Nanosemiconductor-Based Photocatalytic Vapor Generation Systems for Subsequent Selenium Determination and Speciation with Atomic Fluorescence Spectrometry and Inductively Coupled Plasma Mass Spectrometry

We reported novel Ag-TiO2- and ZrO2-based photocatalytic vapor generation (PCVG) systems as effective sample introduction techniques for further improving the sensitivity of the atomic spectrometric determination of selenium for the first time, in which the conduction band electron served as a "reductant" to reduce selenium species including Se-VI and convert them directly into volatile H2Se, which was easily separated from the sample matrix and underwent more effectively subsequent atomization and/or ionization. These two PCVG systems helped us to overcome the problem encountered in the most conventional KBH4/OH--H+ system, in that Se-VI was hardly converted into volatile selenium species without the aid of prereduction procedures. The limits of detection (LODs) (3 sigma) of the four most typical Se-IV, Se-VI, selenocystine ((SeCys)(2)), and selenomethionine (SeMet) species were, respectively, down to 1.2, 1.8, 7.4, and 0.9 ng mL(-1) in UV/Ag-TiO2-HCOOH, and 0.7, 1.0, 4.2, and 0.5 ng mL(-1) in UV/ZrO2-HCOOH with the relative standard deviations (RSDs) lower than 5.1% (n = 9 at 1 mu g mL(-1)) when using atomic fluorescence spectrometry (AFS) under flow injection mode. They reached 10, 14, 18, and 8 pg mL(-1) in UV/Ag-TiO2-HCOOH, and 6, 7, 10, and 5 pg mL(-1) in UV/ZrO2-HCOOH with the RSDs lower than 4.4% (n = 9 at 10 ng mL(-1)) when using inductively coupled plasma mass spectrometry (ICPMS). After the two PCVG systems were validated using certified reference materials GBW(E)080395 and SELM-1, they were applied to determine the total Se in the selenium-enriched yeast sample and used as interfaces between high-performance liquid chromatography (HPLC) and AFS or ICPMS for selenium speciation in the water- and/or enzyme-extractable fractions of the selenium-enriched yeast.National Natural Science Foundation of China [21035006]; National Basic Research 973 Program [2009CB421605

Nanosemiconductor-Based Photocatalytic Vapor Generation Systems for Subsequent Selenium Determination and Speciation with Atomic Fluorescence Spectrometry and Inductively Coupled Plasma Mass Spectrometry

We reported novel Ag–TiO₂- and ZrO₂-based photocatalytic vapor generation (PCVG) systems as effective sample introduction techniques for further improving the sensitivity of the atomic spectrometric determination of selenium for the first time, in which the conduction band electron served as a “reductant” to reduce selenium species including Se^VI and convert them directly into volatile H₂Se, which was easily separated from the sample matrix and underwent more effectively subsequent atomization and/or ionization. These two PCVG systems helped us to overcome the problem encountered in the most conventional KBH₄/OH^––H⁺ system, in that Se^VI was hardly converted into volatile selenium species without the aid of prereduction procedures. The limits of detection (LODs) (3σ) of the four most typical Se^IV, Se^VI, selenocystine ((SeCys)₂), and selenomethionine (SeMet) species were, respectively, down to 1.2, 1.8, 7.4, and 0.9 ng mL^–1 in UV/Ag–TiO₂–HCOOH, and 0.7, 1.0, 4.2, and 0.5 ng mL^–1 in UV/ZrO₂–HCOOH with the relative standard deviations (RSDs) lower than 5.1% (<i>n</i> = 9 at 1 μg mL^–1) when using atomic fluorescence spectrometry (AFS) under flow injection mode. They reached 10, 14, 18, and 8 pg mL^–1 in UV/Ag–TiO₂–HCOOH, and 6, 7, 10, and 5 pg mL^–1 in UV/ZrO₂–HCOOH with the RSDs lower than 4.4% (<i>n</i> = 9 at 10 ng mL^–1) when using inductively coupled plasma mass spectrometry (ICPMS). After the two PCVG systems were validated using certified reference materials GBW­(E)­080395 and SELM-1, they were applied to determine the total Se in the selenium-enriched yeast sample and used as interfaces between high-performance liquid chromatography (HPLC) and AFS or ICPMS for selenium speciation in the water- and/or enzyme-extractable fractions of the selenium-enriched yeast

