Methyl hydrazinocarboxylate as a practical alternative to hydrazine in the Wolff–Kishner reaction

Herein we describe a facile protocol for the reduction of aromatic ketones and aldehydes to the corresponding methylene unit. The procedure involves isolation of a carbomethoxyhydrazone intermediate that is easily decomposed to the reduced product without the requirement for large quantities of pernicious hydrazine.

Kinetics analysis and automated online screening of aminocarbonylation of aryl halides in flow

Temperature, pressure, gas stoichiometry, and residence time were varied to control the yield and product distribution of the palladium-catalyzed aminocarbonylation of aromatic bromides in both a silicon microreactor and a packed-bed tubular reactor. Automation of the system set points and product sampling enabled facile and repeatable reaction analysis with minimal operator supervision. It was observed that the reaction was divided into two temperature regimes. An automated system was used to screen steady-state conditions for offline analysis by gas chromatography to fit a reaction rate model. Additionally, a transient temperature ramp method utilizing online infrared analysis was used, leading to more rapid determination of the reaction activation energy of the lower temperature regimes. The entire reaction spanning both regimes was modeled in good agreement with the experimental data.

Genomic evidence for the Pleistocene and recent population history of Native Americans

How and when the Americas were populated remains contentious. Using ancient and modern genome-wide data, we found that the ancestors of all present-day Native Americans, including Athabascans and Amerindians, entered the Americas as a single migration wave from Siberia no earlier than 23 thousand years ago (ka) and after no more than an 8000-year isolation period in Beringia. After their arrival to the Americas, ancestral Native Americans diversified into two basal genetic branches around 13 ka, one that is now dispersed across North and South America and the other restricted to North America. Subsequent gene flow resulted in some Native Americans sharing ancestry with present-day East Asians (including Siberians) and, more distantly, Australo-Melanesians. Putative “Paleoamerican” relict populations, including the historical Mexican Peric��es and South American Fuego-Patagonians, are not directly related to modern Australo-Melanesians as suggested by the Paleoamerican Model.

Multiprobabilistic prediction in early medical diagnoses

This paper describes the methodology of providing multiprobability predictions for proteomic mass spectrometry data. The methodology is based on a newly developed machine learning framework called Venn machines. Is allows to output a valid probability interval. The methodology is designed for mass spectrometry data. For demonstrative purposes, we applied this methodology to MALDI-TOF data sets in order to predict the diagnosis of heart disease and early diagnoses of ovarian cancer and breast cancer. The experiments showed that probability intervals are narrow, that is, the output of the multiprobability predictor is similar to a single probability distribution. In addition, probability intervals produced for heart disease and ovarian cancer data were more accurate than the output of corresponding probability predictor. When Venn machines were forced to make point predictions, the accuracy of such predictions is for the most data better than the accuracy of the underlying algorithm that outputs single probability distribution of a label. Application of this methodology to MALDI-TOF data sets empirically demonstrates the validity. The accuracy of the proposed method on ovarian cancer data rises from 66.7 % 11 months in advance of the moment of diagnosis to up to 90.2 % at the moment of diagnosis. The same approach has been applied to heart disease data without time dependency, although the achieved accuracy was not as high (up to 69.9 %). The methodology allowed us to confirm mass spectrometry peaks previously identified as carrying statistically significant information for discrimination between controls and cases.

Shape-controlled continuous synthesis of metal nanostructures

A segmented flow-based microreactor is used for the continuous production of faceted nanocrystals. Flow segmentation is proposed as a versatile tool to manipulate the reduction kinetics and control the growth of faceted nanostructures; tuning the size and shape. Switching the gas from oxygen to carbon monoxide permits the adjustment in nanostructure growth from 1D (nanorods) to 2D (nanosheets). CO is a key factor in the formation of Pd nanosheets and Pt nanocubes; operating as a second phase, a reductant, and a capping agent. This combination confines the growth to specific structures. In addition, the segmented flow microfluidic reactor inherently has the ability to operate in a reproducible manner at elevated temperatures and pressures whilst confining potentially toxic reactants, such as CO, in nanoliter slugs. This continuous system successfully synthesised Pd nanorods with an aspect ratio of 6; thin palladium nanosheets with a thickness of 1.5 nm; and Pt nanocubes with a 5.6 nm edge length, all in a synthesis time as low as 150 s.

Clinical and molecular delineation of the 17q21.31 microdeletion syndrome

Background: The chromosome 17q21.31 microdeletion syndrome is a novel genomic disorder that has originally been identified using high resolution genome analyses in patients with unexplained mental retardation. Aim: We report the molecular and/or clinical characterisation of 22 individuals with the 17q21.31 microdeletion syndrome. Results: We estimate the prevalence of the syndrome to be 1 in 16 000 and show that it is highly underdiagnosed. Extensive clinical examination reveals that developmental delay, hypotonia, facial dysmorphisms including a long face, a tubular or pear-shaped nose and a bulbous nasal tip, and a friendly/amiable behaviour are the most characteristic features. Other clinically important features include epilepsy, heart defects and kidney/urologic anomalies. Using high resolution oligonucleotide arrays we narrow the 17q21.31 critical region to a 424 kb genomic segment (chr17: 41046729-41470954, hg17) encompassing at least six genes, among which is the gene encoding microtubule associated protein tau (MAPT). Mutation screening of MAPT in 122 individuals with a phenotype suggestive of 17q21.31 deletion carriers, but who do not carry the recurrent deletion, failed to identify any disease associated variants. In five deletion carriers we identify a <500 bp rearrangement hotspot at the proximal breakpoint contained within an L2 LINE motif and show that in every case examined the parent originating the deletion carries a common 900 kb 17q21.31 inversion polymorphism, indicating that this inversion is a necessary factor for deletion to occur (p< 10(25)). Conclusion: Our data establish the 17q21.31 microdeletion syndrome as a clinically and molecularly well recognisable genomic disorder.

