Deprotonative metalation of substituted aromatics using mixed lithium-cobalt combinations

International audienceThe deprotonation of anisole was attempted using different homo- and heteroleptic TMP/Bu mixed lithium-cobalt combinations. Using iodine to intercept the metalated anisole, an optimization of the reaction conditions showed that in THF at room temperature 2 equiv of base were required to suppress the formation of the corresponding 2,2'-dimer. The origin of the dimer was not identified, but its formation was favored with allyl bromide as electrophile. The metalated anisole was efficiently trapped using iodine, anisaldehyde, and chlorodiphenylphosphine, and moderately employing benzophenone, and benzoyl chloride. 1,2-, 1,3- and 1,4-dimethoxybenzene were similarly converted regioselectively to the corresponding iodides. It was observed that 2-methoxy- and 2,6-dimethoxypyridine were more prone to dimerization than the corresponding benzenes when treated similarly. Involving ethyl benzoate in the metalation-iodination sequence showed the method was not suitable to functionalize substrates bearing reactive functions

Judgment Aggregation with Abstentions under Voters' Hierarchy

International audienceSimilar to Arrow’s impossibility theorem for preference aggregation, judgment aggregation has also an intrinsic impossibility for generating consistent group judgment from individual judgments. Removing some of the pre-assumed conditions would mitigate the problem but may still lead to too restrictive solutions. It was proved that if completeness is removed but other plausible conditions are kept, the only possible aggregation functions are oligarchic, which means that the group judgment is purely determined by a certain subset of participating judges. Instead of further challenging the other conditions, this paper investigates how the judgment from each individual judge affects the group judgment in an oligarchic environment. We explore a set of intuitively demanded conditions under abstentions and design a feasible judgment aggregation rule based on the agents’ hierarchy. We show this proposed aggregation rule satisfies the desirable conditions. More importantly, this rule is oligarchic with respect to a subset of agenda instead of the whole agenda due to its literal-based characteristics

Efficient two-step access to azafluorenones and related compounds

International audienceCrystals of a lithiocuprate prepared from copper(I) chloride and lithium 2,2,6,6-tetramethylpiperidide (2 equiv) were isolated and analyzed by X-ray diffraction as (TMP)2Cu(Cl)Li2*THF. The observation of this species is consistent with its having a role in deprotocupration-aroylation. Phenyl pyridyl ketones, phenyl quinolyl ketones, and phenyl thienyl ketones were prepared in tetrahydrofuran using the lithiocuprate and aroyl chorides as electrophiles. Diaryl ketones bearing a chloro group at the 2 position (of a pyridyl or phenyl group) thus synthesized were next converted through palladium-catalyzed ring closure to polycycles of the 5H-indeno[1,2-b]pyridin-5-one, 11H-indeno[1,2-b]quinolin-11-one, 9H-indeno[2,1-c]pyridin-9-one, and 8H-indeno[2,1-b]thiophen-8-one families

Comparative study of MRI biomarkers in the substantia nigra to discriminate idiopathic Parkinson disease

BACKGROUND AND PURPOSE: Several new MR imaging techniques have shown promising results in patients with Parkinson disease; however, the comparative diagnostic values of these measures at the individual level remain unclear. Our aim was to compare the diagnostic value of MR imaging biomarkers of substantia nigra damage for distinguishing patients with Parkinson disease from healthy volunteers. MATERIALS AND METHODS: Thirty-six patients and 20 healthy volunteers were prospectively included. The MR imaging protocol at 3T included 3D T2-weighted and T1-weighted neuromelanin-sensitive images, diffusion tensor images, and R2* mapping. T2* high-resolution images were also acquired at 7T to evaluate the dorsal nigral hyperintensity sign. Quantitative analysis was performed using ROIs in the substantia nigra drawn manually around the area of high signal intensity on neuromelanin-sensitive images and T2-weighted images. Visual analysis of the substantia nigra neuromelanin-sensitive signal intensity and the dorsolateral nigral hyperintensity on T2* images was performed. RESULTS: There was a significant decrease in the neuromelanin-sensitive volume and signal intensity in patients with Parkinson disease. There was also a significant decrease in fractional anisotropy and an increase in mean, axial, and radial diffusivity in the neuromelanin-sensitive substantia nigra at 3T and a decrease in substantia nigra volume on T2* images. The combination of substantia nigra volume, signal intensity, and fractional anisotropy in the neuromelanin-sensitive substantia nigra allowed excellent diagnostic accuracy (0.93). Visual assessment of both substantia nigra dorsolateral hyperintensity and neuromelanin-sensitive images had good diagnostic accuracy (0.91 and 0.86, respectively). CONCLUSIONS: The combination of neuromelanin signal and volume changes with fractional anisotropy measurements in the substantia nigra showed excellent diagnostic accuracy. Moreover, the high diagnostic accuracy of visual assessment of substantia nigra changes using dorsolateral hyperintensity analysis or neuromelanin-sensitive signal changes indicates that these techniques are promising for clinical practice

