ca3Y2Si3O12:Tb3+,Ce3+的制备及发光特性

采用高温固相法合成了绿色荧光粉Ca₃Y₂Si₃O₁₂:Tb³⁺。XRD检测结果显示,荧光粉主晶相为Ca₃Y₂Si₃O₁₂,属单斜晶系。荧光光谱分析表明:Ca₃Y₂Si₃O₁₂:Tb³⁺硅酸盐荧光粉可以被370nm的近紫外光激发,发射绿光,主发射峰位于490nm(⁵D₄→⁷F₆),544nm(⁵D₄→⁷F₅),585nm(⁵D₄→⁷F₄)和621nm(⁵D₄→⁷F₃)。用544nm最强峰监测,得到主激发峰位于370nm的激发光谱,此光谱覆盖了300~450nm的波长范围。研究了煅烧条件、掺杂浓度及Ce³⁺共掺杂对荧光粉发光性能的影响:在1400℃下经二次煅烧6h得到的样品的发光性能最佳,Tb³⁺离子的最佳掺杂浓度为20mol%,Ce³⁺离子共掺杂能够提高荧光粉的发光强度,其最佳掺杂量为4mol%,说明存在Ce³⁺→Tb³⁺的能量传递。     

电荷补偿对Ba2ZnGe2O7：Bi3+荧光粉发光性质的影响

采用高温固相法制备了2个系列的荧光粉样品：Ba_2-xZnGe₂O₇：xBi³⁺（系列Ⅰ）和Ba_1.994-yK_yZnGe₂O₇：0.006Bi³⁺（系列Ⅱ）。X射线衍射（XRD）测试结果表明,少量Bi³⁺、K⁺的掺杂不会明显改变材料的物相结构。样品的荧光光谱测试结果表明,虽然2个系列样品的发光光谱都随组成成分变化有少量变化,但发光颜色基本上均为黄绿色。在358 nm的激发下,荧光粉的发射光谱呈现一个峰值在500 nm的宽发射带,归属于³P₁→¹S₀能级跃迁。在500 nm监测下,荧光粉的最强激发峰位于358 nm,归属于¹S₀→³P₁能级跃迁,此外还有一个位于320 nm的肩峰归属于O^2--Bi³⁺电荷转移带。系列Ⅰ样品的光谱数据结果指出,Bi³⁺的最佳掺杂量x为0.006。在该基质中,Bi³⁺掺杂取代Ba²⁺属于不等价取代,会在晶格中产生Ba²⁺空位或间隙O^2-,对材料的发光强度产生负面影响。对此,采用K⁺与Bi³⁺协同掺杂起到电荷补偿的作用,填补Ba²⁺空位或捕获间隙O^2-缺陷。空位被填补或间隙被捕获均减少了晶格畸变,从而使发光强度明显提高。系列Ⅱ样品的光谱数据表明,完全电荷补偿的荧光粉样品相比于没有掺K⁺的样品,其发光强度提高了约2.5倍。     

水热合成LuF3∶Yb3+，Er3+微晶及其上转换发射与温度传感特性

通过在不同pH值下的简易水热法合成不同Yb³⁺离子（n_Yb³⁺/n_Lu³⁺=5%~15%）和Er³⁺离子（n_Er³⁺/n_Lu³⁺=1%~5%）掺杂浓度的LuF₃∶Yb³⁺,Er³⁺微晶荧光粉。发现pH值对正交相LuF₃∶Yb³⁺,Er³⁺的合成起着关键作用。在980 nm激发下,LuF₃∶Yb³⁺,Er³⁺荧光体呈现出以523 nm（²H_11/2→⁴I_15/2）和539 nm（⁴S_3/2→⁴I_15/2）为中心的强绿光上转换（UC）发射以及以660 nm（⁴F_9/2→⁴I_15/2）为中心弱红光上转换发射。通过使用X射线衍射（XRD）和光致发光（PL）分析测定了最强发射强度的Er³⁺和Yb³⁺的最佳掺杂浓度。浓度依赖性研究表明,达到最强的绿光上转换发光时最佳掺杂浓度为10% Yb³⁺,2% Er³⁺。通过改变泵浦功率来研究LuF₃∶Yb³⁺,Er³⁺荧光粉UC发光机制。通过980 nm二极管激光器在293~573 K的范围内研究了在523和539 nm处的2个绿光UC发射带的荧光强度比（FIR）的温度依赖性,发现在490 K得到最大灵敏度约为15.3×10^-4 K^-1。这表明LuF₃∶Yb³⁺,Er³⁺荧光体可应用于具有高灵敏度的光学温度传感器。     

