Determination of trace silver by solid substrate-room temperature phosphorescence quenching method based on double catalytic system of meta-nitrophenyfluorone-polyoxyethylene-chromium-potassium bromate-beta-cyclodextrin

A new solid substrate-room temperature phosphorescence (SS-RTP) quenching method for the determination of trace silver has been established. It is based on the fact that when using Mg(2+) as ion perturber and beta-CD as surfactant, the system of meta-nitrophenyfluorone (R)-polyoxyethylene-Cr(III) can emit strong and stable room temperature phosphorescence signal on filter paper whose surface is modified by polyvinyl alcohol (PVA)-H(3)BO(3)-NaOH. Ag(I) can catalyze KBrO(3) oxidizing R-PEO-Cr(III) system which causes the quenching of SS-RTP. The reducing value of phosphorescence intensity (DeltaI(p)) is directly proportional to the concentration of Ag(I) in the range of 3.2-160 ag spot(-1) (corresponding concentration: 2.43 fg ml(-1), the sample volume: 0.40 microl spot(-1)) with a detection limit (LD) of 0.97 ag spot(-1). The regression equation of working curve can be expressed as DeltaI(p)=13.92+0.3089m(Ag)+ (ag spot(-1)) (r=0.9983, n=6). This method has many advantages, such as a wide linear dynamic range, high sensitivity, good repeatability and selectivity. It has been applied to the determination of trace silver in real samples with satisfactory results. What is more, the mechanism of SS-RTP quenching method based on Ag(I) catalyzing KBrO(3) oxidizing meta-nitrophenyfluorone has also been discussed.     

Determination of trace formaldehyde by solid substrate-room temperature phosphorescence quenching method based on the rose bengal-potassium bromate-Tween-80 system

A new method for the determination of trace formaldehyde by solid substrate-room temperature phosphorescence quenching method has been proposed. It is based on the facts that rose bengal (R) can emit intense and stable room temperature phosphorescence on the solid substrate of filter paper (SS-RTP). Potassium bromate (KBrO(3)) can oxidize R, which causes the quenching of RTP. In the presence of HCHO, it can react with KBrO(3) to form Br(2) and Br(2) can oxidize R, which causes smart quenching of RTP. The phosphorescence intensity (DeltaI(p)) is directly proportional to the concentration of HCHO. In the presence of Tween-80, the DeltaI(p) will be increased to 9.1 times higher than that without it. The linear range of this method is 0.016-1.6fgspot(-1) (corresponding concentration: 0.040-4.0 pgml(-1), 0.40 microlspot(-1)) with the detection limit of 4.5agspot(-1) (corresponding concentration: 1.1 x 10(-14) gml(-1)). The regression equation for working curve is DeltaI(p)=136.6+28.28m(HCHO)fgspot(-1) (r=0.9935, n=6). This method is sensitive, simple, rapid and has been applied to the determination of trace formaldehyde in real samples with satisfactory results. The mechanism of determination of trace formaldehyde by SS-RTP quenching method based on the rose bengal-KBrO(3)-Tween-80 system is also discussed.     

蒽醌衍生物在痕量汞固体基质室温燐光猝灭法测定中的应用

该文合成了2,3-二氢-9,10-二羟基-1,4-蒽醌(R),并借助核磁共振谱、红外光谱、质谱及紫外光谱等方法确定其结构.基于R在醋酸纤维素膜固体基质上能产生强而稳定的固体基质室温燐光(SS-RTP),α,α'-联吡啶可活化Hg2+催化H2O2氧化R转化成无燐光化合物,导致固体基质室温燐光急剧猝灭,建立了催化H2O2氧...     

