Unbiased Scanning Method and Data Banking Approach Using Ultra-High Performance Liquid Chromatography Coupled with High-Resolution Mass Spectrometry for Quantitative Comparison of Metabolite Exposure in Plasma across Species Analyzed at Different Dates

An unbiased scanning methodology using ultra high-performance liquid chromatography coupled with high-resolution mass spectrometry was used to bank data and plasma samples for comparing the data generated at different dates. This method was applied to bank the data generated earlier in animal samples and then to compare the exposure to metabolites in animal versus human for safety assessment. With neither authentic standards nor prior knowledge of the identities and structures of metabolites, full scans for precursor ions and all ion fragments (AIF) were employed with a generic gradient LC method to analyze plasma samples at positive and negative polarity, respectively. In a total of 22 tested drugs and metabolites, 21 analytes were detected using this unbiased scanning method except that naproxen was not detected due to low sensitivity at negative polarity and interference at positive polarity; and 4′- or 5-hydroxy diclofenac was not separated by a generic UPLC method. Statistical analysis of the peak area ratios of the analytes versus the internal standard in five repetitive analyses over approximately 1 year demonstrated that the analysis variation was significantly different from sample instability. The confidence limits for comparing the exposure using peak area ratio of metabolites in animal plasma versus human plasma measured over approximately 1 year apart were comparable to the analysis undertaken side by side on the same days. These statistical analysis results showed it was feasible to compare data generated at different dates with neither authentic standards nor prior knowledge of the analytes

Evaluation of the plasticity of soybean (Glycine max (L.) Merrill) under effect of variability of space arrangements.

O presente experimento teve por objetivos, avaliar a maneira como a planta de soja se adapta a diferentes arranjos espaciais (plasticidade) e identificar o arranjo espacial que melhor represente ou possibilite associar o manejo do cultivar MG/BR 46 (Conquista) com alta produtividade agrícola. O experimento foi conduzido em área experimental da Escola Superior de Agricultura "Luiz de Queiroz" (ESALQ/USP), no município de Piracicaba - SP, durante o ano agrícola de 2001/2002. Os tratamentos constaram de diferentes arranjos espaciais, variando-se e combinando-se 6 níveis do fator espaçamento entre linhas (0,20; 0,30; 0,40; 0,50; 0,60 e 0,70 m) e 5 níveis do fator densidade de plantas na linha visando as populações de 70.000; 140.000; 210.000; 280.000 e 350.000 plantas/ha, totalizando 30 tratamentos, delineados em blocos ao acaso com parcelas subdivididas e com três repetições. As características avaliadas foram: tempo de fechamento de entrelinhas; índice de área foliar; altura final de planta; altura de inserção da primeira vagem; número de ramificações; número de vagens por planta; número de grãos por planta; grau de acamamento; massa de 1000 sementes e produtividade agrícola. As principais conclusões são: a) o cultivar MG/BR 46 (Conquista), cultivado em linhas espaçadas entre si de 0,20 a 0,60 m, apresenta índice de área foliar máximo no estádio fenológico correspondente ao início da granação das vagens (R5); b) o número de vagens é o mais importante componente da produção por planta, por ser diretamente influenciado pelo arranjo populacional das plantas na área de produção; c) o cultivar MG/BR 46 (Conquista) apresenta ampla plasticidade, ajustando os seus componentes de produção aos diferentes arranjos espaciais, sem que ocorram significativas diferenças de produtividade; d) para cada combinação entre o espaçamento entre linhas e a densidade de plantas na linha existe uma população de plantas mais bem ajustada, que possibilita maior produtividade de grãos.This research had as purposes to evaluate the soybean plant adaptations (plasticity) to different space arrangements and identify the best space arrangements for higher yields of cultivar MG/BR 46 (Conquista). The experiment was carried out at the experimental fields of Escola Superior de Agricultura "Luiz de Queiroz" (USP/ESALQ), São Paulo State University, in Piracicaba-SP, during the 2001/2002 growing season. The 30 treatments consisted of different space arrangements, combining 6 row spacing (0,20; 0,30; 0,40; 0,50; 0,60; 0,70 m) with 5 different population (70.000; 140.000; 210.000; 280.000; 350.000 plants/ha), in a complete randomized blocks design with subdivided plots and three replications. The evaluated characteristics were: time to achieve closed canopy; leaf area index; final plant height; height of the first pod; number of branches per plant; number of pods per plant; number of grains per plant; lodging; mass of 1,000 grains and yield. The main conclusions are: a) the cultivar MG/BR - 46 (Conquista) cultivated under 0,20 to 0,60 m row spacing shows a leaf area index maximum at the begging of seed-filling stage (R5); b) the number of pods is the best related component to yield per plant, being directly influenced by plant population; c) the cultivar MG/BR - 46 (Conquista) presents wide plasticity, adjusting its yield components to the different space arrangements, without significant yield changes; d) for each row spacing there is a better plant population to achieve higher yield

