苯甲酰三氟乙酰丙酮与铕、铽、钐、镝配合物合成和荧光光谱研究

本文合成了苯甲酰三氟乙酰丙酮(简称L)和三苯基氧化膦(TPPO)、联吡啶(Bipy)、邻菲罗林(Phen).四甲基氢氧化铵(NMe4OH)与Eu、Tb、Sm、Dy的三合型和四合型共十六种配合物,常温下研究了它们的固体粉末荧光光谱,发现四种铕配合物中Eu3+的5D0—7F2跃迁最强,而且EuL3Bipy和EuL3(TPPO)2发光相对强度特别高,其余三种离子的特征跃迁能级:Tb3+是3D4—7F5,Sm3+是4G5/2—6H3/2,Dy3+是4F9/2—6H1/2,除TbL3(TPPO)2外,其余发光强度不大.发现四合型NMe4EuL4在非极性溶剂中荧光强度最大,表明其稳定性高.在PS树脂中添加微量EuL3Bipy或EuL3(TPPO)2,在～365nm光照射下显示鲜艳的红色荧光.     

掺杂镧、钇的铽(Ⅲ)乙酰丙酮三元配合物的合成及荧光性质研究

合成了四个系列稀土掺杂铽乙酰丙酮(Hacac)三元配合物RExTb1-x(acac)3phen和RExTb1-x(acac)3bipy(RE=La,Y;x=0,010,020,030,050,070,090,100;phen1,10邻菲罗啉;bipy2,2’联吡啶)。通过红外光谱、X射线粉末衍射对配合物进行了表征。对各系列配合物进行荧光光谱研究,发现La3+,Y3+对Tb3+离子均有荧光增敏作用,并且La3+>Y3+。当x=01～03,多数掺杂配合物比未掺杂铽三元配合物具有更好的发光性能。     

La（Ⅲ）,Gd（Ⅲ）,Tb（Ⅲ）8—羟基喹啉固体配合物的光声光谱与 …

本文合成Ｌａ（Ⅲ）、Ｇｄ（Ⅲ）、Ｔｂ（Ⅲ）８－羟基喹啉固体配合物，通过对其光声光谱的分析，研究了８－羟基喹啉稀土配合物的荧光性质和驰豫过程。     

钡—偶氮胂Ⅲ—锌（钴）—邻菲罗啉多元配合物显色反应的研究

在近中性环境中，研究了钡与偶氮胂Ⅲ、锌（钴）、邻菲罗啉形成多元配合物的条件及其配合物组成。显色体系的摩尔吸光系数由二元配合物的2.1×10^4L·mol^-1·cm^-1提高到7.4×10^4L·mol^-1·cm^-1。用此方法，经过简单的分离后，可作硅钡合金中钡的光度法测定。     

铕（Ⅲ）—对茴香酸—邻菲罗啉三元配合物的合成及谱学性质

本文合成了ＥｕＬ３．ｐｈｅｎ．Ｈ２Ｏ（Ｌ＝对茴香酸根，ｐｈｅｎ＝邻菲罗啉）固体配合物，对所合成的配合物进行了元素分析，摩尔电导，ＩＲ，ＵＶ，ＮＭＲ等测试，初步研究了配合物的组成结构和性质。     

二（2,4,4—三甲基戊基）膦酸稀土配合物的振动光谱

测定了二（２，４，４－三甲基戊基）膦酸（ＢＴＭＰＰＡ）及其稀土配合物Ｌｎ（ＢＴＭＰＰ）３在４０００～５０ｃｍ＾－１光谱区内的ＦＴ－ＩＲ光谱和部分配合物的激光拉曼光谱，对其谱带进行了经验归属。发现稀土氧键具有较高的离子键特性。由Ｌｎ－Ｏ伸缩振动频率值算出其近似力常数约８ｍ ｄｙｎ／ｎｍ。     