Determination of trace silver by solid substrate room temperature phosphorescence quenching method based on lead carboxymethyl cellulose particles (Pb(CMC)2) containing luminescent salicyl fluorenes molecules

Luminescent particles of lead carboxymethyl cellulose (Pb(CMC)2) containing salicyl fluorones (THBF), Pb(CMC)2-THBF were synthesized by the sol-gel method, using sodium carboxymethyl cellulose (NaCMC) as precursor and Pb2+ as precipitant. Pb(CMC)2-THBF can emit the intense and stable solid substrate room temperature phosphorescence (SS-RTP) on filter paper. And EDTA can chelate Pb2+ in Pb(CMC)2-THBF, causing it to decompose into aqueous soluble components PbY2-, CMC- and THBF, which can react with Ag+ to form Ag(CMC)2-THBF, causing the decrease of phosphorescence intensity. Based on the facts above, a new method for the determination of trace silver by SS-RTP quenching method was established. The linear range of this method is 8.0-40.0 fg spot(-1) (20.0-100.0 pg ml(-1)), with a detection limit (LD) of 2.2 fg spot(-1) (corresponding to a concentration range of 5.5 x 10(-13) g ml(-1)), and the regression equation of working curve is DeltaI(p) = 12.56 + 0.5527C(Ag+) (fg spot(-1), 0.4 microl spot(-1)), n = 8, r = 0.9992. This method has been applied to the determination of trace silver in human hair and tea sample with satisfactory results. The mechanism of SS-RTP emission is also discussed.     

Determination of trace selenium by solid substrate-room temperature phosphorescence enhancing method based on potassium chlorate oxidizing phenyl hydrazine-1,2-dihydroxynaphthalene-3,6-disulfonic acid system

A new method for the determination of trace selenium based on solid substrate-room temperature phosphorimetry (SS-RTP) has been established. This method was based on the fact that in HCl-KCl buffer solution, potassium chlorate could oxidize phenyl hydrazine to form chloridize diazo-ion after being heated at 100 degrees C for 20 min, and then the diazo-ion reacted with 1,2-dihydroxynaphthalene-3,6-disulfonic acid to form red azo-compound which could emit strong room temperature phosphorescence (RTP) signal on filter paper. Selenium could catalyze potassium chlorate oxidizing the reaction between phenyl hydrazine and 1,2-dihydroxynaphthalene-3,6-disulfonic acid, which caused the sharp enhancement of SS-RTP. Under the optimum condition, the relationship between the phosphorescence emission intensity (DeltaIp) and the content of selenium obeyed Beer's law when the concentration of selenium is within the range of 1.60-320 fg spot-1 (or 0.0040-0.80 ng ml-1 with a sample volume of 0.4 microl). The regression equation of working curve can be expressed as DeltaIp=13.12+0.4839CSe(IV) (fg spot-1) (n=6), with correlation coefficient r=0.9991 and a detection limit of 0.28 fg spot-1 (corresponding to a concentration range of 7.0x10(-13) g ml-1 Se(IV), n=11). After 11-fold measurement, R.S.D. were 2.8 and 3.5% for the samples containing 0.0040 and 0.80 ng ml-1 of Se(IV), respectively. This accurate and sensitive method with good repeatability has been successfully applied to the determination of trace selenium in Chinese wolfberry and egg yolk with satisfactory results. The mechanism of the enhancement of phosphorescence was also discussed.     

Determination of trace calcium by solid substrate-room temperature phosphorimetry

A new method for the determination of trace calcium by solid substrate-room temperature phosphorimetry is established. It is based on the fact that chromeazurols azurol S-phenanthroline-NaCMC (CAS-phen-NaCMC) system can emit strong and stable room temperature phosphorescence (RTF) on the solid substrate in the filter paper. Ca2 and phenanthroline can form complex ion Ca(phen)32 , which will form complex [Ca(phen)3(CAS)2] with CAS. In the result, the number of CAS molecules in each spot increased, causing sharp increase of the RTP signal of the CAS-phen-NaCMC system.     

Determination of trace glucose and forecast of human diseases by affinity adsorption solid substrate room temperature phosphorimetry based on Triticum valgaris lectin labeled with 4.0-generation dendrimers