Substrate-Mediated C–C and C–H Coupling after Dehalogenation

Intermolecular C–C coupling after cleavage of C–X (mostly, X = Br or I) bonds has been extensively studied for facilitating the synthesis of polymeric nanostructures. However, the accidental appearance of C–H coupling at the terminal carbon atoms would limit the successive extension of covalent polymers. To our knowledge, the selective C–H coupling after dehalogenation has not so far been reported, which may illuminate another interesting field of chemical synthesis on surfaces besides <i>in situ</i> fabrication of polymers, i.e., synthesis of novel organic molecules. By combining STM imaging, XPS analysis, and DFT calculations, we have achieved predominant C–C coupling on Au(111) and more interestingly selective C–H coupling on Ag(111), which in turn leads to selective synthesis of polymeric chains or new organic molecules

Toward Tunable Electroluminescent Devices by Correlating Function and Submolecular Structure in 3D Crystals, 2D-Confined Monolayers, and Dimers

The synthesis of new Pt­(II) complexes bearing tailored cyclometalated C^N*N^C luminophores is reported along with their photophysical properties. The emission of the monomeric species can be blue shifted upon formal isosteric replacement of two C–H units by N atoms at the two cyclometalating rings. Their remarkable stability upon sublimation was demonstrated by means of scanning tunneling microscopy, which also revealed a defined self-assembly behavior leading to supramolecular arrays, showing a 3-fold symmetry in 2D-confined monolayers. The supramolecular organization is driven by van der Waals interactions of the side chains and does not depend on the nature of the luminophores, as also observed in the crystalline phases showing no significant Pt–Pt interactions in 3D. Conversely, the luminescence properties in glassy matrices at 77 K and in amorphous solids are indicative of intermolecular interactions with sizable intermetallic coupling, which was demonstrated by reproducing the emission spectra of dimeric species by means of (TD)­DFT calculations. The tendency toward aggregation was also traceable by cyclic voltammetry, whereas thermogravimetric analyses confirmed their stability. Solution-processed and vacuum-deposited OLED devices showed a concentration-dependent electroluminescence that red shifts with increasing doping ratios. Due to the stability of the complexes, solution-processed and vacuum-deposited devices showed identical electroluminescence spectra. Besides favoring aggregation, introduction of two N atoms has a detrimental effect on the device performance, due to the prolonged excited-state lifetimes favoring triplet–triplet annihilation

Toward Tunable Electroluminescent Devices by Correlating Function and Submolecular Structure in 3D Crystals, 2D-Confined Monolayers, and Dimers

The synthesis of new Pt­(II) complexes bearing tailored cyclometalated C^N*N^C luminophores is reported along with their photophysical properties. The emission of the monomeric species can be blue shifted upon formal isosteric replacement of two C–H units by N atoms at the two cyclometalating rings. Their remarkable stability upon sublimation was demonstrated by means of scanning tunneling microscopy, which also revealed a defined self-assembly behavior leading to supramolecular arrays, showing a 3-fold symmetry in 2D-confined monolayers. The supramolecular organization is driven by van der Waals interactions of the side chains and does not depend on the nature of the luminophores, as also observed in the crystalline phases showing no significant Pt–Pt interactions in 3D. Conversely, the luminescence properties in glassy matrices at 77 K and in amorphous solids are indicative of intermolecular interactions with sizable intermetallic coupling, which was demonstrated by reproducing the emission spectra of dimeric species by means of (TD)­DFT calculations. The tendency toward aggregation was also traceable by cyclic voltammetry, whereas thermogravimetric analyses confirmed their stability. Solution-processed and vacuum-deposited OLED devices showed a concentration-dependent electroluminescence that red shifts with increasing doping ratios. Due to the stability of the complexes, solution-processed and vacuum-deposited devices showed identical electroluminescence spectra. Besides favoring aggregation, introduction of two N atoms has a detrimental effect on the device performance, due to the prolonged excited-state lifetimes favoring triplet–triplet annihilation

Toward Tunable Electroluminescent Devices by Correlating Function and Submolecular Structure in 3D Crystals, 2D-Confined Monolayers, and Dimers

The synthesis of new Pt­(II) complexes bearing tailored cyclometalated C^N*N^C luminophores is reported along with their photophysical properties. The emission of the monomeric species can be blue shifted upon formal isosteric replacement of two C–H units by N atoms at the two cyclometalating rings. Their remarkable stability upon sublimation was demonstrated by means of scanning tunneling microscopy, which also revealed a defined self-assembly behavior leading to supramolecular arrays, showing a 3-fold symmetry in 2D-confined monolayers. The supramolecular organization is driven by van der Waals interactions of the side chains and does not depend on the nature of the luminophores, as also observed in the crystalline phases showing no significant Pt–Pt interactions in 3D. Conversely, the luminescence properties in glassy matrices at 77 K and in amorphous solids are indicative of intermolecular interactions with sizable intermetallic coupling, which was demonstrated by reproducing the emission spectra of dimeric species by means of (TD)­DFT calculations. The tendency toward aggregation was also traceable by cyclic voltammetry, whereas thermogravimetric analyses confirmed their stability. Solution-processed and vacuum-deposited OLED devices showed a concentration-dependent electroluminescence that red shifts with increasing doping ratios. Due to the stability of the complexes, solution-processed and vacuum-deposited devices showed identical electroluminescence spectra. Besides favoring aggregation, introduction of two N atoms has a detrimental effect on the device performance, due to the prolonged excited-state lifetimes favoring triplet–triplet annihilation