铕（Ⅱ）—噻吩甲酰三氟丙酮—丙烯酸三元配合物及其聚合物发光性质研究

研究了铕（Ⅲ）与噻吩甲酰三氟丙酮（ＨＴＴＡ）、丙烯酸（ＨＡＡ）的三元配合物及与甲基丙烯酸甲酯（ＭＭＡ）成键聚合物（ＣＰＥｕ（ＴＴＡ）２ＡＡ）和掺杂聚合物（Ｅｕ（ＴＴＡ）２ＡＡ／ＰＭＭＡ）发光性质，测量了配合物中Ｅｕ＾３＋的＾５Ｄ０和＾５Ｄ１能级的荧光衰减，对其传能过程和荧光寿命进行了讨论，测量了配合物及聚合物ＴＨＦ溶液的荧光光谱，配合物的聚合有收交配体发生明显红移，且存在配体到中心离子的传能，指出     

掺杂Y3+和Gd3+的 Phen-Eu(Ⅲ)二元固体配合物的红外及荧光光谱研究

合成了掺杂Y^3 和Gd^3 的Phen-Eu(Ⅲ）二元固体配合物，确定了它们的组成，测定了固体配合物的红外光谱和荧光光谱，并首次探讨了掺杂Y^3 和Gd^3 的Phen-Eu(Ⅲ）二元固体配合物荧光强度的影响。     

一种嘧啶铱（Ⅲ）配合物的结构及光电性质研究

合成了一种铱配合物（DFPPM=2-（2,4-二氟苯基）嘧啶,acac=乙酰丙酮）,利用 X 射线单晶衍射仪测定了该化合物的晶体结构。利用紫外-可见吸收光谱、发射光谱对其光物理性质进行研究。结果表明：（DFPPM）₂ Ir（acac）的单晶结构属于三斜晶系,P-1空间群,晶胞参数a=14.444 4（7）nm,b=18.047 9（10）nm,c=19.220 0（9）nm,α=113.115（5）°;,β=90.453（4）°;,γ=90.989（4）°;,V=4 607.0（4）nm³。（DFPPM）₂ Ir（acac）在二氯甲烷溶液中的发射峰为 496 nm。以（DFPPM）₂ Ir（acac）为客体材料,制备了结构为ITO/NPB（40 nm）/CBP：（DFPPM）₂Ir（acac）（质量分数10%,30 nm）/TPBi（15 nm）/Alq₃（50 nm）/Mg：Ag（150 nm,10：1）/Ag（10 nm）的器件,器件的发射峰位于494 nm,最大亮度达到21 400 cd/m²,最大电流效率为12.0 cd/A,最大功率效率为 5.4 lm/W。     

Use of Cerium (IV) in the Spectrophotometric and Spectrofluorimetric Determinations of Penicillins and Cephalosporins in Their Pharmaceutical Preparations

Spectrophotometric and spectrofluorimetric procedures for the quantitative determination of four penicillins [Amoxycillin (AMX), Bacampicillin (BAC), Piperacillin (PPN) and Sultamcillin (SULT)] and ten cephalosporins [Cefadroxil (CDL), Cefamandole nafate (MAN), Cefuroxime axetil or sodium (CFX), Cefaclor (CFCR), Ceftazidime (CZD), Ceftizoxime (CTIZ), Ceftriaxone (CTRX), Cefoperazone (CPZ), Cefixime (CXIM) and Cefpodoxime proxetil (CFPD)] are described. Both methods are based on the acidic oxidation of the antibiotics with cerium (IV) at elevated temperature. The effect of the reagent concentration, volume of the acid,and the heating temperature were studied to optimize the reaction conditions. Each antibiotic was determined by either measuring the absorbance difference at 317 nm or the cerous inherent fluorescence at 256 and 356 nm for excitation and emission wavelengths, respectively. The two procedures have been successfully applied to the assay of these antibiotics in their pharmaceutical dosage forms. The obtained results have been statistically compared with those obtained by the official methods.     