Europium-Labeled Activity-Based Probe through Click Chemistry: Absolute Serine Protease Quantification Using 153Eu Isotope Dilution ICP/MS

National Natural Science Foundation of China [21035006]; National Basic Research 973 Program [2009CB421605]The titled probe was synthesized by conjugating a sulfonyl fluoride and azido unit using click chemistry to give SF-Eu, which can react specifically with serine (Ser) in the active site of serine protease (SP). Combination of the method with 153Eu-isotope dilution ICP/MS enables absolute protein quantification of active SPs in biological samples using only one 153Eu(NO3)3 isotopic standard

Nanosemiconductor-based photocatalytic vapor generation systems for subsequent selenium determination and speciation with atomic fluorescence spectrometry and inductively coupled plasma mass spectrometry

We reported novel Ag-TiO2- and ZrO2-based photocatalytic vapor generation (PCVG) systems as effective sample introduction techniques for further improving the sensitivity of the atomic spectrometric determination of selenium for the first time, in which the conduction band electron served as a 'reductant' to reduce selenium species including SeVI and convert them directly into volatile H2Se, which was easily separated from the sample matrix and underwent more effectively subsequent atomization and/or ionization. These two PCVG systems helped us to overcome the problem encountered in the most conventional KBH 4/OH--H+ system, in that SeVI was hardly converted into volatile selenium species without the aid of prereduction procedures. The limits of detection (LODs) (3蟽) of the four most typical SeIV, SeVI, selenocystine ((SeCys)2), and selenomethionine (SeMet) species were, respectively, down to 1.2, 1.8, 7.4, and 0.9 ng mL-1 in UV/Ag-TiO2-HCOOH, and 0.7, 1.0, 4.2, and 0.5 ng mL-1 in UV/ZrO2-HCOOH with the relative standard deviations (RSDs) lower than 5.1% (n = 9 at 1 渭g mL-1) when using atomic fluorescence spectrometry (AFS) under flow injection mode. They reached 10, 14, 18, and 8 pg mL-1 in UV/Ag-TiO2-HCOOH, and 6, 7, 10, and 5 pg mL-1 in UV/ZrO2-HCOOH with the RSDs lower than 4.4% (n = 9 at 10 ng mL-1) when using inductively coupled plasma mass spectrometry (ICPMS). After the two PCVG systems were validated using certified reference materials GBW(E)080395 and SELM-1, they were applied to determine the total Se in the selenium-enriched yeast sample and used as interfaces between high-performance liquid chromatography (HPLC) and AFS or ICPMS for selenium speciation in the water- and/or enzyme-extractable fractions of the selenium-enriched yeast. 漏 2012 American Chemical Society

Integrin-Targeted Trifunctional Probe for Cancer Cells: A 'Seeing and Counting' Approach

National Natural Science Foundation of China [21035006, 21275120]; National Basic Research 973 Program [2009CB421605]We report the design and synthesis of a trifunctional probe for seeing and counting cancer cells using both fluorescence imaging (FI) and inductively coupled plasma mass spectrometry (ICPMS) for the first time. It consisted of a guiding cyclic RGD peptide unit to catch cancer cells via targeting the alpha(v)beta(3) integrin overexpressed on their surface, a 5-amino-fluorescein moiety for FI using confocal laser scanning microscopy (CLSM) as well as a 2-aminoethyl-monoamide-DOTA group for loading stable europium ion and subsequent ICPMS quantification of the cancer cells without the use of radioactive isotopes. In addition to FI, the LOD (3 sigma) of the alpha(v)beta(3) integrin was down to 69.2-309.4 amol per cell depending on the type of the alpha(v)beta(3)-positive cancer cells when using ICPMS and those of the cancer cell number reached 17-75. This probe developed enables us not only to see but also to count the alpha(v)beta(3)-positive cancer cells ultrasensitively, paving a new way for early diagnosis of cancer

Integrin-Targeted Trifunctional Probe for Cancer Cells: A “Seeing and Counting” Approach

