磷光寿命法研究无保护流体室温磷光的重原子效应和发光动力学参数

以两种卤代萘为模型化合物，基于磷光寿命的定义τ＝τ^-，τ0＝1／kp和其与各速率常数的关系，导出了一种类似于Stern-Volmer方程的线性方程：τ0／τ＝（kp_kic)/kp=1 kic/kp=1 Ksv.c。通过测定不同重原子微扰剂浓度时的磷光寿命，探讨了从两种途径计算流体室温磷光发射相关动力学参数的可行性和方法，通过这些参数对比讨论了KI和TINO3两种重原子微扰剂对这两种卤代萘无保护流体室温磷光发射的重原子效应的差异。     

Room‐Temperature Phosphorescence in Metal‐Free Organic Materials

Purely organic materials with room‐temperature phosphorescence (RTP) have attracted a growing interest for their potential applications in biological imaging, digital encryption, optoelectronic devices, and so on. To date, many strategies have succeeded in designing efficient organic RTP materials by overcoming the spin‐forbidden transition between singlet and triplet states. However, the underlying mechanisms of RTP still remain ambiguous. Such spin prohibition in phosphorescence are clarified, herein, from the perspective of perturbation theory, helping to understand the intrinsic relationship among various phosphorescence parameters, like phosphorescence efficiency, lifetime, intersystem crossing rate, as well as radiative and nonradiative rates. Taking into consideration the recent progress in organic RTP materials, these factors are further illustrated by a selection of the most relevant molecules. In addition, some novel RTP phenomena are also reviewed, thus providing an excellent guideline to constructing efficient RTP materials.     

吲哚-3-丁酸无保护流体室温燐光和胶束增稳室温燐光性质的比较

仔细研究了吲哚-3-丁酸(IBA)的无保护流体室温燐光(NP-RTP)及以高分子分散剂聚乙二醇-200,聚乙二醇-400和非离子表面活性剂Tween-20,Tween-40, Tween-80,Tween-85,Brij35和乳化剂OP为介质的流体室温燐光性质。表面活性剂和高分子分散剂能抑制IBA燐光猝灭,使其具有更低的检出限,同时也使燐光强度-激发光照射时间曲线发生改变,但不影响IBA燐光光谱特性。无论是否存在表面活性剂或高分子分散剂,TlNO₃都不能诱导IBA产生燐光,KI却能诱导其产生强烈燐光。用于强化水样和土壤样品中IBA的测定,回收率95.2%～104%,相对标准偏差2.4%～4.0%。     

苯并咪唑的三维荧光光谱与三维室温磷光光谱

测量了浓度为1×10^-4mol/L苯并咪唑水溶液的三维荧光光谱,三维室温磷光光谱和紫外/可见吸收光谱,还测量了苯并咪唑固体紫外/可见吸收光谱对化合物的荧光和室温磷光进行了分析、比较,发现苯并咪唑在290nm、580nm和870nm区域均有强而丰富的荧光谱线,而室温磷光谱线(RTP)单一地出现在290nm区域,且强度很小;同时还讨论了苯并咪唑的升频转换荧光现象.     

异硫氰酸荧光素标记抗体的固体基质室温磷光性质研究

研究了异硫氰酸荧光素（FITC）标记的羊抗人抗体（GAHAb-FITC)和兔抗羊抗体9RAGAb-FITC)，及其以三种免疫方式与人免疫球蛋白（IgG)反应所得免疫复合物在多种固体薄膜基质上发射室温磷光（RTP）的适宜条件及其光谱，强度和寿命等性质。研究发现，标记抗体及其免疫复合物保留了FITC优良的固体基质室温磷光性质，λ m0643em^(max)=525/650nm，其RTP强度与其浓度线性相关，并有很高的灵敏度，更为重要的是，免疫反应及其RTP检测能结合于同一基质，方便地相继完成，在聚酰胺膜（PM）上，以Pb(Ac)2为重原子微扰剂，稀释比为1：10（ψ）的GAHAb-FITC,RAGAb-FITC及其与人IgG形成的免疫复合物均能发射较强制 RTP信号并有较长的RTP寿命，本结果为建立相应的固体基质室温磷光免疫分析（SS-RTP-IA）新方法奠定了相应的实验基础。     

菲的无保护性介质流体室温磷光性质研究

在无任何保护性介质存在下,以Na2SO3作化学除氧剂,KI为重原子微扰剂,菲即能产生强而稳定的流体室温磷光发射.激光和发射波长λex/λem为283/482,504nm,不同有机溶剂存在对其磷光发射的性质有不同影响.1%乙腈存在时,菲浓度在8.0×10-7～6.0×10-6mol*L-1和6.0×10-6～4.0×10-5mol*L-1范围内分别与磷光发射强度呈良好的线性关系,检出限为2.6×10-8mol*L-1.     