Mitochondrial sequence data and Dipsacales phylogeny: Mixed models, partitioned Bayesian analyses, and model selection

Phylogenetic analyses of chloroplast DNA sequences, morphology, and combined data have provided consistent support for many of the major branches within the angiosperm, clade Dipsacales. Here we use sequences from three mitochondrial loci to test the existing broad scale phylogeny and in an attempt to resolve several relationships that have remained uncertain. Parsimony, maximum likelihood, and Bayesian analyses of a combined mitochondrial data set recover trees broadly consistent with previous studies, although resolution and support are lower than in the largest chloroplast analyses. Combining chloroplast and mitochondrial data results in a generally well-resolved and very strongly supported topology but the previously recognized problem areas remain. To investigate why these relationships have been difficult to resolve we conducted a series of experiments using different data partitions and heterogeneous substitution models. Usually more complex modeling schemes are favored regardless of the partitions recognized but model choice had little effect on topology or support values. In contrast there are consistent but weakly supported differences in the topologies recovered from coding and non-coding matrices. These conflicts directly correspond to relationships that were poorly resolved in analyses of the full combined chloroplast-mitochondrial data set. We suggest incongruent signal has contributed to our inability to confidently resolve these problem areas. (c) 2007 Elsevier Inc. All rights reserved.

Sudden stratospheric warmings seen in MINOS deep underground muon data

The rate of high energy cosmic ray muons as measured underground is shown to be strongly correlated with upper-air temperatures during short-term atmospheric (10-day) events. The effects are seen by correlating data from the MINOS underground detector and temperatures from the European Centre for Medium Range Weather Forecasts during the winter periods from 2003-2007. This effect provides an independent technique for the measurement of meteorological conditions and presents a unique opportunity to measure both short and long-term changes in this important part of the atmosphere. Citation: Osprey, S., et al. (2009), Sudden stratospheric warmings seen in MINOS deep underground muon data, Geophys. Res. Lett., 36, L05809, doi: 10.1029/2008GL036359.

The magnetized steel and scintillator calorimeters of the MINOS experiment

The Main Injector Neutrino Oscillation Search (MINOS) experiment uses an accelerator-produced neutrino beam to perform precision measurements of the neutrino oscillation parameters in the ""atmospheric neutrino"" sector associated with muon neutrino disappearance. This long-baseline experiment measures neutrino interactions in Fermilab`s NuMI neutrino beam with a near detector at Fermilab and again 735 km downstream with a far detector in the Soudan Underground Laboratory in northern Minnesota. The two detectors are magnetized steel-scintillator tracking calorimeters. They are designed to be as similar as possible in order to ensure that differences in detector response have minimal impact on the comparisons of event rates, energy spectra and topologies that are essential to MINOS measurements of oscillation parameters. The design, construction, calibration and performance of the far and near detectors are described in this paper. (C) 2008 Elsevier B.V. All rights reserved.

Finite-momentum condensate of magnetic excitons in a bilayer quantum Hall system

Fundação de Amparo à Pesquisa do Estado de S��o Paulo (FAPESP)

NUMERICAL STUDY OF TRANSPORT IN A DISSIPATIVE MEDIUM

A numerical study of propagation of a particle through a one-dimensional dissipative medium is presented. The medium is composed of several dissipative sections, which are characterized by their friction coefficients eta. In particular, we have considered two types of friction coefficients distributed orderly or disorderly along the chain. For the same relative proportion of the coefficients, we have found that transport can be enhanced in the disordered distribution in comparison with the ordered one. We also show how this can be considered an approximated way to treat the propagation in a dissipative medium with a position-dependent friction coefficient.

Macroscopic quantum tunneling in a dc SQUID: Instanton splitting

The theory of macroscopic quantum tunneling is applied to a current-biased dc SQUID which constitutes a system of two interacting quantum degrees of freedom coupled to the environment. The decay probability is obtained in the exponential approximation for the overdamped case. Close to the critical driving force of the system, the decay of the metastable state is determined by a unique instanton solution describing the symmetric decay of the phases in each of the two Josephson juctions. Upon reducing the external driving force a new regime is reached where the instanton splits. The doubling of the decay channels reduces the decreasing of the decay rate in the quantum regime. A current-temperature phase diagram is constructed based on the Landau theory of phase transitions. Depending on the external parameters the system develops either a first- or a second-order transition to the split-instanton regime. © 1994 The American Physical Society.

Is the prevalence of asthma and related symptoms among Brazilian children related to socioeconomic status?

Objective. To evaluate the relationship between socioeconomic status (SES) and the prevalence of asthma and related symptoms among Brazilian children. Methods. The International Study of Asthma and Allergies in Childhood (ISAAC) written questionnaire was applied to 23,457 six- to seven- year-old schoolchildren (SC) and 58,144 thirteen- to fourteen-year-old adolescents (AD) from 20 Brazilian cities. SES was evaluated by infant mortality index, poverty index, and average nominal income for people older than 10 years of age. Results. Current asthma ranged from 16.5% to 31.2% among SC and from 11.8% to 30.5% among AD and severe asthma from 2.9% to 8.5% (SC) and 2.6% to 9.1% (AD). Higher values were observed in Brazilian-Northern, -Northeastern and -Southeastern centers. No significant association between SES and prevalence of asthma and related symptoms was observed. Conclusions. In Brazil, the prevalence of asthma and related symptoms is quite variable and independent of SES. Copyright © 2008 Informa Healthcare USA, Inc.

Measurement of the W-boson helicity in top-quark decays from t(t)over-bar production in lepton plus jets events in pp collisions at root s=7 TeV

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)