ZnWO4∶Er3+，Yb3+纳米棒的制备及发光性能

采用水热法以聚乙二醇为分散剂合成了Er³⁺,Yb³⁺共掺的ZnWO₄纳米棒。X射线衍射、透射电子显微镜分析结果表明：所得产物为直径约20 nm的ZnWO₄纳米棒。在激发波长为980 nm的半导体激光器做光源激发下,确定样品的3个发射峰的发光中心位于532、553和656 nm,分别对应于铒离子 ²H_11/2→ ⁴I_15/2, ⁴S_3/2→ ⁴I_15/2和 ⁴F_9/2→ ⁴I_15/2的跃迁。     

Er3+，Yb3+共掺杂NaY(WO4)2上转换荧光粉的制备及其发光性能

应用传统水热法合成出具有四方白钨矿结构的NaY（WO₄）₂微米颗粒及一系列Er³⁺/Yb³⁺共掺杂NaY（WO₄）₂上转换荧光粉。利用XRD、SEM、TEM、HRTEM、粒度分布和上转换发光光谱对样品的物相、形貌及上转换发光性能进行分析表征。结果表明,pH值对于制备具有同一形貌的纯相NaY（WO₄）₂微米颗粒发挥重要作用。随着pH值的升高,可以完成从八面体到拟立方体再到片状颗粒的形貌转变。在980 nm近红外光激发下,观测到525及553 nm处的强绿光发射,对应Er³⁺的²H_11/2→⁴I_15/2与⁴S_3/2→ ⁴I_15/2跃迁,以及650~680 nm范围内的弱红光发射,对应Er³⁺的⁴F_9/2→⁴I_15/2跃迁,且绿、红光上转换发射均属于双光子过程。此外,通过调节NaY（WO₄）₂：Er³⁺,Yb³⁺荧光粉中Yb³⁺的浓度,可实现对绿光色度的有效控制。     

Tm3+/Er3+/Ho3+共掺SiO2-Bi2O3-AlF3-BaF2玻璃发光性能

采用高温熔融法制备了Tm³⁺/Er³⁺/Ho³⁺共掺的铋硅酸盐50SiO₂-40Bi₂O₃-5AlF₃-5BaF₂玻璃。研究了在808 nm激光器（Laser Diode）激发下Tm³⁺/Er³⁺/Ho³⁺共掺的铋硅酸盐在2 060 nm处的发光性能,同时测试及分析了该铋硅酸盐玻璃的差热特性、吸收光谱及荧光光谱。根据吸收光谱以及Judd-Oflet理论,计算了Ho³⁺的Judd-Oflet强度参数Ω_t（t=2,4,6）以及Tm³⁺/Er³⁺/Ho³⁺相应的吸收截面。铋硅酸盐玻璃中,Tm₂O₃、Er₂O₃和Ho2O3掺杂浓度分别为0.75%、1.0%和0.5%时,2 060 nm处Ho³⁺∶⁵I₇→⁵I₈发射峰强度达到最大。对Tm³⁺/Er³⁺/Ho³⁺ 3种离子的光谱性质和离子间可能存在的能量传递也做了分析。Ho³⁺在1 953 nm处的最大吸收截面σ_abs为9.08×10^-21 cm²,在2 060 nm处的最大发射截面σem为11.68×10^-21 cm²,辐射寿命τ_mea为2.75 ms,具有良好的增益效应σ_emτ（3.212×10^-20 cm^-2·ms）。     