Room-Temperature Phosphorescence Turn-on Detection of DNA Based on Riboflavin-Modulated Manganese Doped Zinc Sulfide Quantum Dots

A sensitive phosphorescent sensor based on riboflavin (RF)-modulated mercaptopropionic acid (MPA)-capped Mn-doped ZnS quantum dots (QDs) was developed and utilized as room-temperature phosphorescence (RTP) sensor for DNA detection. The RTP of the MPA-capped Mn-doped ZnS QDs was stored via photoinduced electron transfer by RF, and formed an electrochemically nonactive QDs/RF nanohybrids through electrostatic attraction. In the presence of DNA, RF could bind with DNA, which has a double helical structure, via electrostatic interaction and intercalation. RF can be removed from the surface of the QDs, thus releasing the RTP of the QDs. On the basis of this principle, an RTP sensor for DNA detection was developed. Under optimal conditions, the detection limit for DNA was 15 μg mL^?1, the relative standard deviation was 1.9 %, and the method recovery ranged from 97 % to 103 %. The proposed method was applied to biological fluids, in which satisfactory results were obtained.     

黄嘌呤甲基衍生物滤纸基质室温磷光光谱研究

以滤纸为基质,详细讨论了3种黄嘌呤甲基衍生物可可碱、咖啡因、茶碱的固体基质温磷光光谱特性,研究表明：它们的滤纸基质室温磷光（PS－RTP）光谱基本相近,其最大激发波长λem分别为435、432、427nm。40余种无机盐类重原子微扰剂对这3种化合物诱发室温磷光的研究结果为：KI、NaI,Zn(NO3)2,SrCl2对可可碱、咖啡因、茶碱发射PS－RTP都有一定的重原子效应,其中I^-对它们诱发PS－RTP重原子效应最大,酸度实验表明,酸度对可可碱的影响在于咖啡因和茶碱,3种化合物在pH-2-8范围内都有PS－RTP,而且在强酸和强碱笥条件下它们的PS－RTP均发生猝灭,此外,本文也对影响PS－RTP的温度、干燥时间等条件进行了考察。     

Multivariate calibration in TXRF analysis of water

The aim of this paper is the application of multivariate linear calibration for quantitative determination of elements (K, Cd, Co, Hg, As, Pb, Ni, and Al) in water by using Total Reflection X‐ray Fluorescence Analysis with partial least squares (PLS) as a regression method to improve a result of common univariate method. In purpose of elimination of matrix effects in X‐ray fluorescence analysis, experimental design was applied. As a set of standard samples for multivariate calibration, a five‐level eight‐factor calibration design of 25 samples was chosen, ensuring mutual orthogonality of factors. For model's validation, the independent test set of 15 samples was examined. The collection of spectra and quantitative measurements was carried out on S2 PICOFOX. The PLS regression was performed by using software package STATISTICA. Quality indicators of multivariate calibration as slope (b) and intercept (a) of calibration, correlation coefficient (r), determination coefficient (R²), root mean square errors of calibration and of prediction, standard errors of calibration and of prediction, biases of calibration, and biases of prediction were calculated. These results were compared with the univariate model, and as a result, the multivariate calibration method exceeds the univariate one. The obtained results could be applied in a laboratory for an analysis of water solutions in the concentration range 0.05–2.00 mg/L. In many real situations, when analytical chemist deals with multi‐element mixtures, multivariate calibration approach combined with orthogonal design for multivariate calibration set could be successfully used to improve a conventional univariate calibration.     

固相(微)萃取-室温磷光联用技术及其应用

综述了固相(微)萃取-室温磷光技术的主要方法以及在环境分析中的应用。主要从固相萃取的基本原理、装置、操作步骤、分离模式及填料等方面评述了固相(微)萃取技术的特点和应用,评述了室温磷光技术的优点和经典室温磷光技术在操作方法和定量分析方面存在的不足,提出了固相(微)萃取和室温磷光联用技术的必然性及其优点,并对该方法的关键技术和存在的难题进行了分析。该技术结合了富集技术与高选择性的磷光分析方法,使得分析的灵敏度进一步提高,选择性也得到了较大的改进。目前常用的固相萃取填料主要有Whatman 1PS滤纸和填充有C₁₈或C₈盘或(膜),目标分析物主要集中在多环芳烃、多氯联苯和多氯联苯呋喃等物质的分析,应用前景十分广泛。     