Spectrofluorimetric method for the simultaneous determination of zinc and cadmium

The simultaneous determination of zinc and cadmium using derivative synchronous and multiwavelength synchronous spectrofluorimetry is described. Effects of experimental variables on the fluorescence intensities and on the spectral resolution of the fluorescent chelates of these metals with 8-(p-toluenesulfonamido)-quinoline (TSQ) in a sodium lauryl sulfate micellar medium have been studied. Mixtures containing 10–200 g L^–1 Zn and 15–250 g L^–1 Cd have been analyzed with good results. The proposed method has been applied to a biological sample.     

A New Spectrofluorimetric Method for Determination of Trace Amounts 5-Hydroxytryptamine in Human Urine and Serum

A new spectrofluorimetric method was developed for the determination of trace amount of 5-hydroxytryptamine (5-HT) in human urine and serum samples. In the NaAc-HAc buffer solution of pH=5.80, 5-HT can react with formaldehyde-acetylacetone system to form a new compound which sends yellow green fluorescence at 533nm and the enhanced fluorescence intensity is in proportion to the concentration of 5-HT. Optimum conditions for the determination of 5-HT were also investigated. The dynamic range and detection limit for the determination of 5-HT are 5.35×10⁻⁷∼1.07×10⁻⁴ mol/L and 2.08×10⁻⁷ mol/L, respectively. The developed method is simple, practical and can be successfully applied to determination of 5-HT in human urine and serum samples. Moreover, the enhancement mechanisms of the fluorescence intensity in the 5-HT - formaldehyde-acetylacetone system have been also discussed.     

Sensitive Determination of Norfloxacin by the Fluorescence Probe of Terbium (III)- Sodium Dodecylbenzene Sulfonate and Its Luminescence Mechanism

The fluorescence system of the norfloxacin-Tb³⁺- sodium dodecylbenzene sulfonate (SDBS) was investigated in this paper. The experiments indicated that the fluorescence intensity of the Tb³⁺-SDBS was greatly enhanced by the norfloxacin. On the basis of the above findings, a sensitive fluorimetric method for determining the norfloxacin was established. The fluorescence intensity was measured by a 1-cm quartz cell with the excitation wavelength of 290 nm and the emission wavelength of 545 nm. The enhanced fluorescence intensity of the system (Δ F) showed a good linear relationship with the concentration of norfloxacin in the range of 5.0×10⁻⁹ mol L⁻¹–2.0×10⁻⁶ mol L⁻¹, its correlation coefficient was 0.9991 and the detection limit (S/N=3) was 1.2×10⁻⁹ mol L⁻¹. The presented method was used to determine the norfloxacin in real pharmaceutical samples. The luminescence mechanism was also discussed in detail. In the fluorescence system of the norfloxacin-Tb³⁺-SDBS, the SDBS not only acted as the surfactant, but also acted as the energy donor.     

Sensitive determination of enoxacin by its enhancement effect on the fluorescence of terbium(III)-sodium dodecylbenzene sulfonate and its luminescence mechanism

The fluorescence system of enoxacin-Tb³⁺-sodium dodecylbenzene sulfonate (SDBS) was investigated in this paper. The experiments indicated that the fluorescence intensity of Tb³⁺-SDBS was greatly enhanced by enoxacin. Accordingly, a sensitive fluorimetric method for determining enoxacin was established. The fluorescence intensity was measured by a 1-cm quartz cell with an excitation wavelength of 290 nm and an emission wavelength of 545 nm. The enhanced fluorescence intensity of the system (ΔF) showed a good linear relationship with the concentration of enoxacin in the range of 5.0×10⁻⁹ to 2.0×10⁻⁶ mol L⁻¹, its correlation coefficient was 0.9992 and the detection limit (S/N=3) was 2.8×10⁻⁹ mol L⁻¹. The presented method was used to determine enoxacin in real pharmaceutical samples. The luminescence mechanism was also discussed in detail. In the fluorescence system of enoxacin-Tb³⁺-SDBS, SDBS not only acted as the surfactant but also acted as the energy donor.     