SNPServer: a real-time SNP discovery tool

SNPServer is a real-time flexible tool for the discovery of SNPs (single nucleotide polymorphisms) within DNA sequence data. The program uses BLAST, to identify related sequences, and CAP3, to cluster and align these sequences. The alignments are parsed to the SNP discovery software autoSNP, a program that detects SNPs and insertion/deletion polymorphisms (indels). Alternatively, lists of related sequences or pre-assembled sequences may be entered for SNP discovery. SNPServer and autoSNP use redundancy to differentiate between candidate SNPs and sequence errors. For each candidate SNP, two measures of confidence are calculated, the redundancy of the polymorphism at a SNP locus and the co-segregation of the candidate SNP with other SNPs in the alignment. SNPServer is available at

Age and Training-Related Changes on Body Composition and Fitness in Male Amateur Cyclists

Master athletes are considered as a model of healthy aging because they can limit the age-related decline of physiological abilities compared to sedentary individuals. The main objective of this study is to analyze age-related changes and annual training on body composition (BC) and cardiorespiratory fitness (CRF) parameters. The participants in this retrospective cross-sectional study were 176 male cyclists, aged 40–60 years. BC was evaluated through anthropometric measurements and CRF was determined by an incremental cycle ergometer test to exhaustion. A comparative study between age groups was carried out through a one-way ANOVA test and the associations between the variables were assessed by Spearman’s correlation coefficients and multiple regression analysis to estimate the performance. Training was generally associated with a decrease in both body weight and body fat (p 0.05). In the performance prediction model, the included variables explained 52% of the variance. In summary, the changes induced by age were minimal in BC and negligible in CRF, whereas HR decreased with age. Training load was generally associated with a decrease in body weight, BMI and body fat percentage that was particularly notable in the abdominal skin folds. A decrease in HRrest was observed as a vagal effect due to kilometers cycled per year, and age did not seem to have a significant effect. The annual cycling kilometers were associated with to high PPO that is greater in the M40 group and a non-significant upward trend in VO2max

A pedagogic appraisal of the Priority Heuristic

We have explored how science and mathematics teachers made decisions when confronted with a dilemma in which a fictitious young woman, Deborah, may choose to have an operation that might address a painful spinal condition. We sought to explore the extent to which psychological heuristic models, in particular the Priority Heuristic, might successfully describe the decision-making process of these teachers and how an analysis of the role of personal and emotional factors in shaping the decision-making process might inform pedagogical design. A novel aspect of this study is that the setting in which the decision-making process is examined contrasts sharply with those used in psychological experiments. We found that to some extent, even in this contrasting setting, the Priority Heuristic could describe these teachers' decision-making. Further analysis of the transcripts yielded some insights into limitations on scope as well the richness and complexity in how personal factors were brought to bear. We see these limitations as design opportunities for educational intervention

Deproto-metallation using mixed lithium-zinc and lithium-copper bases and computed CH acidity of 2-substituted quinolines

International audience2-Substituted quinolines were synthesized, and their deproto-metallation using the bases prepared by mixing LiTMP with either ZnCl2*TMEDA (1/3 equiv) or CuCl (1/2 equiv) was studied. With phenyl and 2-naphthyl substituents, the reaction occurred at the 8 position of the quinoline ring, affording the corresponding iodo derivatives or 2-chlorophenyl ketones using the lithium-zinc or the lithium-copper combination, respectively. With a 4-anisyl substituent, a dideprotonation at the 8 and 3' position was noted using the lithium-zinc base. With 3-pyridyl, 2-furyl and 2-thienyl substituents, the reaction took place on the subtituent, at a position adjacent to its heteroatom. 2-Chlorophenyl 2-phenyl-8-quinolyl ketone could be cyclized under palladium catalysis. The experimental results were analyzed with the help of the CH acidities of the substrates, determined in THF solution using the DFT B3LYP method

Spatial and temporal variability of the dimethylsulfide to chlorophyll ratio in the surface ocean: an assessment based on phytoplankton group dominance determined from space