A new phosphorescence labeling reagent Triton-100X-4.0G-D (4.0G-D refers to 4.0-generation dendrimers) was found. Quantitative specific affinity adsorption (AA) reaction between Triton-100X-4.0G-D-WGA and glucose (G) was carried out on the surface of nitrocellulose membrane (NCM), and the DeltaI(p) of the product of AA reaction was linear correlation to the content of G. Based on the facts above, a new method for the determination of trace G was established by WGA labeled with Triton-100X-4.0G-D affinity adsorption solid substrate room temperature phosphorimetry (Triton-100X-4.0G-D-WGA-AA-SS-RTP). This research showed that AA-SS-RTP for either direct method or sandwich method could combine very well the characteristics of both the high sensitivity of SS-RTP and the specificity of the AA reaction. Detection limits (LD) were 0.24 fg spot(-1) for direct method and 0.18 fg spot(-1) for sandwich method, indicating both of them were of high sensitivity. The method has been applied to the determination of the content of G in human serum, and the results were coincided with those obtained by glucose oxidize enzyme method. It can also be applied to forecast accurately some human diseases, such as primary hepatic carcinoma, cirrhosis, acute and chronic hepatitis, transfer hepatocellular, etc. Meanwhile, the mechanism for the determination of G with AA-SS-RTP was discussed.     

Catalytic solid substrate room temperature phosphorimetry for the determination of trace rhamnose based on its condensation reaction with calcein

Calcein (R) could not only emit strong and stable room temperature phosphorescence (RTP) on filter paper using I(-) as perturber, but also could be oxidized by H(2)O(2) to form a non-phosphorescence compound (R'), resulting in the quenching of RTP signal of R. Moreover, the ortho-hydrogen of phenolic hydroxyl in R took condensation reaction with rhamnose (Rha) to produce non-phosphorescence compound (R-Rha) causing the RTP signal of R to further quench, and R-Rha was oxidized by H(2)O(2) to form R' and Rha, bringing about the sharp RTP signal quenching of R. Thus, a new solid substrate room temperature phosphorimetry (SSRTP) for the determination of trace Rha based on its strong catalytic effect on H(2)O(2) oxidizing R has been established, with the detection limit (LD) of 7.8zgspot(-1) (corresponding concentration: 2.0×10(-17) gm l(-1), sample volume: 0.40 μl spot(-1)). This method has been applied to determine trace Rha in cigarettes and jujubes, with the results coinciding well with those determined by a high performance liquid chromatography (HPLC). The component of R-Rha also was analyzed by means of HPLC, mass spectrometer and nuclear magnetic resonance (NMR) measurements. The mechanism of catalytic SSRTP for the determination of trace Rha was discussed.     

Determination of trace aluminum by fluorescence quenching method based on catalysis of potassium chlorate oxidizing alizarin red

A new method for the determination of trace aluminum has been proposed. It is based on the fact that alizarin red can emit strong and stable fluorescence at 80 degrees C for 30 min and Al(3+) can effectively catalyze potassium chlorate oxidizing alizarin red to form non-fluorescence complex which cause the fluorescence quenching. The linear dynamic range of this method is 0.040-4.00 ngl(-1) with a detection limit of 5.3 pgl(-1). The regression equation can be expressed as DeltaI(f)=8.731+21.73c(Al(3+)) (ngl(-1)), with the correlation coefficient r=0.9992 (n=6). This sensitive, rapid and accurate method has been applied to the determination of trace aluminum(III) in human hair and tea samples successfully. What is more, the mechanism of catalyzing potassium chlorate oxidizing alizarin red by the fluorescence quenching method is also discussed.     

Preparation for nitrocellulose membrane-poly (vinyl alcohol)-ionic imprinting and its application to determine trace copper by room temperature phosphorimetry

Nitrocellulose membrane-poly (vinyl alcohol)-ionic imprinting (NCM-PVA-I-I) was prepared using Cu²⁺ as template. The cavity in NCM-PVA-I-I matched Cu²⁺ very well and the selectivity was high. Cu²⁺ entered the cavity and then could form ionic association ([Cu²⁺]·[(Fin⁻)₂]) with the anion of fluorescein (Fin⁻) outside the cavity by electrostatic effect. [Cu²⁺]·[(Fin⁻)₂] could emit strong and stable room temperature phosphorescence on NCM-PVA-I-I. Its ΔI_p was proportional to the content of Cu²⁺. Based on the above facts, a new method for the determination of trace copper by solid substrate-room temperature phosphorimetry (NCM-PVA-I-I-SS-RTP, SS-RTP is the abbreviation of solid substrate-room temperature phosphorimetry) using NCM-PVA-I-I technique has been established. The linear range of this method was 2.00-144.00 fg Cu²⁺ spot⁻¹ (sample volume: 0.40 μL spot⁻¹, corresponding concentration: 5.00-360.00 pg mL⁻¹), and the detection limit calculated by 3Sb/k was 0.43 fg Cu²⁺ spot⁻¹ (corresponding concentration: 1.1 × 10⁻¹² g mL⁻¹, n = 11). Samples containing 2.00 and 144.00 fg Cu²⁺spot⁻¹ were measured, respectively, for seven times and R.S.D.s were 3.5% and 4.7%. NCM-PVA-I-I-SS-RTP could combine very well the characteristics of both the high sensitivity of SS-RTP and the high match and selectivity of NCM-PVA-I-I, and it was rapid, accurate, sensitive and with good repeatability. It has been successfully applied to determine trace copper in human hair and tea samples.     

