The application of ICP-MS to the fields of proteomics and genomics has arisen in part due to its ability to detect and quantify trace levels of S and P, which are major constituents in proteins and nucleic acids respectively. The development of collision/reaction cell technology and high resolution instruments has enabled these biologically important elements to be measured and quantified at the pg - ng ml-1 level. Despite these advances, the detection limits of P and S are still inferior compared to other elements. Oligonucleotides containing biotin functionality were labelled with Au nano-particles attached to a streptavidin protein to achieve site specific labelling, with 100% labelling efficiency. Each nano-particle contained ~86 Au atoms, resulting in an 882 fold signal enhancement for 24 base length oligonucleotides. However, this enhancement factor was only observed when one oligonucleotide bound to one nano-particle in a 1:1 ratio. Much lower Au labelling efficiencies and signal enhancements were observed when thiolated oligonucleotides were labelled with maleimide functionalised gold nano-particles. This was attributed to the extensive and difficult sample preparation steps that were required prior to labelling. The detection and quantification of adducts formed between DNA and the Pt anti-cancer drugs cisplatin and oxaliplatin were also investigated with ICP-MS. Acid digestion of the carbon based DNA matrix enabled Pt adducts to be quantified at low dose rates of 1 Pt atom per 1 500 000 nucleotides in ~12 μg DNA. Such sensitive mass spectrometric determinations could be employed in clinical tests to detect and quantify low level adducts formed in patients in-vivo. To complement ICP-MS analysis, electrospray ionisation linear ion trap mass spectrometry was employed to study the interaction of oxaliplatin with the four DNA nucleobases. Multiple stage mass spectrometry enabled detailed Pt-nucleobase adduct fragmentation pathways to be established. The method of DNA detection using P in conjunction with the collision cell, or cool plasma to form PO+ was also demonstrated and the limitations of the method, namely, polyatomic interferences and severe matrix effects were highlighted.

A espectrometria de massas com plasma acoplado indutivamente com simples quadrupolo (q-ICP-MS) e cela de reação dinâmica (DRC-ICP-MS) foi avaliada para determinação seqüencial de Al, As, Cd, Co, Cu, Cr, Mn, Mo, Pb, Pt, Sb, Se, Sn, Te, Tl, V e Zn em sangue. Para as análises, amostras de sangue (200 µL) foram diluídas 1:50 em uma solução contendo 0,01% v/v Triton® X-100 e 0,5% v/v de ácido nítrico. As calibrações foram realizadas com ajuste de matriz, utilizando sangue ovino. Como gás de reação utilizou-se a NH3. O uso do DRC foi fundamental para a determinação de Cr e V. A escolha da melhor vazão do gás e a otimização do parâmetro de rejeição (RPq) foram estudadas utilizando sangue base ovino ou uma solução de matriz sintética (SMS), de acordo com a concentração do analito no sangue base. Os limites de detecção (3s/coeficiente angular) para determinação de 27Al, 75As, 111Cd, 59Co, 63Cu, 55Mn, 98Mo, 208Pb, 195Pt, 123Sb, 82Se, 120Sn, 130Te, 205Tl e 66Zn em sangue por q-ICP-MS foram 0,223; 0,014; 0,003; 0,011; 0,304; 0,009; 0,009; 0,003; 0,001; 0,005; 0,264; 0,006; 0,010; 0,001; 0,834 µg L-1, respectivamente, e para determinação de 52Cr e 51V em sangue por DRC-ICP-MS utilizando o gás de reação amônia os limites de detecção foram de 0,007 e 0,006 µg L-1. Para a determinação de 27Al, 63Cu, 65Cu, 64Zn e 66Zn em sangue por q-ICP-MS através da calibração com ajuste de matriz com SMS os limites de detecção foram 0,083; 0,090; 0,055; 0,281; 0,306 µg L-1, respectivamente. A validação do método foi realizada por meio da análise de materiais de referência do INSP-Canadá, NYSDOH-EUA e Seronorm-Noruega. / The use of inductively coupled plasma mass spectrometry with quadrupole (q-ICP-MS) and dynamic reaction cell (DRC-ICP-MS) was evaluated for sequential determination of Al, As, Cd, Co, Cu, Cr, Mn, Mo, Pb, Pt, Sb, Se, Sn, Te, Tl, V and Zn in whole blood by q-ICP-MS or DRC-ICP-MS methods. Prior to analysis, sample (200 µL) were diluted 1:50 v/v in a solution containing 0.01% v/v Triton® X-100 and 0.5% v/v nitric acid. For all elements, except Cr and V, the instrument was operated in q-ICP-MS mode. The use of DRC was only mandatory for Cr and V. NH3 was evaluated as the reaction gas. Selection of best flow rate of reaction gas and optimization of the quadrupole dynamic bandpass rejection parameter (RPq) were carried out, using base whole blood or synthetic matrix solution (SMS), in according with element base blood concentration. Method detection limits (3s/slope) for 27Al, 75As, 111Cd, 59Co, 63Cu, 55Mn, 98Mo, 208Pb, 195Pt, 123Sb, 82Se, 120Sn, 130Te, 205Tl and 66Zn determination in whole blood by q-ICP-MS against matrix matching calibration (base blood) were 0.223; 0.014; 0.003; 0.011; 0.304; 0.009; 0.009; 0.003; 0.001; 0.005; 0.264; 0.006; 0.010; 0.001; 0.834 µg L-1, respectively, and for 52Cr and 51V determination in whole blood by DRC-ICP-MS the detection limits were 0.007 e 0.006 µg L-1. For 27Al, 63Cu, 65Cu, 64Zn and 66Zn determination by q-ICP-MS through matrix matching calibration with SMS the detection limits were 0.083; 0.090; 0.055; 0.281; 0.306 µg L-1, respectively. Method validation was accomplished by the analysis of reference materials from INSP-Canada, NYSDOH-USA, Seronorm-Norway.