双钙钛矿型Ca2Gd1-xTaO6：xTb3+绿色荧光粉的合成与荧光性质

通过高温固相法合成了双钙钛矿型Ca₂Gd_1-xTaO₆：xTb³⁺（CGTO：xTb³⁺）绿色荧光粉。采用X射线衍射、扫描电镜、荧光光谱、荧光衰减曲线、量子效率（η）测试分别表征了CGTO： xTb³⁺荧光粉的物相、形貌和荧光性质。在紫外光激发下,CGTO： xTb³⁺荧光粉实现了较强的绿光发射,绿光为Tb³⁺离子的⁵D₄-⁷F₅跃迁。通过变温发射光谱研究发现CGTO：0.15Tb³⁺荧光粉的热猝灭活化能为0.181 9 eV。在255 nm的激发下,最佳Tb³⁺掺杂浓度的CGTO：0.15Tb³⁺荧光粉的量子效率为32.32%。     

白光LED用Sr0.955Al2Si2-xTixO8：Eu2+荧光粉的晶体结构和光谱特性

由高温固相反应制得Sr_0.955Al₂Si_2-xTi_xO₈：Eu²⁺（x=0~1.0）系列试样,研究了Ti⁴⁺置换Si⁴⁺对其晶体结构和光谱特性的影响。Ti⁴⁺以类质同相替代Si⁴⁺进入晶体晶格中,形成了连续固溶体,其晶胞参数a,b,c,β和晶胞体积V随Ti⁴⁺置换量呈线性递增。Ti⁴⁺置换Si⁴⁺对晶胞参数c的影响显著,b其次,a最小。荧光激发谱为宽带,位于230~400nm,由267nm、305nm、350nm和375nm 4个峰拟合成,表观峰值位于351nm;随着Ti⁴⁺置换量的增加,半高宽（FWHM）从105nm减小到93nm。发射光谱位于380~600nm,表观峰值位于407nm,可由406nm和441nm两峰拟合而成并且随Ti⁴⁺置换量增加线性红移,Ti⁴⁺进入晶格对长波长发射中心影响较少;Ti⁴⁺置换量为1.0时,表观发射峰位从407nm红移至417nm;利用试样荧光光谱和VanUitert经验公式,得出SrAl₂Si₂O₈：Eu²⁺中Sr²⁺的配位数为9。随着Ti⁴⁺置换量Si⁴⁺进入基质晶格,造成Eu-O距离变小,使得Eu²⁺所处的晶体场强度增强,发光中心Eu²⁺的5d能级分裂增大,造成Eu²⁺最低发射能级重心下移,两拟合谱峰峰位均呈线性红移。     

Recombination of KrD and XeD ions with electrons

Recombination rate coefficients of protonated and deuterated ions KrH⁺, KrD⁺, XeH⁺ and XeD⁺ were measured using Flowing Afterglow with Langmuir Probe (FALP). Helium at 1600 Pa and at temperature 250 K was used as a buffer gas in the experiments. Kr, Xe, H₂ and D₂ were introduced to a flow tube to form the desired ions. Because of small differences in proton affinities of Kr, D₂ and H₂ mixtures of ions, KrD⁺/D₃⁺ and KrH⁺/H₃⁺ are formed in the afterglow plasma, influencing the plasma decay. To obtain a recombination rate coefficient for a particular ion, the dependencies on partial pressures of gases used in the ion formation were measured. The obtained rate coefficients, α_KrD+(250 K) = (0.9 ± 0.3) × 10⁻⁸ cm³ s⁻¹ and α_XeD+(250 K) = (8 ± 2) × 10⁻⁸ cm³ s⁻¹ are compared with α_KrH+(250 K) = (2.0 ± 0.6) × 10⁻⁸ cm³ s⁻¹ and α_XeH+(250 K) = (8 ± 2) × 10⁻⁸ cm³ s⁻¹.     

CO LMR spectrum of14N16O and its analysis with spectra of14N17O and14N18O

LMR spectra for v=1←0 transitions of¹⁴N¹⁶O in X²II_{1/2, 3/2} states were observed at 5.6 μm and 5.4 μm of CO laser. Introducing the advanced isotopic molecular constant scaling function to Hund’s case (a) diatomic structure model, these spectra were analyzed and fitted together with all reliable previous spectral data of¹⁴N¹⁶O as well as¹⁴N¹⁷O and¹⁴N¹⁸O. A full set of precise molecular parameters and their vibrational dependencies have been determined with much higher precision (1–2 orders for most parameters). Many of them have been obtained for the first time. Using isotopic scaling function, the molecular constants of¹⁴N¹⁷O and¹⁴N¹⁸O were deduced.     