Determination of trace tin by solid substrate-room temperature phosphorimetry using sodium dodecyl sulfate as sensitizer

The effects of different surfactants on solid substrate-room temperature phosphorescence (SS-RTP) properties of Sn(4+)-morin systems were investigated. It was found that the SS-RTP intensity of luminescence system was increased greatly in presence of sodium dodecyl sulfate (SDS). A new highly sensitive method for the determination of trace tin has been proposed based on sensitization of SDS on SS-RTP intensity of morin-tin system on the filter paper substrate. The linear dynamic range of this method is 8.0-112 ag per spot (with the volume of 0.4 microl per spot) with a detection limit of 4.0 ag per spot, and the regression equation is DeltaIp=199.7+3.456m(Sn(IV)) (ag per spot), with the correlation coefficient r=0.9998 (n=7). This simple, rapid and reproducible method has been applied to determine the amount of tin in real samples with satisfactory results.     

Determination of trace arsenic(V) by catalytic solid substrate-room temperature phosphorescence quenching method

In the H2SO4 medium and in the presence of dodecylbenzene sulfonic acid sodiumsalt (DBS), dimethyl yellow (R) could emit strong and stable solid substrate room temperature phosphorescence (RTP) on filter paper. And NaIO4 could oxidize R to cause the RTP quenching. Arsenic(V) could catalyze the reaction of NaIO4 oxidizing R, which caused the RTP sharply quenching. The reducing value of phosphorescence intensity (△Ip) for the system with DBS is 3.3 times higher than that without DBS. Moreover, the△Ip is proportional to the concentration of As(V). Based on the facts above, a new RTP quenching method for the determination of trace As(V) has been established.     

Determination of trace glucose and forecast of human diseases by affinity adsorption solid substrate-room temperature phosphorimetry based on triticum vulgaris lectin labeled with dendrimers-porphyrin dual luminescence molecule

In this paper, 3.5-generation polyamidoamine dendrimers (3.5G-D)-porphyrin (P) dual luminescence molecule (3.5G-D-P) was developed as a new phosphorescence-labeling reagent. Meanwhile, the room temperature phosphorescence (RTP) characteristics of 3.5G-D-P and its product of labeling triticum vulgaris lectin (WGA) on the surface of polyamide membrane (PAM) were studied. Results showed that in the presence of heavy atom perturber LiAc, 3.5G-D and P of 3.5G-D-P molecule could emit strong and stable RTP on the PAM. And the Tween-80 would spike thoroughly the phosphorescence signal of 3.5G-D and P; moreover, specific affinity absorption (AA) reaction between the products (Tween-80-3.5G-D-P-WGA) of WGA labeled with Tween-80-3.5G-D-P and glucose (G) was carried out. The products of the AA reaction could keep good RTP characteristics of 3.5G-D and P dual luminescence molecule, and the DeltaI(p) was linear correlation to the content of G. According to the facts above, a new method of affinity adsorption solid substrate-room temperature phosphorimetry (AA-SS-RTP) for the determination of trace G was established, basing on WGA labeled with Tween-80-3.5G-D-P dual luminescence molecule. The detection limit of this method was 0.13fgspot(-1) (1.7x10(-12)moll(-1), 3.5G-D) and 0.14fgspot(-1) (2.2x10(-12)moll(-1), P). Determination of G in human serum using excitation/emission wavelength of either 3.5G-D or P, the result was coincided with enzyme-linked immunosorbent assay (ELISA). Not only the sensitivity and accuracy of this method were higher, but also the flexibility of AA-SS-RTP was obviously improved and the applicability was wider.     