A espectrometria de massas com plasma acoplado indutivamente com simples quadrupolo (q-ICP-MS) e cela de reação dinâmica (DRC-ICP-MS) foi avaliada para determinação seqüencial de Al, As, Cd, Co, Cu, Cr, Mn, Mo, Pb, Pt, Sb, Se, Sn, Te, Tl, V e Zn em sangue. Para as análises, amostras de sangue (200 µL) foram diluídas 1:50 em uma solução contendo 0,01% v/v Triton® X-100 e 0,5% v/v de ácido nítrico. As calibrações foram realizadas com ajuste de matriz, utilizando sangue ovino. Como gás de reação utilizou-se a NH3. O uso do DRC foi fundamental para a determinação de Cr e V. A escolha da melhor vazão do gás e a otimização do parâmetro de rejeição (RPq) foram estudadas utilizando sangue base ovino ou uma solução de matriz sintética (SMS), de acordo com a concentração do analito no sangue base. Os limites de detecção (3s/coeficiente angular) para determinação de 27Al, 75As, 111Cd, 59Co, 63Cu, 55Mn, 98Mo, 208Pb, 195Pt, 123Sb, 82Se, 120Sn, 130Te, 205Tl e 66Zn em sangue por q-ICP-MS foram 0,223; 0,014; 0,003; 0,011; 0,304; 0,009; 0,009; 0,003; 0,001; 0,005; 0,264; 0,006; 0,010; 0,001; 0,834 µg L-1, respectivamente, e para determinação de 52Cr e 51V em sangue por DRC-ICP-MS utilizando o gás de reação amônia os limites de detecção foram de 0,007 e 0,006 µg L-1. Para a determinação de 27Al, 63Cu, 65Cu, 64Zn e 66Zn em sangue por q-ICP-MS através da calibração com ajuste de matriz com SMS os limites de detecção foram 0,083; 0,090; 0,055; 0,281; 0,306 µg L-1, respectivamente. A validação do método foi realizada por meio da análise de materiais de referência do INSP-Canadá, NYSDOH-EUA e Seronorm-Noruega. / The use of inductively coupled plasma mass spectrometry with quadrupole (q-ICP-MS) and dynamic reaction cell (DRC-ICP-MS) was evaluated for sequential determination of Al, As, Cd, Co, Cu, Cr, Mn, Mo, Pb, Pt, Sb, Se, Sn, Te, Tl, V and Zn in whole blood by q-ICP-MS or DRC-ICP-MS methods. Prior to analysis, sample (200 µL) were diluted 1:50 v/v in a solution containing 0.01% v/v Triton® X-100 and 0.5% v/v nitric acid. For all elements, except Cr and V, the instrument was operated in q-ICP-MS mode. The use of DRC was only mandatory for Cr and V. NH3 was evaluated as the reaction gas. Selection of best flow rate of reaction gas and optimization of the quadrupole dynamic bandpass rejection parameter (RPq) were carried out, using base whole blood or synthetic matrix solution (SMS), in according with element base blood concentration. Method detection limits (3s/slope) for 27Al, 75As, 111Cd, 59Co, 63Cu, 55Mn, 98Mo, 208Pb, 195Pt, 123Sb, 82Se, 120Sn, 130Te, 205Tl and 66Zn determination in whole blood by q-ICP-MS against matrix matching calibration (base blood) were 0.223; 0.014; 0.003; 0.011; 0.304; 0.009; 0.009; 0.003; 0.001; 0.005; 0.264; 0.006; 0.010; 0.001; 0.834 µg L-1, respectively, and for 52Cr and 51V determination in whole blood by DRC-ICP-MS the detection limits were 0.007 e 0.006 µg L-1. For 27Al, 63Cu, 65Cu, 64Zn and 66Zn determination by q-ICP-MS through matrix matching calibration with SMS the detection limits were 0.083; 0.090; 0.055; 0.281; 0.306 µg L-1, respectively. Method validation was accomplished by the analysis of reference materials from INSP-Canada, NYSDOH-USA, Seronorm-Norway.

Développement de méthodes analytiques pour l’évaluation de l'impact de l'industrie de fertilisants chimiques sur le milieu marin / Development of Analytical methods for the evaluation of the impact of phosphate fertilizer industry on marine environment