Coordinate Structures of PrIII, GdIII, TmIII, and YbIII Complexes with Nitrilotriacetic Acids

The crystal and molecular structures of the [Pr^III(nta)(H₂O)₂]·H₂O (nta = nitrilotriacetic acids), K₃[Gd^III(nta)₂(H₂O)]·6H₂O, and K₃[Yb^III(nta)₂]·5H₂O complexes have been determined by single-crystal X-ray structure analyses. In [Pr^III(nta)(H₂O)₂]·H₂O, the Pr^IIINO₈ part forms a nine-coordinate pseudo-monocapped square antiprismatic structure in which one N and three O atoms are from one nta ligand in the same molecule, three O atoms from another nta ligand in the neighboring molecule and two O atoms from two coordinate water molecules. In K₃[Gd^III(nta)₂(H₂O)]·6H₂O, the [Gd^III(nta)₂(H₂O)^3- complex anion has a nine-coordinate pseudo-monocapped square antiprismatic structure in which each nta acts as a tetradentate ligand with one N atom of the amino group and three O atoms of the carboxylic groups. In K₃[Yb^III(nta)₂]·5H₂O, each nta also acts as a tetradentate ligand with one N atom of amino group and three O atoms of the carboxylic groups, but the [Yb^III(nta)₂ ^3- complex anion has an eight-coordinate structure with a distorted square antiprismatic prism. All the results including those for [Tm^III(nta)(H₂O)₂]·2H₂O confirm the inferences on the coordinate structures and coordination numbers of rare earth metal complexes with the nta ligand.     

Orthogonal Wavelets Analysis of Electroanalytical Signals

ABSTRACT

A signal processing technique based on orthogonal wavelet analysis is applied to process various simulated electroanalytical signals. The results indicate that if the scale parameters are selected, the orthogonal wavelet processing method (OWPM) can remove high-frequency noise. Experimental signal was recorded by computer and used to test the OWPM procedure. After processing with OWPM, the processed data was used to analyze the mechanism of the electrode reactions. Processed results of the experimental data are also satisfactory.     

Analytical methods to determine Po and Pb in marine samples

This paper describes the methods of sampling, preconcentration, chemical separation and final count of ²¹⁰Po and ²¹⁰Pb present in different marine matrices to determine their background levels in a marine ecosystem. Complex, time consuming and selective radioanalytical methods have been used to prepare final clear sources for alpha spectrometry and beta count; in fact, gamma spectrometry, a method direct and non destructive, cannot be taken into account because the ²¹⁰Pb activity is very low which does not allow to carry out sufficiently accurate measurements and ²¹⁰Po is not a gamma emitter but it emits only alpha particle at 5.40 MeV. The results of ²¹⁰Po and ²¹⁰Pb activity concentrations obtained in different marine samples collected in the first two campaigns are still very few to discuss about the ²¹⁰Po and ²¹⁰Pb behavior in marine environment.     

A kinetic study of the oxidation of hydroxamic acids by compounds I and II of horseradish peroxidase: Effect of transition metal ions

Abstract

Oxidation of hydroxamic acids (HXs) generates HNO, and it is not clear whether it is formed also in the presence of metal ions. The kinetics of the oxidation of HXs, such as acetohydroxamic acid, suberohydroxamic acid, and suberoylanilide hydroxamic acid (SAHA), by compounds I and II of horseradish peroxidase (HRP) at pH 7.0 and 25?°C have been studied using rapid-mixing stopped-flow. The kinetics of these reactions were compared to those observed in the presence of Cu(ClO₄)₂, NiSO₄, or ZnSO₄. The rates decrease upon increasing [Cu^II] at constant [HXs], and no oxidation of HX occurs when [HX]/[Cu^II] ≈ 2, implying that HX oxidation in the presence of Cu^II proceeds through the free ligand since the predominant complex is CuX₂. In the case of Ni^II, the oxidation rate decreases upon increasing the ratio [Ni^II]/[HX] beyond 1, where the predominant complex is Ni^IIX⁺, implying that its oxidation is feasible. The effect of Zn^II could be studied only on the rate of HXs oxidation by compound II demonstrating similar behavior to that of Ni^II. HXs were also oxidized catalytically by HRP/H₂O₂ at pH 7.0, demonstrating that metal ions facilitate the formation of HNO while hardly affecting its yield and the extent of HX oxidation.     