We report the design and synthesis of a trifunctional probe for seeing and counting cancer cells using both fluorescence imaging (FI) and inductively coupled plasma mass spectrometry (ICPMS) for the first time. It consisted of a guiding cyclic RGD peptide unit to catch cancer cells via targeting the α_vβ₃ integrin overexpressed on their surface, a 5-amino-fluorescein moiety for FI using confocal laser scanning microscopy (CLSM) as well as a 2-aminoethyl-monoamide-DOTA group for loading stable europium ion and subsequent ICPMS quantification of the cancer cells without the use of radioactive isotopes. In addition to FI, the LOD (3σ) of the α_vβ₃ integrin was down to 69.2–309.4 amol per cell depending on the type of the α_vβ₃-positive cancer cells when using ICPMS and those of the cancer cell number reached 17–75. This probe developed enables us not only to see but also to count the α_vβ₃-positive cancer cells ultrasensitively, paving a new way for early diagnosis of cancer

ICP-MS-Based Multiplex and Ultrasensitive Assay of Viruses with Lanthanide-Coded Biospecific Tagging and Amplification Strategies

National Natural Science Foundation of China [21035006, 21275120]; National Basic Research 973 Project [2014CB932004]Highly sensitive and a multiplex assay of viruses and viral DNAs in complex biological samples is extremely important for clinical diagnosis and prognosis of pathogenic diseases as well as virology studies. We present an effective ICP-MS-based multiplex and ultrasensitive assay of viral DNAs with lanthanide-coded oligonucleotide hybridization and rolling circle amplification (RCA) strategies on biofunctional magnetic nanoparticles (MNPs), in which single-stranded capture DNA (ss-Cap-DNA)-functionalized MNPs (up to 1.65 X 10(4) ss-Cap-DNA per MNP) were used to recognize and enrich target DNAs, and single-stranded report DNA (ss-Rep-DNA-DOTA-Ln) coded by the lanthanide-DOTA complex hybridized with the targeted DNA for highly sensitive readout of HIV (28 amol), HAV (48 amol), and HBV (19 amol). When utilizing the RCA technique in association with the design and synthesis of a "bridge" DNA and a corresponding ss-Rep-DNA-DOTA-Ho, as low as 90 zmol HBV could be detected. Preliminary applications to the determination of the viral DNAs in 4T1 cell lysates and in serum confirmed the feasibility of this ICP-MS-based multiplex DNA assay for clinical use. One can expect that this element-coded ICP-MS-based multiplex and ultrasensitive DNA assay will play an ever more important role in the fields of bioanalysis and virology and in medical studies after further sophisticated modifications

ICP-MS-Based Multiplex and Ultrasensitive Assay of Viruses with Lanthanide-Coded Biospecific Tagging and Amplification Strategies

Highly sensitive and a multiplex assay of viruses and viral DNAs in complex biological samples is extremely important for clinical diagnosis and prognosis of pathogenic diseases as well as virology studies. We present an effective ICP-MS-based multiplex and ultrasensitive assay of viral DNAs with lanthanide-coded oligonucleotide hybridization and rolling circle amplification (RCA) strategies on biofunctional magnetic nanoparticles (MNPs), in which single-stranded capture DNA (ss-Cap-DNA)-functionalized MNPs (up to 1.65 × 10⁴ ss-Cap-DNA per MNP) were used to recognize and enrich target DNAs, and single-stranded report DNA (ss-Rep-DNA-DOTA-Ln) coded by the lanthanide–DOTA complex hybridized with the targeted DNA for highly sensitive readout of HIV (28 amol), HAV (48 amol), and HBV (19 amol). When utilizing the RCA technique in association with the design and synthesis of a “bridge” DNA and a corresponding ss-Rep-DNA-DOTA-Ho, as low as 90 zmol HBV could be detected. Preliminary applications to the determination of the viral DNAs in 4T1 cell lysates and in serum confirmed the feasibility of this ICP-MS-based multiplex DNA assay for clinical use. One can expect that this element-coded ICP-MS-based multiplex and ultrasensitive DNA assay will play an ever more important role in the fields of bioanalysis and virology and in medical studies after further sophisticated modifications

Europium-labeled activity-based probe through click chemistry: Absolute serine protease quantification using 153Eu isotope dilution ICP/MS

Click and analyze: The titled probe was synthesized by conjugating a sulfonyl fluoride and azido unit using click chemistry to give SF-Eu, which can react specifically with serine (Ser) in the active site of serine protease (SP). Combination of the method with 153Eu-isotope dilution ICP/MS enables absolute protein quantification of active SPs in biological samples using only one 153Eu(NO3)3 isotopic standard. Copyright 漏 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim