Electrocarboxylation of chloroacetonitrile mediated by electrogenerated cobalt(I) phenanthroline

The electrocarboxylation of chloroacetonitrilemediated by [Co(II)(phen)3]2+ has been investigated. Cyclic voltammetry studies of [Co(II)(phen)3]2+ have shown that [Co(I)(phen)3]+, an 18 electron complex, activates chloroacetonitrile by an oxidative addition through the loss of a phenanthroline ligand to give [RCo(III)(phen)2Cl]+. The unstable one-electron-reduced complex underwent Co–C bond cleavage. In carbon dioxide saturated solution, CO2 insertion proceeds after reduction of the alkylcobalt complex. A catalytic current is observed which corresponds to the electrocarboxylation of chloroacetonitrile into cyanoacetic acid. Electrolyses confirmed the process and gave faradic yield of 62% in cyanoacetic acid at potentials that are about 0.3 V less cathodic than the one required for Ni(salen)

Costs and Benefits of Preventing Workplace Accidents : Going from a Mechanical to a Manual Handling System

This paper provides a cost-benefit analysis of the passage from a mechanical to a manual handling system that took place at the beginning of the 1990s at a warehouse of the Société des Alcools du Québec in Montreal. In particular, this change was aimed at reducing workplace accidents among packers. After evaluating the costs of the program, we present a rigorous econometric analysis to assess how many accidents have been prevented by the change so as to compute the direct and indirects costs avoided as a result of such accident reduction. We show that the demechanization of the handling system has indeed been profitable for the firm. Les auteurs de cet article ont effectué l'analyse coûts-avantages du passage d'un système de manutention mécanisé à un système manuel mis en oeuvre en 1990 dans un entrepôt de la Société des Alcools du Québec situé à Montréal. Après avoir estimé les coûts du programme, ils ont conduit une analyse économétrique rigoureuse pour déterminer le nombre d'accidents évités grâce à ce changement. Ils ont pu ainsi calculer les coûts directs et indirects qui n'auront pas à être subis à cause de la réduction du nombre des accidents. Ils en concluent que le changement a été rentable pour l'entreprise.

TET2 inhibits differentiation of embryonic stem cells but does not overcome methylation-induced gene silencing

TET2 is a methylcytosine dioxygenase that is frequently mutated in myeloid malignancies, notably myelodysplasia and acute myeloid leukemia. TET2 catalyses the conversion of 5′-methylcytosine to 5′-hydroxymethylcytosine within DNA and has been implicated in the process of genomic demethylation. However, the mechanism by which TET2 loss of function results in hematopoietic dysplasia and leukemogenesis is poorly understood. Here, we show that TET2 is expressed in undifferentiated embryonic stem cells and that its knockdown results in reduction of 5′-hydroxymethylcytosine in genomic DNA. We also present DNA methylation data from bone marrow samples obtained from patients with TET2-mutated myelodysplasia. Based on these findings, we sought to identify the role of TET2 in regulating pluripotency and differentiation. We show that overexpression of TET2 in a stably integrated transgene leads to increased alkaline phosphatase expression in differentiating ES cells and impaired differentiation in methylcellulose culture. We speculate that this effect is due to TET2-mediated expression of stem cell genes in ES cells via hydroxylation of 5′-methylcytosines at key promoter sequences within genomic DNA. This leads to relative hypomethylation of gene promoters as 5′-hydroxymethylcytosine is not a substrate for DNMT1-mediated maintenance methylation. We sought to test this hypothesis by cotransfecting the TET2 gene with methylated reporter genes. The results of these experiments are presented

Electrically gauged N=4 supergravities in D=4 with N=2 vacua

We study N=2 vacua in spontaneously broken N=4 electrically gauged supergravities in four space-time dimensions. We argue that the classification of all such solutions amounts to solving a system of purely algebraic equations. We then explicitly construct a special class of consistent N=2 solutions and study their properties. In particular we find that the spectrum assembles in N=2 massless or BPS supermultiplets. We show that (modulo U(1) factors) arbitrary unbroken gauge groups can be realized provided that the number of N=4 vector multiplets is large enough. Below the scale of partial supersymmetry breaking we calculate the relevant terms of the low-energy effective action and argue that the special Kahler manifold for vector multiplets is completely determined, up to its dimension, and lies in the unique series of special Kahler product manifolds.Comment: 48 pages; v2: one reference adde