超分子组合流体室温磷光现象（Ⅱ）—醇对环糊精／碘代乙基联 …

在外部重原子微拢剂溴代环己烷存在下，β－ＣＤ／碘代乙基联苯体系可发射一定强度的室温磷光信号，若丁醇作为第四组分存在，则能显著提高体系的室温磷光发射强度。研究了该体系室温磷光发射的适宜条件和多种醇、不同环糊精及其衍生物的影响。认为β－ＣＤ／碘代乙基联苯／溴代环乙烷／丁醇体系属于一种超分子组合的发光体系，醇的作用属典型的分子调控作用。β－ＣＤ／碘代乙基联苯／溴代环乙烷形成主、客三元包结物，可醇则利用其     

多组分复杂体系光谱多元定量分析方法研究

为解决多元分析方法建模成本高及适用性差,严重制约其在光谱分析领域大量应用的难题,提出了一种新的多元定量分析方法。以汽油及其甲基叔丁基醚（MTBE）溶液的红外光谱为研究对象,使用五种汽油及其窄馏分建立背景光谱空间,用斜投影算法分离出混合光谱中纯MTBE光谱分量,建立纯光谱响应值与浓度之间的标准曲线,相关系数为0.995 2,截距仅为0.025,实现了多组分复杂体系中待测物的定量分析。与正交投影方法比较,新方法对五个预测样本的预测结果明显优于正交投影法。对17个实际油样的预测结果显示,新方法比PLS模型具有更好的适用性。新方法无需收集大量样本和建立复杂模型,方法简单,准确,适用性好。     

Optimization of Verapamil Drug Analysis by Excitation-Emission Fluorescence in Combination with Second-order Multivariate Calibration

Excitation emission fluorescence matrices (EEMs) of Verapamil drug were obtained by direct and by derivatization fluorescence spectroscopy. The fluorescence excitation and emission wavelengths were displaced to longer wavelengths and the fluorescence intensity was enhanced upon derivation with respect to the native fluorescence of the drug. The complete EEM of the native fluorescence of the drug and of the derivatization product were rapidly acquired by using a charged-coupled device detector (CCD), which is advantageous in terms of speed in the analysis, with respect to the use of a conventional photomultiplier detector. The EEMs were analyzed by several second-order multivariate calibration methods exploiting the second order advantage. The three-dimensional decomposition methods used, based in different assumptions about the trilinearity of the three way data structure under analysis, were parallel factor analysis (PARAFAC), bilinear least squares (BLLS), parallel factor analysis 2 (PARAFAC2) and multivariate curve resolution—alternating least squares (MCR-ALS). The determination was performed by using the standard addition approach. The figures of merit of the PARAFAC and BLLS methods were calculated, obtaining a lower limit of detection with the derivatization procedure, when compared with the direct measurement of the fluorescence of the drug. In Verapamil drug the best estimations were found with the BLLS and the MCR-ALS models. In the quantification of Verapamil in a pharmaceutical formulation the best estimation, when compared with the result obtained by the US Pharmacopeia high performance liquid chromatography approach, was obtained by direct fluorescence spectroscopy with MCR-ALS and by derivatization fluorescence spectroscopy with the PARAFAC2 model.     

Determination of Trace Bismuth by a Solid Substrate Room Temperature Phosphorescence Quenching Method Based on Anionic Polymeric Acryclic Acid Lead Particles Containing Luminescent Eosine Molecules

Abstract

Luminescent particles of Anionic Polymeric Acryclic Acid Lead (Pb(PAA)₂) which containing eosine(HFInBr₄), Eosine nanomicroball of anionic polypropylene acid lead contained luminophores (short for E.N.PAA.L.C.L), were synthesized by a sol‐gel method, using anionic polymeric acryclic acid sodium (PAANa) as the precursor and Pb²⁺ as the precipitant. NH₄Ac‐HAc can react with the Pb²⁺ in E.N.PAA.L.C.L, causing it to decompose into aqueous soluble components. E.N.PAA.L.C.L‐ NH₄Ac‐HAc can emit strong and stable solid substrate room temperature phosphorescence (SS‐RTP) on filter paper, and bismuth, mercury or iodine can cause a decrease in phosphorescence intensity. Based on the facts above, a new method for the determination of trace bismuth by an SS‐RTP quenching method was established. The linear range of this method was 0.01–0.20(pg spot^?1) (4.0×10^?12 g ml^?1) of Bi³⁺, with a detection limit (LD) of 0.0016 pg spot^?1, and the regression equation of the working curve was ΔIp=61.01+237.8 m_Bi3+ (pg spot^?1), r=0.9992. This method was applied to the determination of trace bismuth in human hair and well water samples with satisfactory results. The mechanism of SS‐RTP emission was also discussed.     

The Triplet State: Emerging Applications of Room Temperature Phosphorescence Spectroscopy

Room‐temperature phosphorescence (RTP) has been exploited for analytical research for over 30 years now due to the widespread recognition of its unique properties as a selective and sensitive technique, complementary to fluorescence. Recent years have seen the awakening of medical, geological, industrial, and technological interest in its application. The trend continues, driven by the achievements that have already been made and the promise of future achievements. This review attempts to cover specifically emerging applications of RTP in areas such as medicine, geological dating, forensics, and technology, illustrating the advantages that can be derived from the use of the technique and stressing its potential for novel applications.     