The Synthesis of Dibenzo[3n]crown-n by Novel Methods and their Cation Binding Studied by Fluorescence Spectroscopy. Part IV

The dibenzo[3n]crown-n were synthesised from1,2-bis(o-hydroxyphenoxy)ethane obtained from 1,2-bis(o-formylphenoxy)ethane via Bayer-Willigeroxidations with H₂O₂/CH₃COOH in good yields. The cyclic condensation of 1,2-bis(o-hydroxyphenoxy)ethanewith dichlorides, and ditosylates of polyethylene glycols in DMF/Me₂CO₃ gave the macrocyclesdibenzo[15]crown-5, dibenzo[18]crown-6, dibenzo[21]crown-7 anddibenzo[24]crown-8. The structures were identified using IR, mass, ¹H and ¹³C NMR spectroscopy. Therecognition of the molecules for the cations, Li⁺, Na⁺, K⁺, Rb⁺ and Zn²⁺were conducted quantitatively with steady state fluorescencespectroscopy. The 1:1 association constants in acetonitrileshowed a good relation of the appropriate size of the macrocyclic ether towards the fitting cationradii. Namely, dibenzo[15]crown-5 was the best for Li⁺ binding and more than 100 times better thanNa⁺ and K⁺. Dibenzo[21]crown-7 was excellent for Rb⁺ binding while K⁺ is 100 timesless preferred. The largest crown ether studied, dibenzo[24]crown-8, exhibited the order of binding power,Rb⁺ > K⁺ > Na⁺. Zn²⁺ displayed, however, a marked binding with only dibenzo[18]crown-6.p>     

Rotational molecular motion and solvation of Na+ and Cs+ in water-dimethylacetamide. A nuclear magnetic relaxation study

Nuclear magnetic relaxation by intra- and intermolecular quadrupoleelectric field gradient interaction has been used for the study of the systems DMA-water-NaI and DMA-water-CsI at 25°C.¹⁴N relaxation of DMA and²H relaxation of D₂O measured over the complete mixture range reveal the behavior of the rotational molecular motion of the two solvent components. For both solvent components a marked maximum of the reorientational correlation time has been found, reflecting hydrophobic effects and strong DMA-water interaction. The quadrupolar relaxation rates of²³Na⁺ and¹³³Cs⁺ in pure DMA were evaluated giving an indication that the electric solvent dipoles in the solvation shell are not located on positions of cubic symmetry. A quantitative study of preferential solvation of the cations in the mixed solvent has been performed by using the H₂O-D₂O isotope effect on²³Na⁺ and¹³³Cs⁺ relaxation. For both cations an obviously typical change in the selectivity occurs. In the range l>x _{H2 O}>0.7 we find weak preferential hydration, but in the range 0.7>xH ₂ O>0 strong preferential solvation by DMA is reflected.     

The preparation and analysis of fluoro-polyphosphates by F, P, 2D F-P HETCOR and 2D P-P COSY NMR

A complex mixture of fluoro-polyphosphates (FPPs) and polyphosphates was prepared by heating a mixture of NaF and sodium tripolyphosphate (STPP) at 600 °C in nitrogen atmosphere. Two-dimensional ³¹P-¹⁹F heteronuclear correlation spectroscopy (HETCOR) NMR was developed in identifying the atomic connection between F and P in the mixed FPPs. ¹⁹F, ³¹P and ³¹P-³¹P correlation spectroscopy (COSY) NMR methods were employed to identify the components of the mixture and measure the chain length of each FPP ingredient. NMR results clearly demonstrated that the mixture contains four kinds of fluoro-phosphates with different chain length of polyphosphate, which are monofluoro-phosphate (MFP), monofluoro-dipolyphosphate (MFDPP), monofluoro-tripolyphosphate (MFTPP) and difluoro-tripolyphosphate (DFTPP). Other phosphates and polyphosphates also were found in the mixture.     

Possibilities of multinuclear NMR in the chemistry of heteroorganic compounds

Results of multinuclear NMR studies of some heteroorganic compounds have been presented.According to a report at the conference «Current problems of organometallic chemistry» (May 8–13,1994, Moscow).Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 4, pp. 614–616, April, 1994.