Rcapture: Loglinear Models for Capture-Recapture in R

This article introduces Rcapture, an R package for capture-recapture experiments. The data for analysis consists of the frequencies of the observable capture histories over the t capture occasions of the experiment. A capture history is a vector of zeros and ones where one stands for a capture and zero for a miss. Rcapture can fit three types of models. With a closed population model, the goal of the analysis is to estimate the size N of the population which is assumed to be constant throughout the experiment. The estimator depends on the way in which the capture probabilities of the animals vary. Rcapture features several models for these capture probabilities that lead to different estimators for N. In an open population model, immigration and death occur between sampling periods. The estimation of survival rates is of primary interest. Rcapture can fit the basic Cormack-Jolly-Seber and Jolly-Seber model to such data. The third type of models fitted by Rcapture are robust design models. It features two levels of sampling; closed population models apply within primary periods and an open population model applies between periods. Most models in Rcapture have a loglinear form; they are fitted by carrying out a Poisson regression with the R function glm. Estimates of the demographic parameters of interest are derived from the loglinear parameter estimates; their variances are obtained by linearization. The novel feature of this package is the provision of several new options for modeling capture probabilities heterogeneity between animals in both closed population models and the primary periods of a robust design. It also implements many of the techniques developed by R. M. Cormack for open population models.

Landau's function for one million billions

Let ${\mathfrak S}_n$ denote the symmetric group with $n$ letters, and $g(n)$ the maximal order of an element of ${\mathfrak S}_n$. If the standard factorization of $M$ into primes is M=q_1^{\al_1}q_2^{\al_2}... q_k^{\al_k}, we define $\ell(M)$ to be q_1^{\al_1}+q_2^{\al_2}+... +q_k^{\al_k}; one century ago, E. Landau proved that $g(n)=\max_{\ell(M)\le n} M$ and that, when $n$ goes to infinity, $\log g(n) \sim \sqrt{n\log(n)}$. There exists a basic algorithm to compute $g(n)$ for $1 \le n \le N$; its running time is \co(N^{3/2}/\sqrt{\log N}) and the needed memory is \co(N); it allows computing $g(n)$ up to, say, one million. We describe an algorithm to calculate $g(n)$ for $n$ up to $10^{15}$. The main idea is to use the so-called {\it $\ell$-superchampion numbers}. Similar numbers, the {\it superior highly composite numbers}, were introduced by S. Ramanujan to study large values of the divisor function \tau(n)=\sum_{d\dv n} 1

Electrocarboxylation of chloroacetonitrile by a Cobalt(I) complex of terpyridine

The electrocarboxylation of chloroacetonitrile (NC–CH2–ClRCl) mediated by [CoIIL2]2+ (L = terpyridine) was investigated by cyclic voltammetry. Electrochemical studies under argon atmosphere showed that the monoelectronic reduction of [CoIIL2]2+ yielded a Cobalt(I) complex which after the loss of a terpyridine ligand reacted with chloroacetonitrile. The oxidative addition of chloroacetonitrile on [CoIL]+ gave an alkylCobalt(III) complex [R–CoIIIL]2+ which was reduced into an alkylCobalt(II) complex, highly unstable and decomposed into an alkyl anion and a Cobalt(II) complex. Under carbon dioxide atmosphere, Cobalt(I) complex was shown to be unreactive towards CO2 but CO2 insertion was observed in the alkylCobalt(III) complex [R–CoIIIL] 2+ giving probably a CO2 adduct [R–CoIIIL(CO2)]2+. This adduct presented a strong adsorption at the carbon electrode and was reduced at potential less cathodic than the one of alkylCobalt(III) complex. After reduction, the carboxylate RCO2− (NC–CH2–CO2−) was released and a catalytic bielectronic carboxylation of chloroacetonitrile took place. Controlled potential electrolyses confirmed the catalytic process and gave for cyanoacetic acid faradic yields up to 60% under low overpotential conditions