Dimethylsulfoniopropionate (DMSP) is produced in surface seawater by phytoplankton. Phytoplankton culture experiments have shown that nanoeucaryotes (NANO) display much higher mean DMSP-to-Carbon or DMSP-to-Chlorophyll (Chl) ratios than Prochlorococcus (PRO), Synechococcus (SYN) or diatoms (DIAT). Moreover, the DMSP-lyase activity of algae which cleaves DMSP into dimethylsulfide (DMS) is even more group specific than DMSP itself. Ship-based observations have shown at limited spatial scales, that sea surface DMS-to-Chl ratios (DMS:Chl) are dependent on the composition of phytoplankton groups. Here we use satellite remote sensing of Chl (from SeaWiFS) and of Phytoplankton Group Dominance (PGD from PHYSAT) with ship-based sea surface DMS concentrations (8 cruises in total) to assess this dependence on an unprecedented spatial scale. PHYSAT provides PGD (either NANO, PRO, SYN, DIAT, Phaeocystis (PHAEO) or coccolithophores (COC)) in each satellite pixel (1/4° horizontal resolution). While there are identification errors in the PHYSAT method, it is important to note that these errors are lowest for NANO PGD which we typify by high DMSP:Chl. In summer, in the Indian sector of the Southern Ocean, we find that mean DMS:Chl associated with NANO + PHAEO and PRO + SYN + DIAT are 13.6±8.4 mmol g−1 (n=34) and 7.3±4.8 mmol g−1 (n=24), respectively. That is a statistically significant difference (P<0.001) that is consistent with NANO and PHAEO being relatively high DMSP producers. However, in the western North Atlantic between 40° N and 60° N, we find no significant difference between the same PGD. This is most likely because coccolithophores account for the non-dominant part of the summer phytoplankton assemblages. Meridional distributions at 22° W in the Atlantic, and 95° W and 110° W in the Pacific, both show a marked drop in DMS:Chl near the equator, down to few mmol g−1, yet the basins exhibit different PGD (NANO in the Atlantic, PRO and SYN in the Pacific). In tropical and subtropical Atlantic and Pacific waters away from the equatorial and coastal upwelling, mean DMS:Chl associated with high and low DMSP producers are statistically significantly different, but the difference is opposite of that expected from culture experiments. Hence, in a majority of cases PGD is not of primary importance in controlling DMS:Chl variations. We therefore conclude that water-leaving radiance spectra obtained simultaneously from ocean color sensor measurements of Chl concentrations and dominant phytoplankton groups can not be used to predict global fields of DMS

Duhemian Themes in Expected Utility Theory

This monographic chapter explains how expected utility (EU) theory arose in von Neumann and Morgenstern, how it was called into question by Allais and others, and how it gave way to non-EU theories, at least among the specialized quarters of decion theory. I organize the narrative around the idea that the successive theoretical moves amounted to resolving Duhem-Quine underdetermination problems, so they can be assessed in terms of the philosophical recommendations made to overcome these problems. I actually follow Duhem's recommendation, which was essentially to rely on the passing of time to make many experiments and arguments available, and evebntually strike a balance between competing theories on the basis of this improved knowledge. Although Duhem's solution seems disappointingly vague, relying as it does on "bon sens" to bring an end to the temporal process, I do not think there is any better one in the philosophical literature, and I apply it here for what it is worth. In this perspective, EU theorists were justified in resisting the first attempts at refuting their theory, including Allais's in the 50s, but they would have lacked "bon sens" in not acknowledging their defeat in the 80s, after the long process of pros and cons had sufficiently matured. This primary Duhemian theme is actually combined with a secondary theme - normativity. I suggest that EU theory was normative at its very beginning and has remained so all along, and I express dissatisfaction with the orthodox view that it could be treated as a straightforward descriptive theory for purposes of prediction and scientific test. This view is usually accompanied with a faulty historical reconstruction, according to which EU theorists initially formulated the VNM axioms descriptively and retreated to a normative construal once they fell threatened by empirical refutation. From my historical study, things did not evolve in this way, and the theory was both proposed and rebutted on the basis of normative arguments already in the 1950s. The ensuing, major problem was to make choice experiments compatible with this inherently normative feature of theory. Compability was obtained in some experiments, but implicitly and somewhat confusingly, for instance by excluding overtly incoherent subjects or by creating strong incentives for the subjects to reflect on the questions and provide answers they would be able to defend. I also claim that Allais had an intuition of how to combine testability and normativity, unlike most later experimenters, and that it would have been more fruitful to work from his intuition than to make choice experiments of the naively empirical style that flourished after him. In sum, it can be said that the underdetermination process accompanying EUT was resolved in a Duhemian way, but this was not without major inefficiencies. To embody explicit rationality considerations into experimental schemes right from the beginning would have limited the scope of empirical research, avoided wasting resources to get only minor findings, and speeded up the Duhemian process of groping towards a choice among competing theories