Vibration Spectra of Coprecipitated Fe(III)-Ni(II) and Fe(III)-Cu(II) Hydroxides and of the Products of Their Thermolysis

A range of coprecipitated Fe(III)-Me(II) (Me(II) = Ni, Cu) hydroxides and of the products of their thermolysis have been investigated by the IR spectroscopy method. The basic absorption bands has been assigned, and the chemistry of the process of formation of coprecipitated hydroxides has been discussed from the standpoint of generation of heteronuclear hydrococomplexes.     

N-(1-萘基)-乙二胺荧光光度法测定痕量亚硝酸根

研究了盐酸介质中N-(1-萘基)-乙二胺(NED)与亚硝酸根的反应。基于NED的荧光强度被亚硝酸根猝灭的现象,建立了一种荧光测定NO-₂的新方法,并对反应机理进行了讨论。在优化实验条件下,NO-₂在1.07～214.0 μg·L-1范围内与NED的荧光猝灭强度呈线性关系,方法的检出限为0.069 μg·L-1。该法用于测定水样中痕量亚硝酸根的含量,结果令人满意。     

Nonlinear refractive index measurement of tris(acetylacetonato) manganese(III) solution

We present the results from investigations of the nonlinear refractive index and nonlinear absorption coefficient of tris(acetylacetonato)manganese(III) solution, using Z-scan technique with a low-power continuous-wave laser at 514 nm. We demonstrate that the light-induced nonlinear refractive index variation leads to strong self-focusing and self-defocusing. A pump and probe technique was used to investigate the cause of nonlinearity. Furthermore, the nonlinear absorption effect was utilized to demonstrate all optical switching.     

Theoretical Calculations of Transition Probabilities and Oscillator Strengths for Sc(III) and Y(III)

利用最弱受约束电子势模型理论计算了二价钪离子和二价钇离子的能级间跃迁几率和振子强度的数值. 二价钪离子的计算结果与美国国家标准技术研究院(NIST)所给出的可接受值吻合良好. 二价钇离子的计算结果也与现有的其他理论方法的计算结果十分接近.     

Kinetics and mechanism of uncatalysed and ruthenium(III) catalysed oxidation of allyl alcohol by diperiodatoargentate(III) in aqueous alkaline medium

The oxidation of allyl alcohol by diperiodatoargentate(III) (DPA) is carried out both in the absence and presence of ruthenium(III) catalyst in alkaline medium at 298 K and a constant ionic strength of 1.1 mol dm^?3 was studied spectrophotometrically. The oxidation products in both the cases were acrolein and Ag(I), identified by spectral studies. The stoichiometry is same in both the cases, that is, [AA]/[DPA] = 1:1. The reaction shows first order in [DPA] and has less than unit order dependence each in both [AA] and [Alkali] and retarding effect of [IO] in both the catalysed and uncatalysed cases. The order in [Ru(III)] is unity. The active species of DPA is understood to be as monoperiodatoargentate(III) (MPA) in both the cases. The uncatalysed reaction in alkaline medium has been shown to proceed via a MPA–allyl alcohol complex, which decomposes in a rate determining step to give the products. In catalysed reaction, it has been shown to proceed via a Ru(III)‐allyl alcohol complex, which further reacts with one molecule of MPA in a rate determining step to give the products. The reaction constants involved in the different steps of the mechanisms were calculated for both reactions. The catalytic constant (K_c) was also calculated for catalysed reaction at different temperatures. The activation parameters with respect to slow step of the mechanisms were computed and discussed for both the cases. The thermodynamic quantities were also determined for both reactions. Copyright © 2007 John Wiley & Sons, Ltd.