Determination of trace gastrin and diagnosis of human diseases using CdTe quantum dots labelled gastrin antibodies as phosphorescence sensors

CdTe quantum dots (CdTe-QDs) can emit strong and stable room temperature phosphorescence (RTP) via the perturbation effect of a Pb(2+) ion on the surface of a nitrocellulose membrane (NCM). CdTe-QDs-Ab(GAS), the product of CdTe-QDs labelled gastrin antibodies (Ab(GAS)), can not only maintain good RTP characteristics, but can also be used as a RTP sensor and carry out highly specific immunoreactions with gastrin (GAS) to form GAS-Ab(GAS)-CdTe-QDs causing the ΔI(p) of the system to sharply enhance. Thus, a new solid substrate room temperature phosphorescence immunoassay (SSRTPIA) for the determination of GAS was established based on the linear relativity between the ΔI(p) of the system and the content of GAS. The limit of quantification (LOQ) of this method was 0.43 fg spot(-1) with the corresponding concentration being 1.1 × 10(-12) g mL(-1) and sampling quantity being 0.40 per spot(-1). This highly specific, accurate, selective and sensitive RTP sensor has been applied to the determination of GAS in biological samples and the diagnosis of diseases, and the results agreed well with those obtained by radioimmunometric assay (RIA). Meanwhile, the mechanism of SSRTPIA for the determination of GAS using CdTe-QDs-Ab(GAS) as the RTP sensor was discussed.     

Determination of Trace Titanium by Solid Substrate－Room Temperature Phosphorimetry with 4,5－Dibromophenylfluorone as Luminescent Ligand and Triton X－100 as Sensitizer

A new highly sensitive solid substrate room temperature phosphorimetry for the determination of trace titanium is proposed based on the sensitization of Triton X-100 to the SS-RTP intensity of 4, 5-dibro-mophenylfluorone-titanium complex adsorbed on the filter paper substrate modified by gelatin. When Triton X-100 was added into the luminescence system, the RTP intensity was raised 3 times stronger than that of the system without Triton X-100. The linear dynamic range of the new method is 0. 64 ～ 3.2 fg/spot (0. 4 μL) with a detection limit of 12.8 ag/spot, and the regression equation of the working curve is △Ip = 482. 0 119.5mTi（Ⅳ) (fg/spot), the correlation coefficient r= 0. 9992, n = 6. The phosphorescence lifetime (r= 0. 85 ms) was also determined. The recoveriesCand RSD) for the determinations of titanium in human hair and tea samples were 101.0% (3. 0%) and 99. 97% (4. 2%), respectively.     

Studies on the spectroscopic behavior of cryptotanshinone, tanshinone IIA, and tanshinone I

A comparative study on the spectroscopic behavior of cryptotanshinone (CTan), tanshinone IIA (Tan IIA), and tanshinone I (Tan I) has been investigated, including UV-Vis absorption, low temperature phosphorescence (LTP), low temperature fluorescence (LTF), paper substrate-room temperature phosphorescence (PS-RTP), paper substrate-room temperature fluorescence (PS-RTF) and fluorescence in liquid (LF). The effect of pH on the luminescence intensity is discussed. Lifetime and polarization of the LTP and RTP have been examined with phosphorescence lifetime in the range of 0.6-0.9s and polarization in the range of 0.10-0.27. Analytical characteristics of LF, PS-RTF and PS-RTP of CTan, Tan IIA, and Tan I have been studied.     