不除氧条件下环糊精诱导室温磷光法测定喹啉

在不除氧条件下，１０ｍＬ含喹啉／β－ＣＤ溶液中只需加入１５μＬ１，２－二溴丙烷（ＤＢＰ）作重原子微扰剂，就能产生强而稳定的室温磷光信号。最大λｅｘ／λｅｍ＝２７３／４９６ｎｍ。喹啉浓度在５．０×１０＾－７￣５．０×１０＾－５ｍｏｌ／Ｌ，５．０×１０＾－４ｍｏｌ／Ｌ，两段三个数量级范围与室温磷光信号有良好的线性关系，最低检测限７．４×１０＾－８ｍｏｌ／Ｌ。本体系的特点是ＤＢＰ用量少，从而减少了因过量     

A Promising CdSe@CdS-Quantum Dots-Cysteine for the Determination of Trace IgE by Solid Substrate Room Temperature Phosphorescence Immunoassay

The labelling reagent CdSe@CdS-QDs-Cys (QDs-Cys) with the grain diameter of 4.5 nm was synthesized by modifying CdSe@CdS quantum dots (QDs) with cysteine (Cys). At the same time, QDs-Cys-Ab_IgE, a phosphorescent quantum dot probe, was developed based on the labelling reaction between -COOH of QDs-Cys and -NH₂ of goat anti human IgE antibody (Ab_IgE). This probe with excellent biocompatibility and high specificity could not only emit strong and stable room temperature phosphorescence (RTP), but also could carry out specific immunoassay (IA) with immunoglobulin E (IgE), causing the RTP of the system to sharply enhance. Thus, a new solid substrate room temperature phosphorescence immunoassay (SSRTPIA) for the determination of IgE was established. The limit of quantification (LOQ) of the method was 0.12 fg spot⁻¹, corresponding concentration was 3.0 × 10⁻¹³ g mL⁻¹ and sampling quantity was 0.40 μL spot⁻¹. This highly selective, sensitive and accurate SSRTPIA has been applied to determine IgE in biological samples and diagnose diseases, and the results agreed well with those obtained by enzyme-link immunoassay (ELISA). Meanwhile, the mechanisms of QDs-Cys labelling Ab_IgE and the determination of IgE by SSRTPIA were also discussed.     

Optical Method for the in-situ Measurement of the pH-value During High Pressure Treatment of Foods

This contribution presents a novel optical method to determine the pH-value during the high pressure treatment of foods. Up to date an appropriate online measurement device does not exist. The present study makes use of a multivariate approach, using the optical properties of pH indicators. An indicator mix of 16 different pH-sensitive substances is applied. The calibration of the system is performed taking five different buffer substances (TRIS, CAPS, citric, phosphoric and acetic acid buffers), applying thermodynamical considerations, to calculate the pH-value at high pressure. The corresponding spectra of the indicator mix is measured and fed to a multivariate data model together with calculated pH values. Different chemometric models have been constructed to estimate the pH value based upon the spectrum of the indicator mix. The calibration device covers a pH range from 2 to 8. After calibration it was possible to determine the pH value at pressures up to 450 MPa with an accuracy of 0.02 pH units in 9 different test media.     

心得宁的丹磺酰氯衍生—室温磷光分析

心得宁的丹磺酰氯衍生物具有强的荧光及磷光，可用于心得宁的发光分析。本文详细研究了心得宁同丹磺酰氯衍生的反应条件及检测衍生物的最佳光谱条件。利用一阶导数光谱技术，无需对衍生物溶液进行任何分离，实现了心得宁的室温磷光检测。     

Multivariate calibration for the improvement of the quantification of cadmium in the presence of potassium as interferent by total reflection X-ray fluorescence

A multivariate calibration method was applied to improve the accuracy of the determination of cadmium in the presence of potassium by total reflection X-ray fluorescence (TXRF). Due to TXRF's relatively low resolution, a particular interference caused by potassium at line Kα 3.31 keV as interference can compromise the cadmium determination at line Lα 3.13 keV, respectively. The method is based on the hypothesis that the application of a multivariate calibration method, for example, partial least squares, could reduce variations due to interference and, consequently, improve the selectivity and accuracy in Cd determination. In this work, this strategy was evaluated on the X-ray fluorescence emission signals between 2.50 and 3.90 keV for a set of 26 different synthetic calibration mixtures and eight different mixtures for external calibration. Based on a certified reference material (Clay 2—CRM051) with high potassium levels, a significant improvement of accuracy for cadmium determination was observed, overcoming the problems associated with spectral interferences by potassium.