Applications of tritium and oxygen-17 labelled molecules for the study of molecular interactions

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Chemical Exchange in Novel SpiroBicyclic Zwitterionic Janovsky Complexes using Dynamic 1H NMR Spectroscopy

Highly coloured Janovsky complexes have been known for over 120 years, being used in many colourimetric analytical procedures. In this present study, two novel and stable nitrocyclohexadienyl spirobicyclic, zwitterionic Janovsky anionic hydantoin \u3c3-complexes, rac-1,3-diisopropyl-6-nitro-2,4-dioxo-1,3-diazaspiro[4.5]deca-6,9-dien-8-ylideneazinate, ammonium internal salt (1) and 1,3-diisopropyl-2,4-dioxo-1,3-diazaspiro[4.5]deca-6,9-dien-8-ylideneazinate, ammonium internal salt (2) have been prepared and characterised by NMR, electrospray ionization mass spectrometry (ESI-MS) and UV/visible methods. For the p-mononitro-substituted complex (2), we discovered chemical exchange behaviour using 1D saturation transfer and 2D exchange spectroscopy (EXSY) 1H NMR techniques. The coalescence temperature was determined to be 62 \u25e6C ind3-acetonitrile. Analysis of these data provided a Gibbs free energy of activation, 06G\u2021, of +67 kJ mole 121, a rate constant, k, coalescence of 220 Hz and an equilibrium constant, Keqm, of 0.98 as estimates of the exchange process in this solvent. Of the two mechanisms proposedfor this fluxional behaviour, ringopeningto a substituted benzene or proton exchange, a further theoretical modelling study of 1D 1H NMR spectra was able to confirm that simple proton exchange between the two nitrogen sites of the hydantoin ring provided an accurate simulation of the observed experimental evidence. Interestingly, the o,p-dinitro-substituted complex (1) did not show any chemical exchange behaviour up to 150 \u25e6C in d3-acetonitrile (to 75 \u25e6C) and d6-dimethyl sulfoxide (DMSO). Molecular modelling at the MM2 level suggests that steric collisions of anN-acyl isopropyl substituent of the hydantoin ringwith the ortho-nitro group of the spirofused cyclohexadienyl ring prevents the proposed proton exchange mechanism occurring in this case.Peer reviewed: YesNRC publication: Ye

Fast Deprotection of Synthetic Oligodeoxyribonucleotides Using Standard Reagents under Microwave Irradiation

Fast methods for the removal of permanent amide exo-cyclic protective groups widely used in phosphoramidite- method DNA synthesis are desirable for many genomics and proteomics applications. In this communication, we present a method for the deprotection of a range of N-acyl deoxyribonucleosides (T, dABz, dCBz, dCAc, dGibu, dGPAC) and synthetic oligodeoxyribonucleotides, ranging in length from 5-mer to 50-mer. Oligodeoxyribonucleotides were synthesized using standard amide protecting groups (dABz, dCBz, dGibu) and phosphoramidite chemistry on cis-diol solid phase support. This deprotection method utilizes 29% aqueous ammonia solution at 170\ub0C for 5 minutes under monomode microwave irradiation at a 20-nmole reaction scale. Reaction products were analyzed by TLC, RP-HPLC, CE, ESI-MS, real-time PCR, agarose gel electrophoresis, and by DNA uracil glycosylase (UDG) and phosphodiesterase I (PDE) enzymatic digestions.Peer reviewed: YesNRC publication: Ye

Macro-nutrientes no lençol freático em Floresta Intacta, Floresta de Manejo e Pastagem no norte de Mato Grosso Macro-nutrients in the water sheet in Mature Forest, Management Forest and Pasture in the north of Mato Grosso

A remoção de uma cobertura florestal e sua substituição por outras formas de uso do solo tem sido uma constante no norte do estado de Mato Grosso podendo alterar os ciclos hidrológicos e biogeoquímicos dos ecossistemas. Neste contexto, o presente trabalho visou identificar a variação do fósforo e nitrogênio das águas do lençol freático em áreas de Floresta de Transição madura e intacta (Floresta Intacta), Floresta de Transição Manejada (Floresta Manejada) e Pastagem localizadas no norte de Mato Grosso. Foram realizadas mensalmente medidas do nível do lençol freático, de coletas de amostras de água para análises físico-químicas e medições de precipitação e temperatura do ar, no período de janeiro/2005 a novembro/2006. Verificou-se uma sazonalidade na precipitação e na temperatura do ar. No período de estiagem as águas do lençol freático apresentaram maiores teores de nitrogênio e de fósforo total nas três áreas em estudo. Os maiores valores de nitrogênio e fósforo foram detectados nos ecossistemas florestais (Florestas Intacta e Manejada) como indicativo da função da cobertura vegetal na ciclagem dos nutrientes.<br>Forest removal for other land uses has been a constant in the north of Mato Grosso and can alter the hydrological and biochemical cycles. In this context, the present work aims to identify the variation of phosphorus and nitrogen in the water sheet in areas of Mature Forest, Management Forest and Pasture in the north of Mato Grosso. The water level was measured monthly and water samples for analysis were collected monthly from January/2005 to November/2006. We verified the precipitation and the air temperature seasonality, and in the dry season the quality of the water sheet presented greater values of total phosphorus and total Kjeldhal nitrogen in the studied areas. The phosphorus and nitrogen presented greater values in forest ecosystems (Forest and Management Forest) as indicative of the function of the vegetal covering in the nutrient cycle