Determination of trace mercury by solid substrate-room temperature phosphorimetry based on catalytic effect of Hg(2+) on formation of the ion association complex [Fe(bipy)(3)](2+)[(FinBr(4))(2)](2-)

A new solid substrate-room temperature phosphorimetry method for the determination of trace mercury has been established. It bases on the fact that in acetic acid medium, Hg²⁺ ion can catalyze the substitute reaction of CN⁻ ligand in [Fe(CN)₆]⁴⁻ by 2,2′-bipyridyl (bipy), and the resultant [Fe(bipy)₃]²⁺ cation can react with FinBr₄⁻ anion of tetrabromofluorescein (HFinBr₄) to form ion association complex [Fe(bipy)₃]²⁺[(FinBr₄)₂]²⁻ which can emit phosphorescent signal on filter paper substrate. Under the optimum condition, the linear dynamic range of this method is 1.6-16 fg per spot with a detection limit (LD) of 0.18 fg per spot (0.4 μl sample solution per spot), and the regression equation of working curve is ΔI_p=1.058+7.671 C_Hg²⁺ (fg per spot ), n=7, correlation coefficient is 0.9990. This method has been applied to the determination of trace mercury in hair and cigarette samples with satisfactory result. The reaction mechanism for formation of the ion association complex is also discussed.     

Determination of human IgG by solid substrate room temperature phosphorescence immunoassay based on an antibody labeled with nanoparticles containing Rhodamine 6G luminescent molecules

Luminescent silicon dioxide nanoparticles (R-SiO2) with size of 50 nm containing Rhodamine 6G (R) were synthesized by sol-gel method. In the presence of Pb(Ac)2 as a heavy atom perturber, the particle can emit intense and stable room temperature phosphorescence signal of R, respectively, on polyamide membrane, with the lambda(ex)(max)/lambda(em)(max) = 470/635 nm for R. Our research indicates that the specific immune reaction between goat-anti-human IgG antibody labeled with R-SiO2 and human IgG can be carried on polyamide membrane quantitatively, and the phosphorescence intensity was enhanced after the immunoreactions. Thus, a new method of solid substrate room temperature phosphorescence immunoassay (SS-RTP-IA) for the determination of human IgG was established basing on antibody labeled with the nanoparticles containing binary luminescent molecules. The linear range of this method is 0.0624-20.0 pg spot(-1) of human IgG (corresponding concentration, 0.156-50.0 ng mL(-1); sample volume, 0.40 microL spot(-1)). The regression equations of working curves are delta I(p) = 88.16. + 16.79 m(IgG) (pg spot(-1)) (485/646 nm, r = 0.9997). Detection limits calculated by 3Sb/k are 0.017 pg spot(-1). For samples containing 0.156 and 50.0 ng mL(-1) of IgG, we measured repeatedly for 11 times, RSDs are 3.9 and 2.8%, respectively. This method is sensitive, accurate and of high precision.     

Catalytic solid substrate-room temperature phosphorimetry for the determination of trace As(V) based on oxidising reaction between hydrogen peroxide and fullerenol using tween-80 as sensitizer

A new catalytic solid substrate-room temperature phosphorimetry (SS-RTP) for the determination of trace arsenic(V) has been established. It is based on the fact that fullerenol (F-ol) emitted strong and stable room temperature phosphorescence (RTP) on nitric acid cellulose membrane (NCM) substrate. H₂O₂ could oxidise F-ol to cause the quenching of RTP. As(V) could catalyse H₂O₂ to oxidise F-ol and decrease the RTP signal of F-ol sharply. After adding tween-80 in the system, its ΔI _p enhanced 7.7 times compared with the without-tween-80 levels. Under the optimum conditions, the linear dynamic range of this method was 0.016?11.2 ag spot^?1 with a detection limit (LD) of 9.3 zg spot^?1 (corresponding concentration: 2.3 × 10^?17 g mL^?1). This sensitive, simple and selective method has been successfully applied to the determination of trace As(V) in human hair and tea samples. The reaction mechanism for SS-RTP is also discussed.     

导数-固体基质室温燐光法同时测定痕量对位三联苯和间位三联苯

本文提出间三联苯和对三联苯的二阶导数-固体基质室温燐光法(d²SS-RTP)。本法在λ_ax=288nm,用448nm处正峰和460nm处负峰的峰峰高度值定量测定间三联苯,对三联苯不干扰测定.线性范围0.46～46ng.检出限为0.1ng/斑点.对三联苯用526nm处正峰和548nm处负峰的峰峰高度值测定.间三联苯不干扰.线性范围0.46～46ng.检出限0.07ng/斑点.